阅读说明：本技术 化合物、树脂、组合物和图案形成方法 (Compound, resin, composition, and pattern forming method ) 是由 越后雅敏 冈田悠 泷川具明 牧野岛高史 于 2019-01-18 设计创作，主要内容包括：本发明的课题在于,提供：能应用湿式工艺、为了形成耐热性、溶解性和耐蚀刻性优异的光致抗蚀剂和光致抗蚀剂用下层膜而有用的化合物等。前述课题可以通过下述式(1)所示的化合物而解决。<Image he="481" wi="700" file="DDA0002589918940000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The subject of the present invention is to provide a novel,providing: a compound useful for forming a photoresist and an underlayer film for a photoresist excellent in heat resistance, solubility and etching resistance by applying a wet process. The above object can be achieved by a compound represented by the following formula (1).)

1. A compound represented by the following formula (1) or (1'),

in the formula (1), the reaction mixture is,

R^Yis a hydrogen atom, an alkyl group having 1 to 60 carbon atoms and optionally having a substituent and/or a heteroatom, or an aryl group having 6 to 60 carbon atoms and optionally having a substituent and/or a heteroatom,

R^Zis a C1-60N-valent group or a single bond optionally having a substituent and/or a heteroatom,

or, R^YAnd R^ZOptionally containing the carbon atoms to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms,

a is a group having 1 to 60 carbon atoms and optionally having a substituent and/or a hetero atom,

R^Teach independently is an alkyl group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an aryl group having 6 to 40 carbon atoms optionally having a substituent and/or a heteroatom, an alkenyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkynyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkoxy group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkylthio group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, a halogen atom, a nitro group, an amino group, a cyano group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group and the aryl group optionally contain an ether bond, a ketone bond or an ester bond,

x is an oxygen atom, a sulfur atom or is unbridged,

here, the number of the first and second electrodes,

selected from A, R^Y、R^Z、R^TAnd at least 1 of X comprises a sulfur atom,

R^Tat least one of which contains a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group,

m is each independently an integer of 0 to 9,

n is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

in the formula (1'), in the presence of a catalyst,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an aryl group having 6 to 40 carbon atoms optionally having a substituent and/or a heteroatom, an alkenyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkynyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatomAn alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group, and the aryl group optionally include an ether bond, a ketone bond, or an ester bond,

R⁰each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or an aryl group having 6 to 30 carbon atoms and optionally having a substituent and/or a hetero atom,

or, 2R⁰Optionally containing the carbon atom to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms, 2R⁰A double bond bonded to a carbon atom to which they are bonded, the double bond being optionally bonded to an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, or an aryl group having 6 to 30 carbon atoms and optionally having a substituent and/or a heteroatom,

a and A' are groups having 1 to 60 carbon atoms and optionally having a substituent and/or a hetero atom,

l is an integer of 1 to 9,

k and L' are each independently an integer of 0 to 9.

2. The compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1),

in the formula (1-1),

R^Y、R^Za, X and N are as defined in claim 1,

R^3Aeach independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkynyl group having 2 to 30 carbon atoms, a halogen atom, a nitro groupAn amino group, a carboxylic acid group or a mercapto group,

R^4Aeach independently a hydrogen atom, an acid-crosslinkable group or an acid-dissociable group,

here, it is selected from A, R^Y、R^Z、R^3A、R^4AAnd at least 1 of X comprises a sulfur atom,

m^6Aeach independently an integer of 0 to 5,

m^7Aeach independently an integer of 0 to 5,

wherein, 2 m^7ANot simultaneously 0.

3. The compound according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (2),

in the formula (2), the reaction mixture is,

R^Yis a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms,

R^Zis a C1-60N-valent group or a single bond,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 40 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group and the aryl group may have an ether bond, a ketone bond or an ester bond, and R represents an ether bond, a ketone bond or an ester bond^TAt least one of which is a mercapto group,

x represents an oxygen atom, a sulfur atom or is unbridged,

m is each independently an integer of 0 to 9, where at least one of m is an integer of 1 to 9,

n is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

r is an integer of 0 to 2.

4. The compound according to claim 3, wherein the compound represented by the formula (2) is a compound represented by the following formula (3),

in the formula (3), the reaction mixture is,

R⁰and R in claim 3^YAre used in the same sense and have the same meaning,

R¹is an n-valent group or single bond having 1 to 60 carbon atoms,

R²～R⁵each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein R represents a group²～R⁵At least one of which is a mercapto group,

m²and m³Each independently an integer of 0 to 8,

m⁴and m⁵Each independently an integer of 0 to 9,

wherein m is²、m³、m⁴And m⁵When the temperature is not simultaneously 0, the temperature is not increased,

n is the same as N in claim 3, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

p²～p⁵the same meaning as r in claim 3.

5. The compound according to claim 3, wherein the compound represented by the formula (2) is a compound represented by the following formula (4),

in the formula (4), the reaction mixture is,

R^0Aand R in claim 3^YAre used in the same sense and have the same meaning,

R^1An is a carbon number of 1 to 60^AA group of valency or a single bond,

R^2Aeach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein R represents a group^2AAt least one of which is a mercapto group,

n^Athe same meaning as N in claim 3, wherein N is^AWhen n is an integer of 2 or more, n^A2]The structural formulae in (a) and (b) are optionally the same or different,

X^Arepresents an oxygen atom, a sulfur atom or is unbridged,

m^2Aeach independently an integer of 0 to 7, wherein at least 1m^2AIs an integer of 1 to 7, and,

q^Aeach independently 0 or 1.

6. The compound according to claim 4, wherein the compound represented by the formula (3) is a compound represented by the following formula (3-1),

in the formula (3-1),

R⁰、R¹、R⁴、R⁵、n、p²～p⁵、m⁴and m⁵As defined in claim 4，

R⁶And R⁷Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, or a mercapto group,

m⁶and m⁷Each independently an integer of 0 to 7.

7. The compound according to claim 6, wherein the compound represented by the formula (3-1) is a compound represented by the following formula (3-2),

in the formula (3-2),

R⁰、R¹n and p²～p⁵As defined in claim 4, the first and second,

R⁶、R⁷、m⁶and m⁷As defined in claim 6, the first and second,

R⁸and R⁹And R⁶And R⁷Are used in the same sense and have the same meaning,

m⁸and m⁹Each independently is an integer of 0 to 8.

8. The compound according to claim 5, wherein the compound represented by the formula (4) is a compound represented by the following formula (4-1),

in the formula (4-1),

R^0A、R^1A、n^A、q^Aand X^AAs defined in claim 5, the first and second,

R^3Aeach independently a halogen atom, optionally having a substituent, having 1 to 30 carbon atomsAn alkyl group, an aryl group having 6 to 30 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent, or an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent,

m^6Aeach independently an integer of 0 to 5.

9. A resin comprising the compound of claim 1 or 2 as a structural unit.

10. The resin according to claim 9, which is represented by the following (5),

in the formula (5), the reaction mixture is,

R^Y、R^Z、A、R^Tx and N are as defined in claim 1,

m is each independently an integer of 0 to 8,

here, the number of the first and second electrodes,

selected from A, R^Y、R^Z、R^TAnd at least 1 of X comprises a sulfur atom,

R^Tat least one of which contains a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group,

when N is an integer of 2 or more, the structural formulae in the N [ ] are optionally the same or different,

l is an alkylene group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, an arylene group having 6 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, an alkyleneoxy group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or a single bond, and the alkylene group, the arylene group, and the alkyleneoxy group optionally include an ether bond, a thioether bond, a ketone bond, or an ester bond.

11. A resin comprising the compound according to any one of claims 3 to 8 as a structural unit.

12. The resin according to claim 11, which has a structure represented by the following formula (6),

in the formula (6), the reaction mixture is,

l is a linear or branched alkylene group having 1 to 30 carbon atoms which may be optionally substituted, or a single bond,

R⁰and R in claim 3^YAre used in the same sense and have the same meaning,

R¹is an n-valent group or single bond having 1 to 60 carbon atoms,

R²～R⁵each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein R represents a group²～R⁵At least one of which is a mercapto group,

m²and m³Each independently an integer of 0 to 8,

m⁴and m⁵Each independently an integer of 0 to 9,

wherein m is²、m³、m⁴And m⁵When the temperature is not simultaneously 0, the temperature is not increased,

n is the same as N in claim 3, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

p²～p⁵the same meaning as r in claim 3.

13. The resin according to claim 11, which has a structure represented by the following formula (7),

in the formula (7), the reaction mixture is,

l is a linear or branched alkylene group having 1 to 30 carbon atoms which may be optionally substituted, or a single bond,

R^0Aand R in claim 3^YAre used in the same sense and have the same meaning,

R^1An is a carbon number of 1 to 60^AA group of valency or a single bond,

R^2Aeach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein R represents a group^2AAt least one of which is a mercapto group,

n^Athe same meaning as N in claim 3, wherein N is^AWhen n is an integer of 2 or more, n^A2]The structural formulae in (a) and (b) are optionally the same or different,

X^Arepresents an oxygen atom, a sulfur atom or is unbridged,

m^2Aeach independently an integer of 0 to 7, wherein at least 1m^2AIs an integer of 1 to 6, and,

q^Aeach independently 0 or 1.

14. A composition comprising: 1 or more selected from the group consisting of the compounds according to claims 1 to 8 and the resins according to claims 9 to 13.

15. The composition of claim 14, further comprising a solvent.

16. The composition of claim 14 or 15, further comprising an acid generator.

17. The composition of any one of claims 14 to 16, further comprising an acid crosslinking agent.

18. The composition of any one of claims 14 to 17, further comprising a free radical generator.

19. The composition according to any one of claims 14 to 18, which is used for forming a film for lithography.

20. The composition according to claim 19, which is used for forming a resist underlayer film.

21. The composition according to claim 19, which is used for forming a resist film.

22. The composition of claim 19, for use in forming a permanent resist film.

23. A composition according to any one of claims 14 to 18 for use in forming an optical component.

24. A method for forming a resist pattern, comprising the steps of:

a step of forming a photoresist layer on a substrate using the composition according to claim 19; and the combination of (a) and (b),

and a step of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer.

25. A method for forming an insulating film, comprising the steps of:

a step of forming a photoresist layer on a substrate using the composition according to claim 19; and the combination of (a) and (b),

and a step of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer.

26. A method for forming a resist pattern, comprising the steps of:

a step of forming an underlayer film on a substrate using the composition according to claim 19;

forming at least 1 photoresist layer on the underlayer film; and the combination of (a) and (b),

and a step of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer.

27. A circuit pattern forming method includes the steps of:

a step of forming an underlayer film on a substrate using the composition according to claim 19;

forming an intermediate layer film on the underlayer film using a resist intermediate layer film material;

forming at least 1 photoresist layer on the interlayer film;

a step of forming a resist pattern by irradiating a predetermined region of the photoresist layer with radiation and developing the resist pattern;

etching the intermediate layer film using the resist pattern as a mask;

etching the lower layer film using the obtained intermediate layer film pattern as an etching mask; and the combination of (a) and (b),

and forming a pattern on the substrate by etching the substrate using the obtained lower layer film pattern as an etching mask.

28. A method for purifying the compound according to any one of claims 1 to 8 or the resin according to any one of claims 9 to 13,

the purification method comprises the following extraction procedures: the extraction is carried out by contacting a solution comprising the compound or resin and an organic solvent which is not optionally miscible with water, with an acidic aqueous solution.

Technical Field

The present invention relates to compounds having specific structures, resins, and compositions containing them. The present invention also relates to a pattern forming method (resist pattern forming method and circuit pattern forming method) using the composition.

Background

In the manufacture of semiconductor devices, microfabrication by photolithography using a photoresist material is performed, and in recent years, further miniaturization based on pattern rules has been demanded with higher integration and higher speed of LSIs. Further, a light source for lithography used for forming a resist pattern is shortened from KrF excimer laser light (248nm) to ArF excimer laser light (193nm), and introduction of extreme ultraviolet light (EUV, 13.5nm) is also expected.

However, in photolithography using a conventional polymer resist material, since the molecular weight is about 1 to 10 ten thousand and the molecular weight distribution is wide, roughness is generated on the surface of a pattern, and control of the pattern size is difficult, which has a limit in miniaturization.

Therefore, various low molecular weight resist materials have been proposed so far in order to provide a resist pattern with higher resolution. Since the low molecular weight resist material has a small molecular size, it is expected to provide a resist pattern having high resolution and small roughness.

Various materials have been known as such low molecular weight resist materials. For example, an alkali-developable negative-type radiation-sensitive composition using a low-molecular-weight polynuclear polyphenol compound as a main component has been proposed (for example, see patent documents 1 and 2), and an alkali-developable negative-type radiation-sensitive composition using a low-molecular-weight cyclic polyphenol compound as a main component has been proposed as a candidate for a low-molecular-weight resist material having high heat resistance (for example, see patent documents 3 and 1). Further, as a base compound of a resist material, it is known that a polyphenol compound is useful for improving the resolution and roughness of a resist pattern because it has a low molecular weight and can impart high heat resistance (for example, see non-patent document 2).

The present inventors have proposed a resist composition containing a compound having a specific structure and an organic solvent as a material which is excellent in etching resistance, soluble in a solvent, and applicable to a wet process (see patent document 4).

Further, if the resist pattern is miniaturized, a problem of resolution or a problem of collapse of the resist pattern after development is gradually caused, and thus, it is desired to make the resist thinner. However, if the resist is simply thinned, it becomes difficult to obtain a sufficient thickness of the resist pattern in the substrate processing. Therefore, a process is required in which not only a resist pattern but also a resist underlayer film is formed between a resist and a semiconductor substrate to be processed, and the resist underlayer film also functions as a mask during substrate processing.

Various resist underlayer films are known as resist underlayer films for such processes. For example, as a resist underlayer film for lithography which realizes a resist underlayer film having a higher etching rate than a conventional one and a selection ratio close to the dry etching rate of a resist, the following underlayer film forming materials for a multilayer resist process are proposed: which contains a resin component having at least a substituent group which generates a sulfonic acid residue by leaving a terminal group by applying a predetermined energy, and a solvent (see patent document 5). As a resist underlayer film material for lithography that realizes a selection ratio of a dry etching rate smaller than that of a resist, the following resist underlayer film materials have been proposed: which comprises a polymer having a specific repeating unit (see patent document 6). Further, as a resist underlayer film material for lithography that realizes a selection ratio of a dry etching rate smaller than that of a semiconductor substrate, the following resist underlayer film materials are proposed: which comprises a polymer obtained by copolymerizing an acenaphthylene repeating unit with a repeating unit having a substituted or unsubstituted hydroxyl group (see patent document 7).

On the other hand, as a material having high etching resistance in such a resist underlayer film, there are known: an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas, or the like as a raw material. However, from the viewpoint of the process, a resist underlayer film material capable of forming a resist underlayer film by a wet process such as spin coating or screen printing is required.

The present inventors have also proposed a composition for forming a lower layer film for lithography, which contains a compound having a specific structure and an organic solvent, as a material having excellent etching resistance and high heat resistance, being soluble in a solvent and being usable in a wet process (see patent document 8).

As a method for forming an intermediate layer used for forming a resist underlayer film in a 3-layer process, for example, a method for forming a silicon nitride film is known (see patent document 9); a CVD method for forming a silicon nitride film (see patent document 10). As an interlayer material for a 3-layer process, a material containing a silsesquioxane-based silicon compound is known (see patent documents 11 and 12).

Further, various compositions have been proposed as optical member-forming compositions. For example, acrylic resins can be cited (see patent documents 13 and 14).

Disclosure of Invention

Problems to be solved by the invention

As described above, although a large number of resist-oriented film-forming compositions and underlayer film-oriented resist-oriented film-forming compositions have been proposed, they do not have high solvent solubility to which wet processes such as spin coating and screen printing can be applied, and do not satisfy both solvent solubility, heat resistance and etching resistance with high dimensional accuracy, and development of new materials has been demanded.

In addition, although a large number of compositions for optical members have been proposed, development of new materials has not been demanded since heat resistance, transparency, and refractive index are compatible with each other at high dimensions.

The present invention has been made to solve the above problems, and an object of the present invention is to provide: the compounds, resins, and compositions (for example, compositions used for forming films for lithography or optical members) useful for forming photoresists and underlayer films for photoresists that can be applied by wet processes and are excellent in heat resistance, solubility, and etching resistance, and pattern forming methods (resist pattern forming methods and circuit pattern forming methods) using the compositions.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems, and as a result, they have found that: the present inventors have completed the present invention by using a compound or a resin having a specific structure to solve the above-described problems. Namely, the present invention is as follows.

[1]

A compound represented by the following formula (1) or (1').

(in the formula (1),

R^Yis a hydrogen atom, an alkyl group having 1 to 60 carbon atoms and optionally having a substituent and/or a heteroatom, or an aryl group having 6 to 60 carbon atoms and optionally having a substituent and/or a heteroatom,

R^Zis a C1-60N-valent group or a single bond optionally having a substituent and/or a heteroatom,

or, R^YAnd R^ZOptionally containing the carbon atoms to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms,

a is a group having 1 to 60 carbon atoms and optionally having a substituent and/or a hetero atom,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an aryl group having 6 to 40 carbon atoms optionally having a substituent and/or a heteroatom, an alkenyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkynyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkoxy group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, a carbon group optionally having a substituent and/or a heteroatomA number of 1 to 30 of alkylthio groups, halogen atoms, nitro groups, amino groups, cyano groups, carboxylic acid groups, mercapto groups, hydroxyl groups, or groups in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group, and the aryl group optionally contain an ether bond, a ketone bond, or an ester bond, X is an oxygen atom, a sulfur atom, or is an unbridged group,

here, the number of the first and second electrodes,

selected from A, R^Y、R^Z、R^TAnd at least 1 of X comprises a sulfur atom,

R^Tat least one of which contains a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group,

m is each independently an integer of 0 to 9,

n is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different. )

(in the formula (1'),

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, an aryl group having 6 to 40 carbon atoms and optionally having a substituent and/or a heteroatom, an alkenyl group having 2 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, an alkylthio group having 1 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group, and the aryl group optionally contain an ether bond, a ketone bond or an ester bond,

R⁰each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or an alkyl group having a substituent and/or a hetero atomAn aryl group having 6 to 30 carbon atoms,

or, 2R⁰Optionally containing the carbon atom to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms, 2R⁰A double bond bonded to a carbon atom to which they are bonded, the double bond being optionally bonded to an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a heteroatom, or an aryl group having 6 to 30 carbon atoms and optionally having a substituent and/or a heteroatom,

a and A' are groups having 1 to 60 carbon atoms and optionally having a substituent and/or a hetero atom,

l is an integer of 1 to 9,

k and L' are each independently an integer of 0 to 9)

[2]

The compound according to [1], wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(in the formula (1-1),

R^Y、R^Za, X and N are as in [1]]The method according to the definition in (1),

R^3Aeach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a mercapto group,

R^4Aeach independently a hydrogen atom, an acid-crosslinkable group or an acid-dissociable group,

here, it is selected from A, R^Y、R^Z、R^3A、R^4AAnd at least 1 of X comprises a sulfur atom,

m^6Aeach independently an integer of 0 to 5,

m^7Aeach independently an integer of 0 to 5,

wherein, 2 m^7ANot simultaneously 0. )

[3]

The compound according to [1], wherein the compound represented by the formula (1) is a compound represented by the following formula (2).

(in the formula (2),

R^Yis a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms,

R^Zis a C1-60N-valent group or a single bond,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 40 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group and the aryl group may have an ether bond, a ketone bond or an ester bond, and R represents an ether bond, a ketone bond or an ester bond^TAt least one of which is a mercapto group,

x represents an oxygen atom, a sulfur atom or is unbridged,

m is each independently an integer of 0 to 9, where at least one of m is an integer of 1 to 9,

n is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

r is an integer of 0 to 2. )

[4]

The compound according to [3], wherein the compound represented by the formula (2) is a compound represented by the following formula (3).

(in the formula (3),

R⁰and [3]R in (1)^YAre used in the same sense and have the same meaning,

R¹is an n-valent group or single bond having 1 to 60 carbon atoms,

R²～R⁵each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein R represents a group²～R⁵At least one of which is a mercapto group,

m²and m³Each independently an integer of 0 to 8,

m⁴and m⁵Each independently an integer of 0 to 9,

wherein m is²、m³、m⁴And m⁵When the temperature is not simultaneously 0, the temperature is not increased,

n is the same as N in [3], wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

p²～p⁵and [3]R in (A) has the same meaning. )

[5]

The compound according to [3], wherein the compound represented by the formula (2) is a compound represented by the following formula (4).

(in the formula (4),

R^0Aand [3]R in (1)^YAre used in the same sense and have the same meaning,

R^1An is a carbon number of 1 to 60^AA group of valency or a single bond,

R^2Aeach independently is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted alkyl group having 2 to 30 carbon atoms30 alkenyl group, optionally substituted alkynyl group having 2 to 30 carbon atoms, optionally substituted alkoxy group having 1 to 30 carbon atoms, halogen atom, cyano group, mercapto group, hydroxyl group or group in which hydrogen atom of hydroxyl group is substituted by acid-dissociable group, wherein R is^2AAt least one of which is a mercapto group,

n^Aand [3]Wherein N is the same meaning, and wherein N is^AWhen n is an integer of 2 or more, n^A2]The structural formulae in (a) and (b) are optionally the same or different,

X^Arepresents an oxygen atom, a sulfur atom or is unbridged,

m^2Aeach independently an integer of 0 to 7, wherein at least 1 m^2AIs an integer of 1 to 7, and,

q^Aeach independently 0 or 1. )

[6]

The compound according to [4], wherein the compound represented by the formula (3) is a compound represented by the following formula (3-1).

(in the formula (3-1),

R⁰、R¹、R⁴、R⁵、n、p²～p⁵、m⁴and m⁵Such as [4]]The method according to the definition in (1),

R⁶and R⁷Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, or a mercapto group,

m⁶and m⁷Each independently an integer of 0 to 7. )

[7]

The compound according to [6], wherein the compound represented by the formula (3-1) is a compound represented by the following formula (3-2).

(in the formula (3-2),

R⁰、R¹n and p²～p⁵Such as [4]]The method according to the definition in (1),

R⁶、R⁷、m⁶and m⁷Such as [6]]The method according to the definition in (1),

R⁸and R⁹And R⁶And R⁷Are used in the same sense and have the same meaning,

m⁸and m⁹Each independently is an integer of 0 to 8. )

[8]

The compound according to [5], wherein the compound represented by the formula (4) is a compound represented by the following formula (4-1).

(in the formula (4-1),

R^0A、R^1A、n^A、q^Aand X^ASuch as [5]]The method according to the definition in (1),

R^3Aeach independently represents a halogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent, an aryl group having 6 to 30 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent, or an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent,

m^6Aeach independently an integer of 0 to 5. )

[9]

A resin comprising the compound of [1] or [2] as a structural unit.

[10]

The resin according to [9], which is represented by the following (5).

(in the formula (5),

R^Y、R^Z、A、R^Tx and N are as defined in [1]]The method according to the definition in (1),

m is each independently an integer of 0 to 8,

here, the number of the first and second electrodes,

selected from A, R^Y、R^Z、R^TAnd at least 1 of X comprises a sulfur atom,

R^Tat least one of which contains a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group,

when N is an integer of 2 or more, the structural formulae in the N [ ] are optionally the same or different,

l is an alkylene group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, an arylene group having 6 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, and an alkyleneoxy group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or a single bond, and the alkylene group, the arylene group, and the alkyleneoxy group may contain an ether bond, a thioether bond, a ketone bond, or an ester bond. )

[11]

A resin comprising the compound according to any one of [3] to [8] as a structural unit.

[12]

The resin according to [11], which has a structure represented by the following formula (6).

(in the formula (6),

l is a linear or branched alkylene group having 1 to 30 carbon atoms which may be optionally substituted, or a single bond,

R⁰and [3]R in (1)^YAre used in the same sense and have the same meaning,

R¹is an n-valent group or single bond having 1 to 60 carbon atoms,

R²～R⁵each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted aryl groupAn alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with an acid-dissociable group, wherein R is²～R⁵At least one of which is a mercapto group,

m²and m³Each independently an integer of 0 to 8,

m⁴and m⁵Each independently an integer of 0 to 9,

wherein m is²、m³、m⁴And m⁵When the temperature is not simultaneously 0, the temperature is not increased,

n is the same as N in [3], wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

p²～p⁵and [3]R in (A) has the same meaning. )

[13]

The resin according to [11], which has a structure represented by the following formula (7).

(in the formula (7),

l is a linear or branched alkylene group having 1 to 30 carbon atoms which may be optionally substituted, or a single bond,

R^0Aand [3]R in (1)^YAre used in the same sense and have the same meaning,

R^1An is a carbon number of 1 to 60^AA group of valency or a single bond,

R^2Aeach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein R represents a group^2AAt least one of which is a mercapto group,

n^Aand [3]Wherein N is the same meaning, and wherein N is^AWhen n is an integer of 2 or more, n^A2]The structural formulae in (a) and (b) are optionally the same or different,

X^Arepresents an oxygen atom, a sulfur atom or is unbridged,

m^2Aeach independently an integer of 0 to 7, wherein at least 1 m^2AIs an integer of 1 to 6, and,

q^Aeach independently 0 or 1. )

[14]

A composition comprising: 1 or more selected from the group consisting of the compounds described in [1] to [8] and the resins described in [9] to [13 ].

[15]

The composition according to [14], which further contains a solvent.

[16]

The composition according to [14] or [15], which further contains an acid generator.

[17]

The composition according to any one of [14] to [16], which further contains an acid crosslinking agent.

[18]

The composition according to any one of [14] to [17], which further contains a radical generator.

[19]

The composition according to any one of [14] to [18], which is used for forming a film for lithography.

[20]

The composition according to [19], which is used for forming a resist underlayer film.

[21]

The composition according to [19], which is used for forming a resist film.

[22]

The composition according to [19], which is used for forming a permanent resist film.

[23]

The composition according to any one of [14] to [18], which is used for forming an optical member.

[24]

A method for forming a resist pattern, comprising the steps of:

forming a photoresist layer on a substrate using the composition according to [19 ]; and a step of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer.

[25]

A method for forming an insulating film, comprising the steps of:

forming a photoresist layer on a substrate using the composition according to [19 ]; and the combination of (a) and (b),

and a step of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer.

[26]

A method for forming a resist pattern, comprising the steps of:

a step of forming an underlayer film on a substrate using the composition according to [19 ];

forming at least 1 photoresist layer on the underlayer film; and the combination of (a) and (b),

and a step of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer.

[27]

A circuit pattern forming method includes the steps of:

a step of forming an underlayer film on a substrate using the composition according to [19 ];

forming an intermediate layer film on the underlayer film by using a resist intermediate layer film material;

forming at least 1 photoresist layer on the interlayer film;

a step of forming a resist pattern by irradiating a predetermined region of the photoresist layer with radiation and developing the resist pattern;

etching the intermediate layer film using the resist pattern as a mask;

etching the lower layer film using the obtained intermediate layer film pattern as an etching mask; and the combination of (a) and (b),

and forming a pattern on the substrate by etching the substrate using the obtained lower layer film pattern as an etching mask.

[28]

A method for purifying the compound according to any one of [1] to [8] or the resin according to any one of [9] to [13],

the purification method comprises the following extraction procedures: the extraction is carried out by contacting a solution comprising the compound or resin and an organic solvent which is not optionally miscible with water, with an acidic aqueous solution.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: the present invention relates to a compound, a resin, and a composition (for example, a composition used for forming a film for lithography or an optical member) useful for forming a photoresist and an underlayer film for a photoresist, which can be applied to a wet process and are excellent in heat resistance, solubility, and etching resistance, and a pattern forming method (a resist pattern forming method and a circuit pattern forming method) using the composition.

Detailed Description

As will be described later, the compound and the resin of the present embodiment have high solubility in a safe solvent, and are excellent in heat resistance and etching resistance, and the resist composition of the present embodiment provides a good resist pattern shape.

Further, the compound and the resin of the present embodiment can realize a compound, a resin, and a film-forming composition for lithography, which are useful for forming a photoresist underlayer film that can be applied to a wet process and has excellent heat resistance and etching resistance. Further, the composition for forming a film for lithography has high heat resistance and high solvent solubility, and uses a compound or a resin having a specific structure, so that deterioration of the film at the time of high-temperature baking is suppressed, and a resist and an underlayer film having excellent etching resistance to oxygen plasma etching and the like can be formed. In addition, when an underlayer film is formed, since the adhesion to a resist layer is also excellent, an excellent resist pattern can be formed. Further, since the refractive index is high and coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, the composition is also useful as various optical forming compositions.

Hereinafter, embodiments of the present invention will be described. The following embodiments are examples for illustrating the present invention, and the present invention is not limited to the embodiments.

The structural formula described in the present specification means that, when a line bonded to C is brought into contact with the ring a and the ring B, the C is bonded to either or both of the ring a and the ring B, for example, as described below.

[ Compound represented by the formula (1) ]

The compound of the present invention is represented by the following formula (1) or the formula (1') described later. The compound of the present invention has such a structure, and therefore, has high heat resistance, a high carbon concentration, a low oxygen concentration, and high solvent solubility. Further, the refractive index is high by containing a sulfur atom. Further, the cured product had a low viscosity before curing and excellent planarization properties.

(in the formula (1),

R^Yis a hydrogen atom, an alkyl group having 1 to 60 carbon atoms and optionally having a substituent and/or a heteroatom, or an aryl group having 6 to 60 carbon atoms and optionally having a substituent and/or a heteroatom,

R^Zis a C1-60N-valent group or a single bond optionally having a substituent and/or a heteroatom,

or, R^YAnd R^ZOptionally containing the carbon atoms to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms,

a is a group having 1 to 60 carbon atoms and optionally having a substituent and/or a hetero atom,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms optionally having a substituent and/or a hetero atom, an aryl group having 6 to 40 carbon atoms optionally having a substituent and/or a hetero atom, an aryl group optionally having a substituent and/or a hetero atomAn alkenyl group having 2 to 30 carbon atoms as a hetero atom, an alkynyl group having 2 to 30 carbon atoms as an optional substituent, an alkoxy group having 1 to 30 carbon atoms as an optional substituent and/or a hetero atom, an alkylthio group having 1 to 30 carbon atoms as an optional substituent and/or a hetero atom, a halogen atom, a nitro group, an amino group, a cyano group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group, and the aryl group optionally contain an ether bond, a ketone bond, or an ester bond,

x is an oxygen atom, a sulfur atom or is unbridged,

here, the number of the first and second electrodes,

selected from A, R^Y、R^Z、R^TAnd at least 1 of X comprises a sulfur atom,

R^Tat least one of which contains a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group,

m is each independently an integer of 0 to 9,

n is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different. )

The term "alkyl" includes linear, branched and cyclic alkyl groups unless otherwise specified.

Examples of the "alkyl group" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl and the like.

Examples of the substituent on the alkyl group include a halogen atom, a nitro group, an amino group, a mercapto group, a hydroxyl group, and a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group.

Examples of the "aryl group" include a phenyl group and a naphthyl group.

Examples of the substituent on the aryl group include a halogen atom, a nitro group, an amino group, a mercapto group, a hydroxyl group, a phenyl group, and a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group.

Examples of the "alkenyl group" include propenyl and butenyl.

Examples of the substituent on the alkenyl group include a halogen atom, a nitro group, an amino group, a mercapto group, a hydroxyl group, and a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group.

Examples of the "alkynyl group" include propargyl and butynyl.

Examples of the substituent on the alkynyl group include a halogen atom, a nitro group, an amino group, a mercapto group, a hydroxyl group, and a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group.

Examples of the "alkoxy group" include methoxy, ethoxy, propoxy, cyclohexyloxy, phenoxy, and naphthyloxy.

Examples of the substituent on the alkoxy group include a halogen atom, a nitro group, an amino group, a mercapto group, a hydroxyl group, and a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group.

Examples of the "alkylthio group" include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, cyclopropylthio, cyclobutylthio and the like.

Examples of the substituent on the alkylthio group include a halogen atom, a nitro group, an amino group, a mercapto group, a hydroxyl group, and a group in which a hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Examples of the "hetero atom" include a sulfur atom, a nitrogen atom, and an oxygen atom.

The "acid-dissociable group" is a characteristic group that is cleaved in the presence of an acid to generate a functional group that changes solubility, such as an alkali-soluble group. The alkali-soluble group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group, among which, from the viewpoint of easiness of availability of an introduction reagent, the phenolic hydroxyl group and the carboxyl group are preferable, and the phenolic hydroxyl group is particularly preferable.

The acid-dissociable reactive group preferably has a property of causing the cleavage reaction in the presence of an acid in a chain manner so that high-sensitivity/high-resolution patterning can be achieved. The acid-dissociable reactive group is not particularly limited, and can be suitably selected from, for example, hydroxystyrene resins, (meth) acrylic resins, and the like proposed for use in chemical amplification resist compositions for KrF and ArF.

Preferred examples of the acid-dissociable reactive group include groups having a property of being dissociated by an acid and selected from the group consisting of a substituted methyl group, a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group. The acid-dissociable reactive group preferably does not have a crosslinkable functional group from the viewpoint of roughness.

The substituted methyl group is not particularly limited, but is usually a substituted methyl group having 2 to 20 carbon atoms, preferably a substituted methyl group having 4 to 18 carbon atoms, and more preferably a substituted methyl group having 6 to 16 carbon atoms. Specific examples of the substituted methyl group include, but are not limited to, methoxymethyl, methylthiomethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, t-butoxymethyl, 2-methylpropoxymethyl, ethylthiomethyl, methoxyethoxymethyl, phenoxymethyl, 1-cyclopentyloxymethyl, 1-cyclohexyloxymethyl, benzylthiomethyl, phenacyl, 4-bromobenzoylmethyl, 4-methoxybenzoylmethyl, piperonyl, and a substituent represented by the following formula (Y-1).

In the above formula (Y-1), R^2AIs an alkyl group having 1 to 4 carbon atoms. As R^2ASpecific examples of (A) include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl,T-butyl, n-butyl, and the like.

The 1-substituted ethyl group is not particularly limited, but is usually a 1-substituted ethyl group having 3 to 20 carbon atoms, preferably a 1-substituted ethyl group having 5 to 18 carbon atoms, and more preferably a substituted ethyl group having 7 to 16 carbon atoms. Specific examples of the 1-substituted ethyl group include, but are not limited to, 1-methoxyethyl, 1-methylthioethyl, 1-dimethoxyethyl, 1-ethoxyethyl, 1-ethylthioethyl, 1-diethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, tert-butoxyethyl, 2-methylpropoxyethyl, 1-phenoxyethyl, 1-phenylthioethyl, 1-diphenoxyethyl, 1-cyclopentyloxyethyl, 1-cyclohexyloxyethyl, 1-phenylethyl, 1-diphenylethyl, and a substituent represented by the following formula (Y-2).

In the above formula (Y-2), R^2AThe same as described above.

The 1-substituted-n-propyl group is not particularly limited, and is usually a 1-substituted-n-propyl group having 4 to 20 carbon atoms, preferably a 1-substituted-n-propyl group having 6 to 18 carbon atoms, and more preferably a 1-substituted-n-propyl group having 8 to 16 carbon atoms. Specific examples of the 1-substituted-n-propyl group include, but are not limited to, 1-methoxy-n-propyl group, 1-ethoxy-n-propyl group, and the like.

The 1-branched alkyl group is not particularly limited, and is usually a 1-branched alkyl group having 3 to 20 carbon atoms, preferably a 1-branched alkyl group having 5 to 18 carbon atoms, and more preferably a branched alkyl group having 7 to 16 carbon atoms. Specific examples of the 1-branched alkyl group include, but are not limited to, isopropyl group, sec-butyl group, tert-butyl group, 1-dimethylpropyl group, 1-methylbutyl group, 1-dimethylbutyl group, 2-methyladamantyl group, and 2-ethyladamantyl group.

The silyl group is not particularly limited, and is usually a silyl group having 1 to 20 carbon atoms, preferably a silyl group having 3 to 18 carbon atoms, and more preferably a silyl group having 5 to 16 carbon atoms. Specific examples of the silyl group include, but are not limited to, trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, t-butyldimethylsilyl, t-butyldiethylsilyl, t-butyldiphenylsilyl, tri-t-butylsilyl, and triphenylsilyl groups.

The acyl group is not particularly limited, and is usually an acyl group having 2 to 20 carbon atoms, preferably an acyl group having 4 to 18 carbon atoms, and more preferably an acyl group having 6 to 16 carbon atoms. Specific examples of the acyl group include, but are not limited to, acetyl, phenoxyacetyl, propionyl, butyryl, heptanoyl, hexanoyl, pentanoyl, pivaloyl, isovaleryl, lauroyl, adamantylcarbonyl, benzoyl, naphthoyl, and the like.

The 1-substituted alkoxymethyl group is not particularly limited, but is usually a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms, preferably a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms, and more preferably a 1-substituted alkoxymethyl group having 6 to 16 carbon atoms. Specific examples of the 1-substituted alkoxymethyl group include, but are not limited to, 1-cyclopentylmethoxymethyl, 1-cyclopentylethoxymethyl, 1-cyclohexylmethoxymethyl, 1-cyclohexylethoxymethyl, 1-cyclooctylmethoxymethyl and 1-adamantylmethoxymethyl.

The cyclic ether group is not particularly limited, and is usually a cyclic ether group having 2 to 20 carbon atoms, preferably a cyclic ether group having 4 to 18 carbon atoms, and more preferably a cyclic ether group having 6 to 16 carbon atoms. Specific examples of the cyclic ether group include, but are not limited to, tetrahydropyranyl groups, tetrahydrofuranyl groups, tetrahydrothiopyranyl groups, tetrahydrothienyl groups, 4-methoxytetrahydropyranyl groups, and 4-methoxytetrahydrothiopyranyl groups.

The alkoxycarbonyl group is usually an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonyl group having 6 to 16 carbon atoms. Specific examples of the alkoxycarbonyl group include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, and an acid-dissociable reactive group represented by n ═ 0 in the following formula (Y-3).

The alkoxycarbonylalkyl group is not particularly limited, and is usually an alkoxycarbonylalkyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonylalkyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonylalkyl group having 6 to 16 carbon atoms. Specific examples of the alkoxycarbonylalkyl group include, but are not limited to, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, and acid-dissociable reactive groups represented by the following formula (Y-3) in which n is 1 to 4.

In the above formula (Y-3), R^3AIs a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 4.

Among these acid-dissociable reactive groups, substituted methyl groups, 1-substituted ethyl groups, 1-substituted alkoxymethyl groups, cyclic ether groups, alkoxycarbonyl groups, and alkoxycarbonylalkyl groups are preferred, and from the viewpoint of achieving higher sensitivity, substituted methyl groups, 1-substituted ethyl groups, alkoxycarbonyl groups, and alkoxycarbonylalkyl groups are more preferred, and acid-dissociable reactive groups having a structure selected from the group consisting of cycloalkanes having 3 to 12 carbon atoms, lactones, and aromatic rings having 6 to 12 carbon atoms are still more preferred.

The cycloalkane having 3 to 12 carbon atoms may be monocyclic or polycyclic, and polycyclic is preferable.

Specific examples of the cycloalkane having 3 to 12 carbon atoms include, but are not limited to, monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, and the like, and more specifically, include, but are not limited to, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like, polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclodecane, and the like. Among them, adamantane, tricyclodecane and tetracyclodecane are preferable, and adamantane and tricyclodecane are more preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent.

The lactone is not limited to the following, and examples thereof include butyrolactone and cycloalkyl groups having 3 to 12 carbon atoms and having a lactone group.

The aromatic ring having 6 to 12 carbon atoms is not limited to the following, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is more preferable.

Among the above, acid-dissociable reactive groups selected from the group consisting of the groups represented by the following formula (Y-4) tend to have higher resolution, and are particularly preferred.

In the above formula (Y-4), R^5AIs a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, R^6AIs a hydrogen atom, a straight or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen atom or a carboxyl group, n_1AIs an integer of 0 to 4, n_2AIs an integer of 1 to 5, n_0AIs an integer of 0 to 4.

The term "acid-crosslinkable group" as used herein means a group which can be crosslinked in the presence or absence of a catalyst. The acid-crosslinkable group is not particularly limited, and examples thereof include alkoxy groups having 1 to 20 carbon atoms, groups having allyl groups, groups having (meth) acryloyl groups, groups having epoxy (meth) acryloyl groups, groups having hydroxyl groups, groups having urethane (meth) acryloyl groups, groups having glycidyl groups, groups having vinylphenylmethyl groups, groups having various alkynyl groups, groups having carbon-carbon double bonds, and groups having carbon-carbon triple bonds.

The group having an allyl group is not particularly limited, and examples thereof include a group represented by the following general formula (X-1).

(in the general formula (X-1), n^X1Is an integer of 1 to 5. )

The group having a (meth) acryloyl group is not particularly limited, and examples thereof include those represented by the following general formula (X-2).

(in the general formula (X-2), n^X2Is an integer of 1 to 5, R^XIs a hydrogen atom or a methyl group. )

The group having an epoxy (meth) acryloyl group is not particularly limited, and examples thereof include groups represented by the following general formula (X-3). Here, the epoxy (meth) acryloyl group means a group formed by reacting an epoxy (meth) acrylate with a hydroxyl group.

(in the general formula (X-3), n^x3Is an integer of 0 to 5, R^XIs a hydrogen atom or a methyl group. )

The group having a urethane (meth) acryloyl group is not particularly limited, and examples thereof include groups represented by the following general formula (X-4).

(in the general formula (X-4), n^x4Is an integer of 0 to 5, s is an integer of 0 to 3, R^XIs a hydrogen atom or a methyl group. )

The group having a hydroxyl group is not particularly limited, and examples thereof include a group represented by the following general formula (X-5).

(in the general formula (X-5), n^x5Is an integer of 1 to 5. )

The group having a glycidyl group is not particularly limited, and examples thereof include a group represented by the following general formula (X-6).

(in the general formula (X-6), n^x6Is an integer of 1 to 5. )

The group having a vinylphenylmethyl group is not particularly limited, and examples thereof include groups represented by the following general formula (X-7).

(in the general formula (X-7), n^x7Is an integer of 1 to 5. )

The group having various alkynyl groups is not particularly limited, and examples thereof include groups represented by the following general formula (X-8).

(in the general formula (X-8), n^x8Is an integer of 1 to 5. )

Examples of the group having a carbon-carbon double bond include a (meth) acryloyl group, a substituted or unsubstituted vinylphenyl group, and a group represented by the following formula (X-9-1). Examples of the group having a carbon-carbon triple bond include a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, and groups represented by the following formulae (X-9-2) and (X-9-3).

In the above formula (X-9-1), R^X9A、R^X9BAnd R^X9CEach independently represents a hydrogen atom or a C1-20 hydrocarbon group. In the above formulae (X-9-2) and (X-9-3), R^X9D、R^X9EAnd R^X9FEach independently represents a hydrogen atom or a C1-20 hydrocarbon group.

Among the above, from the viewpoint of ultraviolet curability, (meth) acryloyl, epoxy (meth) acryloyl, urethane (meth) acryloyl, a group having a glycidyl group, and a styryl group are preferable, and (meth) acryloyl, epoxy (meth) acryloyl, and urethane (meth) acryloyl are more preferable, and (meth) acryloyl is even more preferable. In addition, from the viewpoint of heat resistance, groups having various alkynyl groups are also preferable.

R^YThe alkyl group is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms optionally having a substituent and/or a hetero atom, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

R^ZThe group having a carbon number of 1 to 30 is preferable, the group having a carbon number of 3 to 30 is more preferable, the group having a carbon number of 3 to 12 is further preferable, and the group having a carbon number of 3 to 12 is particularly preferable. The N-valent group optionally contains a sulfur atom. The ring or aromatic ring optionally contains a sulfur atom and/or a nitrogen atom as a ring atom. The ring or the aromatic ring is optionally substituted with a substituent containing a sulfur atom (e.g., alkylthio), a hydroxyl group, a phenyl group, or an alkyl group having 1 to 6 carbon atoms. The N is preferably 1 to 3, more preferably 1 or 2.

R^ZFor example, it is optionally an alkyl group having 1 to 60 carbon atoms, an alkylene group having 1 to 60 carbon atoms, an alkanetriyl group having 2 to 60 carbon atoms, an alkanetetrayl group having 3 to 60 carbon atoms, or an aromatic group having 6 to 60 carbon atoms. These groups optionally have alicyclic hydrocarbon groups, double bonds, hetero atoms, or aromatic groups having 6 to 60 carbon atoms. The alicyclic hydrocarbon group is optionally a bridged alicyclic hydrocarbon group.

R^YAnd R^ZIt preferably contains the carbon atoms to which they are bonded to form a four-to twenty-one membered ring, and more preferably contains the carbon atoms to which they are bonded to form a six-to thirteen-membered ring. The ring is optionally an alicyclic hydrocarbon ring, an aromatic ring, or a fused ring thereof. The alicyclic hydrocarbon ring is optionally a bridged alicyclic hydrocarbon ring. The ring optionally contains a sulfur atom and/or a nitrogen atom as a ring atom. The ring is optionally substituted with a substituent containing a sulfur atom (e.g., alkylthio), a hydroxyl group, a phenyl group, or an alkyl group having 1 to 6 carbon atoms.

As R^ZOr R^Y-C-R^ZExamples thereof include those having the following skeletons. From the viewpoint of improving the refractive index, it is preferable that the skeleton contains a sulfur atom.

A is preferably an aryl group having 6 to 14 carbon atoms, more preferably a phenyl group or naphthyl group.

R^TPreferably each independently is a mercapto group, a hydroxyl group, or a phenyl group. The phenyl group is optionally substituted with a mercapto group and/or a hydroxyl group. The phenyl group is optionally bonded to a via a thioether or disulfide bond.

X is preferably an oxygen atom or is unbridged.

m is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

N is preferably an integer of 1 to 3, more preferably 1 or 2.

The compound represented by the above formula (1) has a relatively low molecular weight, but has high heat resistance due to rigidity of its structure, and therefore can be used under high-temperature baking conditions. Is suitably used as a film-forming composition for lithography which can be used for producing a film for lithography.

In addition, the compound represented by the above formula (1) has high solubility in a safe solvent and is excellent in heat resistance and etching resistance, and therefore, a resist-forming composition for lithography containing the compound represented by the above formula (1) can provide an excellent resist pattern shape. Further, since sulfur atoms are contained, a sensitizing effect can be expected in EUV lithography.

Further, since the composition has a low molecular weight and a low viscosity, even if the substrate has a level difference (particularly, fine spaces, hole patterns, and the like), the composition can be easily uniformly filled in the level difference, and the film flatness can be easily improved. In addition, since the compound having a high carbon concentration contains a sulfur atom, high etching resistance can be imparted.

Further, since the aromatic compound has a high aromatic density and contains a sulfur atom, the compound has a high refractive index and is inhibited from being colored by a heat treatment in a wide range from a low temperature to a high temperature, and therefore, the compound is also useful as a composition for forming various optical members. The optical member is useful as a plastic lens (prism lens, lenticular lens, microlens, fresnel lens, viewing angle control lens, contrast improvement lens, etc.), a retardation film, an electromagnetic wave shielding film, a prism, an optical fiber, a solder resist for a flexible printed circuit board, a plating resist, an interlayer insulating film for a multilayer printed circuit board, a photosensitive optical waveguide, a liquid crystal display, an organic Electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin-film solar cell, a dye-sensitized solar cell, and an organic thin-film transistor (TFT), in addition to being used in a film form or a sheet form. The present invention can be suitably used as a member of a solid-state imaging device which requires a high refractive index, in particular, a filling film and a planarizing film on a photodiode, planarizing films before and after a color filter, a microlens, a planarizing film on a microlens, and a conformal film.

The compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1) from the viewpoint of solubility in an organic solvent.

In the above-mentioned (1-1),

R^Y、R^Za, X and N are as defined in formula (1),

R^3Aeach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a mercapto group,

R^4Aeach independently a hydrogen atom, an acid-crosslinkable group or an acid-dissociable group,

here, it is selected from A, R^Y、R^Z、R^3A、R^4AAnd at least 1 of X comprises a sulfur atom,

m^6Aeach independently an integer of 0 to 5,

m^7Aeach independently an integer of 0 to 5.

Further, specific examples of the compound represented by the above formula (1) are shown below, but the compound represented by the formula (1) is not limited to the specific examples listed herein.

From the viewpoint of heat resistance and solubility, the formula (1-1) is preferably the following formula (1-2), or (1-3), (1-3-1), (1-3-2), (1-4), or (1-4-1).

(in the formula (1-2),

R^Yis a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms,

R^Zis a C1-60N-valent group or a single bond,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 40 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group and the aryl group may have an ether bond, a ketone bond or an ester bond,

x represents an oxygen atom, a sulfur atom or is unbridged,

here, is selected from R^T、R^Y、R^ZAnd at least 1 of X comprises a sulfur atom,

m is each independently an integer of 0 to 9, where at least one of m is an integer of 1 to 9,

n is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

r is an integer of 0 to 2. )

The compound represented by the formula (1-2) is not particularly limited, and preferably satisfies 1 or more of the following (a) to (e) from the viewpoints of suppression of coloring properties and suppression of decomposition properties of the compound.

(a) The method comprises the following steps In the formula (1-2), r in the structural formula in [ ] is the same, that is, the sites shown by 2 aryl structures in the structural formula in [ ] are the same structure.

(b) The method comprises the following steps In the formula (1-2)]R bonded to the site shown in each aryl structure in the inner structural formula^TAnd the same, and further the bond in the site shown by each aryl structureThe parts are the same.

(c) The method comprises the following steps In the formula (1-2), N is 1-2, and further 1.

(d) The method comprises the following steps In the formula (1-2), R^YIs a straight-chain alkyl group or phenyl group having 1 to 30 carbon atoms, and further is a methyl group or phenyl group.

(e) The method comprises the following steps In the formula (1-2), R^ZIs a C1-60N-valent group.

When the compound has the following structure, the compound has high heat resistance and high solvent solubility.

In the above formula (1-3), R⁰And the aforementioned R^YThe same meaning, hydrogen atom, alkyl group having 1 to 30 carbon atoms optionally having substituent, or aryl group having 6 to 30 carbon atoms optionally having substituent. R⁰When the alkyl group has 1 to 30 carbon atoms and optionally has a substituent or the aryl group has 6 to 30 carbon atoms and optionally has a substituent, the compound is inhibited from oxidative decomposition and coloring, and the heat resistance is increased and the solvent solubility is improved.

R¹Is a group having a carbon number of 1 to 60 and a valence of n or a single bond, with the aid of R¹Each aromatic ring is bonded.

R²～R⁵Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid dissociable group.

Here, is selected from R⁰、R¹、R²、R³、R⁴And R⁵At least 1 of which comprises a sulfur atom,

m²and m³Each independently an integer of 0 to 8, m⁴And m⁵Each independently an integer of 0 to 9. Wherein m is²、m³、m⁴And m⁵Not simultaneously become 0.

n is an integer of 1 to 4.

p²～p⁵Each independently an integer of 0 to 2. In addition, p is²～p⁵When 0, the site represented by the naphthalene structure in the formula (3) represents a benzene structure, p²～p⁵In the case of 1, p represents a naphthalene structure²～p⁵In the case of 2, a tricyclic structure such as anthracene or phenanthrene is represented.

N is the same as N, and when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different.

The aforementioned n-valent group is as follows: when n is 1, it means an alkyl group having 1 to 60 carbon atoms, when n is 2, it means an alkylene group having 1 to 60 carbon atoms, when n is 3, it means an alkanetriyl group having 2 to 60 carbon atoms, and when n is 4, it means an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, and an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. The n-valent group optionally has an aromatic group having 6 to 60 carbon atoms.

The n-valent hydrocarbon group optionally has an alicyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 60 carbon atoms. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

In the formula (1-3-1),

R⁰、R¹、R⁴、R⁵、n、p²～p⁵、m⁴and m⁵The same meanings as those in the formulae (1-3),

R⁶and R⁷Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, or a substituted alkynyl groupAn alkoxy group having 1 to 30 carbon atoms, a halogen atom, or a mercapto group,

R^Uindependently a hydroxyl group or a mercapto group,

is selected from R⁰、R¹、R⁴、R⁵、R⁶、R⁷And R^UAt least 1 of which comprises a sulfur atom,

m⁶and m⁷Each independently an integer of 0 to 7.

In the formula (1-3-2),

R⁰、R¹、n、p²～p⁵the same as that described for the formula (1-3), R⁶、R⁷、m⁶And m⁷The same meanings as those in the formula (1-3-1),

R⁸and R⁹And the aforementioned R⁶And R⁷Are used in the same sense and have the same meaning,

R^Uindependently a hydroxyl group or a mercapto group,

is selected from R⁰、R¹、R⁶、R⁷、R⁸、R⁹And R^UAt least 1 of which comprises a sulfur atom,

m⁸and m⁹Each independently is an integer of 0 to 8.

In the formula (1-4), R^0AAnd the aforementioned R^YThe same meaning, hydrogen atom, alkyl group having 1 to 30 carbon atoms optionally having substituent, or aryl group having 6 to 30 carbon atoms optionally having substituent.

R^1AN is a carbon number of 1 to 60^AA group of valency or a single bond,

R^2Aeach independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or an optionally substituted aryl groupAn alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with an acid-dissociable group,

in the formula (1-4), selected from R^0A、R^1A、R^2AAt least 1 of which comprises a sulfur atom,

n^Ais an integer of 1 to 4, where in the formula (1-4), n^AWhen n is an integer of 2 or more, n^A2]The internal structural formulae are optionally the same or different.

X^AEach independently represents an oxygen atom, a sulfur atom or is unbridged. Here, X^AOxygen atoms or sulfur atoms are preferred because they tend to exhibit high heat resistance, and oxygen atoms are more preferred. From the viewpoint of solubility, X^APreferably unbridged.

m^2AEach independently an integer of 0 to 6. Wherein, at least 1 m^2AIs an integer of 1 to 6.

q^AEach independently 0 or 1. In addition, q is^AWhen 0, the site represented by the naphthalene structure in the formula (1-4) represents a benzene structure, q^AWhen the number is 1, it represents a naphthalene structure.

In addition, n is^AThe valency groups are as follows: n is^AWhen 1, it means an alkyl group having 1 to 60 carbon atoms, n^AWhen 2, it means an alkylene group having 1 to 30 carbon atoms, n^AWhen 3, n is an alkanetriyl group having 2 to 60 carbon atoms^AWhen 4, it means an alkanetetrayl group having 3 to 60 carbon atoms. As the aforementioned n^AExamples of the valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, and an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. In addition, the above n^AThe valence group optionally has an aromatic group having 6 to 60 carbon atoms.

In addition, the above n^AThe hydrocarbon group has an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 or 6 to 30 carbon atoms. Here, the alicyclic hydrocarbon group also includesA bridged alicyclic hydrocarbon group.

In the formula (1-4-1), R^0A、R^1A、n^A、q^AAnd X^AThe same meanings as those in the above formulae (1-4).

R^3AEach independently represents a halogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent, an aryl group having 6 to 30 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent, or an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent,

R^Uindependently a hydroxyl group or a mercapto group,

is selected from R^0A、R^1A、R^3AAnd R^UAt least 1 of which comprises a sulfur atom,

m^6Aeach independently an integer of 0 to 5.

[ Compound represented by the formula (1') ]

The compound of the present invention is also represented by the following formula (1'). The compound of the present invention has such a structure, and therefore, has high heat resistance, a high carbon concentration, a low oxygen concentration, and high solvent solubility. In addition, a sulfur atom is contained, thereby being a high refractive index. Further, the cured product had a low viscosity before curing and excellent planarization properties.

(in the formula (1'),

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an aryl group having 6 to 40 carbon atoms optionally having a substituent and/or a heteroatom, an alkenyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkynyl group having 2 to 30 carbon atoms optionally having a substituent and/or a heteroatom, an alkoxy group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom, or an alkoxy group having 1 to 30 carbon atoms optionally having a substituent and/or a heteroatom1 to 30 of an alkylthio group, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group, and the aryl group optionally contain an ether bond, a ketone bond, or an ester bond,

R⁰each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or an aryl group having 6 to 30 carbon atoms and optionally having a substituent and/or a hetero atom,

or, 2R⁰Optionally containing the carbon atom to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms, 2R⁰A double bond bonded to a carbon atom to which they are bonded, the double bond being optionally bonded to an alkyl group having 1 to 30 carbon atoms and having a substituent and/or a heteroatom, or an aryl group having 6 to 30 carbon atoms and optionally having a substituent and/or a heteroatom,

a and A' are groups having 1 to 60 carbon atoms and optionally having a substituent and/or a hetero atom,

l is an integer of 1 to 9,

k and L' are each independently an integer of 0 to 9. )

The terms such as "alkyl group", "aryl group", "alkenyl group", "alkynyl group", "alkoxy group", "alkylthio group", "halogen atom", "hetero atom", "acid-dissociable group" and "acid-crosslinkable group" in the above formula (1') have the same meanings as those described in the formula (1).

The compound represented by the above formula (1 ') is preferably a compound represented by the following formula (1-1') from the viewpoint of solubility in an organic solvent.

(in the formula (1-1'),

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms optionally having a substituent and/or a hetero atom, an aryl group having 6 to 40 carbon atoms optionally having a substituent and/or a hetero atom, or a compound having a substituentAn alkenyl group having 2 to 30 carbon atoms which is a group and/or a heteroatom, an alkynyl group having 2 to 30 carbon atoms which is optionally a substituent and/or a heteroatom, an alkoxy group having 1 to 30 carbon atoms which is optionally a substituent and/or a heteroatom, an alkylthio group having 1 to 30 carbon atoms which is optionally a substituent and/or a heteroatom, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group, or a group in which a hydrogen atom of a mercapto group or a hydroxyl group is substituted with an acid crosslinkable group or an acid dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group, and the aryl group optionally contain an ether bond, a ketone bond, or an ester bond,

R⁰each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or an aryl group having 6 to 30 carbon atoms and optionally having a substituent and/or a hetero atom,

or, 2R⁰Optionally containing the carbon atom to which they are bonded to form a four-to thirty-membered ring optionally having substituents and/or heteroatoms, 2R⁰A double bond bonded to a carbon atom to which they are bonded, the double bond being bonded to an alkyl group having 1 to 30 carbon atoms which may have a substituent and/or a heteroatom, or an aryl group having 6 to 30 carbon atoms which may have a substituent and/or a heteroatom,

r is each independently an integer of 0 to 2,

L¹is an integer of 1 to (4+2r),

k' and L^1’Each independently is an integer of 0 to (3+2 r). )

The compound represented by the above formula (1-1 ') is not particularly limited, and is exemplified by the following formula (1-2').

The above formula (1-2') has high etching resistance, high refractive index and high transmittance.

[ Compound represented by the formula (2) ]

The compound of the present embodiment is preferably represented by the following formula (2).

(in the formula (2),

R^Yis a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms,

R^Zis a C1-60N-valent group or a single bond,

R^Teach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 40 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a nitro group, an amino group, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid-dissociable group, wherein the alkyl group, the alkenyl group, the alkynyl group and the aryl group may have an ether bond, a ketone bond or an ester bond, and R represents an ether bond, a ketone bond or an ester bond^TAt least one of which is a mercapto group,

x represents an oxygen atom, a sulfur atom or is unbridged,

m is each independently an integer of 0 to 9, where at least one of m is an integer of 1 to 9,

n is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

r is an integer of 0 to 2. )

The compound represented by formula (2) is not particularly limited, and preferably satisfies 1 or more of the following (a) to (e) from the viewpoint of suppression of coloring properties and suppression of decomposition properties of the compound.

(a) The method comprises the following steps In the formula (2), r in the structural formula in [ ] is the same, that is, the sites shown by 2 aryl structures in the structural formula in [ ] are the same structure.

(b) The method comprises the following steps In the formula (2)]R bonded to the site shown in each aryl structure in the inner structural formula^TThe same applies to the binding sites among the sites represented by the aryl structures.

(c) The method comprises the following steps In the formula (2), N is 1-2, and further 1.

(d) The method comprises the following steps Formula (2)) In, R^YIs a straight-chain alkyl group or phenyl group having 1 to 30 carbon atoms, and further is a methyl group or phenyl group.

(e) The method comprises the following steps In the formula (2), R^ZIs a C1-60N-valent group.

The compound represented by the formula (2) is preferably a compound represented by the following formula (2-1) from the viewpoints of ease of crosslinking and solubility in an organic solvent.

(in the formula (2-1),

R^Y’is a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms,

R^Zis a C1-60N-valent group or a single bond,

R^T’each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with an acid-dissociable group,

here, R^T’At least one of which is a mercapto group,

x represents an oxygen atom, a sulfur atom or is unbridged,

m is each independently an integer of 0 to 9, where at least one of m is an integer of 1 to 9,

n is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different,

r is an integer of 0 to 2. )

Hereinafter, the compound represented by the formula (2) and the compound represented by the formula (2-1) will be described centering on the compound represented by the formula (3) and the compound represented by the formula (4). The compound represented by the formula (2) and the compound represented by the formula (2-1) are not limited to the compounds described below.

[ Compound represented by the formula (3) ]

The compound of the present embodiment is preferably represented by the following formula (3). The compound of the present embodiment has the following structure, and further, has high heat resistance and high solvent solubility.

In the above formula (3), R⁰And the aforementioned R^YThe same meaning, hydrogen atom, alkyl group having 1 to 30 carbon atoms optionally having substituent, or aryl group having 6 to 30 carbon atoms optionally having substituent. R⁰When the alkyl group having 1 to 30 carbon atoms optionally having a substituent or the aryl group having 6 to 30 carbon atoms optionally having a substituent is used, the oxidative decomposition of the present compound is suppressed, the coloring is suppressed, the heat resistance is increased, and the solvent solubility is improved.

R¹Is a group having a carbon number of 1 to 60 and a valence of n or a single bond, with the aid of R¹Each aromatic ring is bonded.

R²～R⁵Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted by an acid dissociable group. Wherein, in the formula (3), R²～R⁵At least one of them is a mercapto group.

m²And m³Each independently an integer of 0 to 8, m⁴And m⁵Each independently an integer of 0 to 9. Wherein m is²、m³、m⁴And m⁵Not simultaneously become 0.

n is an integer of 1 to 4.

p²～p⁵Each independently an integer of 0 to 2. In addition, p is²～p⁵When 0, the site represented by the naphthalene structure in the formula (3) represents a benzene bondStructure, p²～p⁵In the case of 1, p represents a naphthalene structure²～p⁵In the case of 2, a tricyclic structure such as anthracene or phenanthrene is represented.

N is the same as N, and when N is an integer of 2 or more, the structural formulae in N [ ] are optionally the same or different.

It is to be noted that the aforementioned n-valent group is optionally: when n is 1, it means an alkyl group having 1 to 60 carbon atoms, when n is 2, it means an alkylene group having 1 to 60 carbon atoms, when n is 3, it means an alkanetriyl group having 2 to 60 carbon atoms, and when n is 4, it means an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, and an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. The n-valent group optionally has an aromatic group having 6 to 60 carbon atoms.

The n-valent hydrocarbon group optionally has an alicyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 60 carbon atoms. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

The compound represented by the above formula (3) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used even under high-temperature baking conditions. Further, the composition has a tertiary carbon or quaternary carbon in the molecule, and is suppressed in crystallinity, and therefore, is suitable for use as a composition for forming a film for lithography which can be used for producing a film for lithography. From the viewpoint of suppressing crystallinity, it is preferable to have a quaternary carbon.

In addition, the compound represented by the formula (3) has high solubility in a safe solvent and is excellent in heat resistance and etching resistance, and therefore, the resist-forming composition for lithography of the present embodiment provides an excellent resist pattern shape.

Further, since the compound represented by the formula (3) has a low molecular weight and a low viscosity, even in the case of a substrate having a level difference (particularly, a fine space, a hole pattern, or the like), the compound can be easily uniformly filled in all over the level difference, and the flatness of the film can be easily improved. In addition, since the compound has a high carbon concentration, high etching resistance can be imparted.

The compound represented by formula (3) has a high refractive index and is inhibited from being colored by a heat treatment in a wide range from a low temperature to a high temperature, and therefore, is also useful as a composition for forming various optical members. The optical member is useful as a plastic lens (prism lens, lenticular lens, microlens, fresnel lens, viewing angle control lens, contrast improvement lens, etc.), a retardation film, an electromagnetic wave shielding film, a prism, an optical fiber, a solder resist for a flexible printed circuit board, a plating resist, an interlayer insulating film for a multilayer printed circuit board, a photosensitive optical waveguide, a liquid crystal display, an organic Electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin-film solar cell, a dye-sensitized solar cell, and an organic thin-film transistor (TFT), in addition to being used in a film form or a sheet form. The present invention can be suitably used as a member of a solid-state imaging device which requires a high refractive index, in particular, a filling film and a planarizing film on a photodiode, planarizing films before and after a color filter, a microlens, a planarizing film and a conformal film on a microlens.

The compound represented by the formula (3) is preferably a compound represented by the following formula (3-1) from the viewpoints of ease of crosslinking and solubility in an organic solvent.

In the formula (3-1),

R⁰、R¹、R⁴、R⁵、n、p²～p⁵、m⁴and m⁵The same meanings as those in the formula (3),

R⁶and R⁷Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, or a mercapto group,

m⁶and m⁷Each independently an integer of 0 to 7.

In addition, the compound represented by the formula (3-1) is preferably a compound represented by the following formula (3-2) from the viewpoint of further ease of crosslinking and solubility in organic solvents.

In the formula (3-2),

R⁰、R¹、n、p²～p⁵the same as that described in the formula (3), R⁶、R⁷、m⁶And m⁷The same meanings as those in the formula (3-1),

R⁸and R⁹And the aforementioned R⁶And R⁷Are used in the same sense and have the same meaning,

m⁸and m⁹Each independently is an integer of 0 to 8.

From the viewpoint of raw material availability, a compound represented by the following formula (3a) is preferred.

In the above formula (3a), R⁰～R⁵、m²～m⁵And n is the same as that described in the aforementioned formula (3).

The compound represented by the formula (3a) is more preferably a compound represented by the following formula (3b) from the viewpoint of solubility in an organic solvent.

In the above formula (3b), R⁰、R¹、R⁴、R⁵、m⁴、m⁵And n is as defined in the above formula (3), R⁶、R⁷、m⁶And m⁷In phase with that described in the above formula (3-1)The same meaning is given.

From the viewpoint of reactivity, the compound represented by the above formula (3a) is more preferably a compound represented by the following formula (3 b').

In the above formula (3 b'), R⁰、R¹、R⁴、R⁵、m⁴、m⁵And n is as defined in the above formula (3), R⁶、R⁷、m⁶And m⁷The same meanings as those in the above formula (3-1).

From the viewpoint of solubility in organic solvents, the compound represented by the formula (3b) is more preferably a compound represented by the following formula (3 c).

In the above formula (3c), R⁰、R¹And n is as defined for formula (3), R⁶、R⁷、m⁶And m⁷The same as that described for the formula (3-1), R⁸、R⁹、m⁸And m⁹The same meanings as those in the formula (3-2).

From the viewpoint of reactivity, the compound represented by the above formula (3b ') is more preferably a compound represented by the following formula (3 c').

In the above formula (3 c'), R⁰、R¹And n is as defined for formula (3), R⁶、R⁷、m⁶And m⁷The same as that described for the formula (3-1), R⁸、R⁹、m⁸And m⁹The same meanings as those in the formula (3-2).

The compound represented by the above formula (3) is particularly preferably a compound represented by the following formula (3d-1) or (3d-2) from the viewpoint of further solubility in an organic solvent.

In the above formula (3d-1), R⁰、R¹And n is as defined for formula (3), R^4’And R^5’Each independently represents an alkyl group having 1 to 30 carbon atoms optionally having a substituent, an aryl group having 6 to 30 carbon atoms optionally having a substituent, an alkenyl group having 2 to 30 carbon atoms optionally having a substituent, an alkynyl group having 2 to 30 carbon atoms optionally having a substituent, an alkoxy group having 1 to 30 carbon atoms optionally having a substituent, or a halogen atom. m is^4’And m^5’Is an integer of 0 to 8, m^10’And m^11’Is an integer of 1 to 9, m^4’+m^10’And m^5’+m^11’Each independently an integer of 1 to 9.

As R⁰Examples thereof include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, phenyl group, naphthyl group, anthryl group, pyrenyl group, biphenyl group, and heptenyl group.

As R^4’And R^5’Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, a naphthyl group, an anthracyl group, a pyrenyl group, a biphenyl group, a heptenyl group, a vinyl group, an allyl group, a triacontenyl group, a methoxy.

R mentioned above⁰、R^4’、R^5’Each example of (a) includes isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula (3d-2), R⁰、R^4’、R^5’、m^4’、m^5’、m^10’And m^11’R is as defined in the above formula (3d-1)^1’Is a 1-valent group having 1 to 60 carbon atoms.

As the compound represented by the formula (3), a compound represented by the following formula can be used.

In the above compounds, R¹⁴Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom or a mercapto group, m¹⁴Is an integer of 0 to 5, m^14’Is an integer of 0 to 4, m¹⁴"is an integer of 0 to 3.

As R¹⁴Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, a naphthyl group, an anthracyl group, a pyrenyl group, a biphenyl group, a heptenyl group, a vinyl group, an allyl group, a triacontenyl group, a methoxy.

R mentioned above¹⁴Each example of (a) includes isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

As the compound represented by the formula (3), a compound represented by the following formula can be further used.

In the above chemical formula, R¹⁵The alkyl group is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkynyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom or a mercapto group.

As R¹⁵Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, a naphthyl group, an anthracyl group, a pyrenyl group, a biphenyl group, a heptenyl group, a vinyl group, an allyl group, a triacontenyl group, a methoxy.

R mentioned above¹⁵Each example of (a) includes isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

As the compound represented by the formula (3), a compound represented by the following formula can be further used.

In the above compounds, R¹⁶The compound is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms and optionally having a substituent, a 2-valent aryl group having 6 to 30 carbon atoms and optionally having a substituent, a 2-valent alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, or an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent.

As R¹⁶Examples thereof include methylene, ethylene, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenylA carbanyl group, a triacontenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group, a cyclodecenyl group, a cycloundecenyl group, a cyclododecenyl group, a cyclotriacontenyl group, a 2-valent norbornyl group, a 2-valent adamantyl group, a 2-valent phenyl group, a 2-valent naphthyl group, a 2-valent anthracenyl group, a 2-valent pyrenyl group, a 2-valent biphenyl group, a 2-valent heptenyl group, a 2-valent vinyl group, a 2-valent allyl group, and a 2-valent triacontenyl group.

R mentioned above¹⁶Each example of (a) includes isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

As the compound represented by the formula (3), a compound represented by the following formula can be further used.

In the compounds of the formula R¹⁴Each independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom or a mercapto group, m¹⁴Is an integer of 0 to 5, m^14’Is an integer of 0 to 4.

R¹⁴Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, a naphthyl group, an anthracyl group, a pyrenyl group, a biphenyl group, a heptenyl group, a vinyl group, an allyl group, a triacontenyl group, a.

R mentioned above¹⁴Each example of (a) includes isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

As the compound represented by the formula (3), a compound represented by the following formula can be further used.

As the compound represented by the formula (3), a compound represented by the following formula can be further used.

From the viewpoint of availability of raw materials, the following compounds are more preferable.

[ Compound represented by the formula (4) ]

The compound of the present embodiment is preferably represented by the following formula (4). The compound of the present embodiment has the following structure, and further, has high heat resistance and solvent solubility.

In the formula (4), R^0AAnd the aforementioned R^YThe same meaning, hydrogen atom, alkyl group having 1 to 30 carbon atoms optionally having substituent, or aryl group having 6 to 30 carbon atoms optionally having substituent.

R^1AN is a carbon number of 1 to 60^AA group of valency or a single bond,

R^2Aeach independently represents an alkyl group having 1 to 30 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an alkenyl group having 2 to 30 carbon atoms which may be substituted, an alkynyl group having 2 to 30 carbon atoms which may be substituted, an alkoxy group having 1 to 30 carbon atoms which may be substituted, a halogen atom, a cyano group, a mercapto group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with an acid-dissociable group,

in the formula (4), R^2AAt least one of them is a mercapto group.

n^AIs an integer of 1 to 4, where in formula (4), n^AWhen n is an integer of 2 or more, n^A2]The internal structural formulae are optionally the same or different.

X^AEach independently represents an oxygen atom, a sulfur atom or is unbridged. Here, X^AOxygen atoms or sulfur atoms are preferred because they tend to exhibit high heat resistance, and oxygen atoms are more preferred. From the viewpoint of solubility, X^APreferably unbridgedAnd (6) connecting.

m^2AEach independently an integer of 0 to 6. Wherein, at least 1 m^2AIs an integer of 1 to 6.

q^AEach independently 0 or 1. In addition, q is^AWhen 0, the site represented by the naphthalene structure in the formula (4) represents a benzene structure, q^AWhen the number is 1, it represents a naphthalene structure.

In addition, n is^AThe valency groups are as follows: n is^AWhen 1, it means an alkyl group having 1 to 60 carbon atoms, n^AWhen 2, it means an alkylene group having 1 to 30 carbon atoms, n^AWhen 3, n is an alkanetriyl group having 2 to 60 carbon atoms^AWhen 4, it means an alkanetetrayl group having 3 to 60 carbon atoms. As the aforementioned n^AExamples of the valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, and an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. In addition, the above n^AThe valence group optionally has an aromatic group having 6 to 60 carbon atoms.

In addition, the above n^AThe hydrocarbon group has an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 or 6 to 30 carbon atoms. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

The compound represented by the above formula (4) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used even under high-temperature baking conditions. Further, the composition has quaternary carbon in the molecule, and is suppressed in crystallinity, and thus is suitable for use as a composition for forming a film for lithography, which can be used for producing a film for lithography.

In addition, the compound represented by the above formula (4) has high solubility in a safe solvent and is excellent in heat resistance and etching resistance, and therefore, the resist-forming composition for lithography of the present embodiment provides an excellent resist pattern shape.

Further, since the compound represented by the above formula (4) has a low molecular weight and a low viscosity, even in the case of a substrate having a level difference (particularly, a fine space, a hole pattern, or the like), the compound can be easily uniformly filled in all over the level difference, and the flatness of the film can be easily improved. In addition, since the compound has a high carbon concentration, high etching resistance is also imparted.

The compound represented by the above formula (4) has a high refractive index and is inhibited from being colored by a heat treatment in a wide range from a low temperature to a high temperature, and therefore, is also useful as a composition for forming various optical members. The optical member is useful as a plastic lens (prism lens, lenticular lens, microlens, fresnel lens, viewing angle control lens, contrast improving lens, etc.), a retardation film, an electromagnetic wave shielding film, a prism, an optical fiber, a solder resist for a flexible printed circuit board, a plating resist, an interlayer insulating film for a multilayer printed circuit board, and a photosensitive optical waveguide, in addition to being used in the form of a film or a sheet.

The compound represented by the formula (4) is preferably a compound represented by the following formula (4-1) from the viewpoints of ease of crosslinking and solubility in an organic solvent.

In the formula (4-1), R^0A、R^1A、n^A、q^AAnd X^AThe same meanings as those in the above formula (4) are given.

R^3AEach independently represents a halogen atom, an alkyl group having 1 to 30 carbon atoms and optionally having a substituent, an aryl group having 6 to 30 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent, or an alkoxy group having 1 to 30 carbon atoms and optionally having a substituent.

m^6AEach independently an integer of 0 to 5.

From the viewpoint of the availability of raw materials, a compound represented by the following formula (4a) is preferred.

In the above formula (4a), X^A、R^0A～R^2A、m^2AAnd n^AThe same meanings as those in the above formula (4) are given.

From the viewpoint of solubility in organic solvents, compounds represented by the following formula (4b) are more preferable.

In the above formula (4b), X^A、R^0A、R^1AAnd n^AR is as defined in the above formula (4)^3AAnd m^6AThe same meanings as those in the above formula (4-1).

From the viewpoint of solubility in organic solvents, compounds represented by the following formula (4c) are more preferable.

In the above formula (4c), X^A、R^0A、R^1AAnd n^AR is as defined in the above formula (4)^3AAnd m^6AThe same meanings as those in the above formula (4-1).

The compound represented by the above formula (4) is particularly preferably a compound represented by the following formula (4d-1) or (4d-2) from the viewpoint of further solubility in an organic solvent.

In the above formula (4d-1), R^0A、R^1A、n^A、q^AAnd X^AR is as defined in the above formula (4)^3A’Each independently is an alkyl group having 1 to 30 carbon atoms optionally having a substituent, an aryl group having 6 to 30 carbon atoms optionally having a substituent, an alkenyl group having 2 to 30 carbon atoms optionally having a substituent, an alkynyl group having 1 to E carbon atoms optionally having a substituent30 alkoxy group or halogen atom. m is^3A’Is an integer of 0 to 6, m^4A’Is an integer of 1 to 7, m^3A’+m^4A’Each independently an integer of 1 to 7.

As R^0AExamples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, triacontyl, phenyl, naphthyl, anthryl, pyrenyl, biphenyl, heptenyl.

As R^3A’Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, a naphthyl group, an anthracyl group, a pyrenyl group, a biphenyl group, a heptenyl group, a vinyl group, an allyl group, a triacontenyl group.

R mentioned above^0A、R^3A’Each example of (a) includes isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula (4d-2), R^0A、q^AAnd X^AR is as defined in the above formula (4)^3A’、m^3A’And m^4A’R is as defined for the above formula (4d-1)^1A’Is a 1-valent group having 1 to 60 carbon atoms.

From the viewpoint of raw material availability, the compound represented by the formula (4) preferably has the following structure.

In the above compounds, R^0AWith the frontIn the formula (4), R is the same as R^1A’The same meanings as those in the above formula (4 d-2).

When the compound has a xanthene skeleton or a thioxanthene skeleton, it is preferable from the viewpoint of heat resistance.

The compound represented by formula (4) preferably has the following structure from the viewpoint of etching resistance.

In the above compounds, R^0AR is as defined in the above formula (4)^1A’The same meanings as those in the above formula (4 d-2).

When the compound has a dibenzoxanthene skeleton, it is preferable from the viewpoint of heat resistance.

Examples of the compound represented by formula (4) include compounds having the following structures.

In the above compounds, R¹⁴Is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkynyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom or a mercapto group, m¹⁴Is an integer of 0 to 5, m^14’Is an integer of 0 to 4.

R¹⁵The alkyl group is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkynyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom or a mercapto group.

R¹⁶The compound is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms and optionally having a substituent, a 2-valent aryl group having 6 to 30 carbon atoms and optionally having a substituent, a 2-valent alkenyl group having 2 to 30 carbon atoms and optionally having a substituent, or an alkynyl group having 2 to 30 carbon atoms and optionally having a substituent.

When the compound has a xanthene skeleton, it is preferable from the viewpoint of heat resistance.

[ Process for producing Compound represented by formula (1) ]

The compound represented by the formula (1) in the present embodiment can be synthesized by applying a known method, and the synthesis method is not particularly limited.

For example, a polyphenol compound can be obtained by subjecting a phenol and a corresponding aldehyde or ketone to a polycondensation reaction under normal pressure in the presence of an acid catalyst. Phenols containing a sulfur atom and/or aldehydes or ketones containing a sulfur atom are preferably used. Further, the reaction may be carried out under pressure, if necessary.

Examples of the phenols include phenol, cresol, methoxybenzene, catechol, resorcinol, hydroquinone, trimethylhydroquinone, pyrogallol, phenylphenol, biphenol, methyl biphenol, methoxybiphenol, naphthol, methylnaphthol, methoxynaphthol, naphthalenediol, and naphthalenetriol, but are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among them, phenol, cresol, catechol, resorcinol, hydroquinone, phenylphenol, biphenol, naphthol, naphthalenediol, and naphthalenetriol are preferably used from the viewpoint of stable supply of raw materials, and phenylphenol, biphenol, naphthol, naphthalenediol, and naphthalenetriol are more preferably used from the viewpoint of high heat resistance.

Examples of the aldehyde include, but are not particularly limited to, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phenylpropionaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenyl aldehyde, naphthalene formaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, pyrene formaldehyde, furfural, methylthiobenzaldehyde, thiophenecarbaldehyde, methylthiothiophenecarbaldehyde, formyltetrathiafulvalene, benzothiophenecarboxaldehyde, and the like. These can be used alone in 1 kind, or in combination of 2 or more. Among them, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthalene formaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, pyrene formaldehyde, furfural, methylthiobenzaldehyde, thiophene formaldehyde, methylthiothiophene formaldehyde, formyltetrathiafulvalene, benzothiophene formaldehyde are preferably used, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthalene formaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, pyrene formaldehyde, furfural, methylthiobenzaldehyde, thiophene formaldehyde, methylthiothiophene formaldehyde, formyltetrathiafulvalene, and the like are more preferably used, The benzothiophenecarboxaldehyde is more preferably methylthiobenzaldehyde, thiophenecarboxaldehyde, methylthiothiophenecarboxaldehyde, formyltetrathiafulvalene, or benzothiophenecarboxaldehyde, into which a sulfur atom has been introduced, from the viewpoint of improving the refractive index.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norborneone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetophenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, mercaptobenzoic acid, methylthioacetophenone, acetylthiophene, and acetylbenzothiophene, but are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among them, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetophenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, mercaptobenzoic acid, methylthioacetophenone, acetylthiophene, acetylbenzothiophene are preferably used, and from the viewpoint of improving etching resistance, acetophenone, diacetylbenzene, triacetylbenzene, acetophenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene are more preferably used, Benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, mercaptobenzoic acid, methylthioacetophenone, acetylthiophene, and acetylbenzothiophene, into which a sulfur atom has been introduced, are more preferable from the viewpoint of improving the refractive index.

As the aldehyde or ketone, an aldehyde having an aromatic ring or a ketone having an aromatic ring is preferably used from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be suitably selected from known ones and used, and is not particularly limited. As such an acid catalyst, inorganic acids, organic acids, lewis acids, solid acids, and the like are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; examples of the metal salt include, but are not limited to, Lewis acids such as zinc chloride, aluminum chloride, ferric chloride and boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid and phosphomolybdic acid. Among them, organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is more preferable from the viewpoint of production such as availability and ease of handling. The acid catalyst may be used alone in 1 kind or in combination of 2 or more kinds. The amount of the acid catalyst to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the raw material for reaction.

In the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde or ketone and the phenol is carried out, and may be suitably selected from known ones. Examples of the reaction solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and a mixed solvent thereof. The solvent may be used alone in 1 kind or in combination of 2 or more kinds.

The amount of the reaction solvent to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the raw material. The reaction temperature in the above reaction is not particularly limited, and is usually in the range of 10 to 200 ℃.

The reaction temperature is preferably high for obtaining the polyphenol compound, and specifically, the range of 60 to 200 ℃ is preferred. The reaction method may be appropriately selected from known methods, and is not particularly limited, and the following methods may be mentioned: a method of simultaneously charging phenols, aldehydes or ketones and a catalyst; gradually dripping phenols, aldehydes or ketones in the presence of a catalyst. After the completion of the polycondensation reaction, the obtained compound can be isolated by a conventional method, and is not particularly limited. For example, the compound to be targeted can be separated by a general method such as raising the temperature of the reaction vessel to 130 to 230 ℃ and removing volatile components at about 1 to 50mmHg in order to remove unreacted raw materials, catalysts, and the like present in the system.

Preferable reaction conditions include reaction at 50 to 150 ℃ for about 20 minutes to 100 hours under normal pressure using 1 mol to excess amount of the phenol and 0.001 to 1 mol of the acid catalyst based on 1 mol of the aldehyde or ketone.

After the reaction is completed, the target substance can be isolated by a known method. For example, the target compound represented by the formula (1) can be obtained by concentrating the reaction solution, precipitating the reaction product by adding pure water, cooling to room temperature, separating by filtration, filtering and drying the obtained solid, separating and purifying the by-product by column chromatography, distilling off the solvent, filtering, and drying.

[ Process for producing Compound represented by formula (3) ]

The compound represented by the formula (3) used in the present embodiment can be synthesized by applying a known method, and the synthesis method is not particularly limited. For example, the following methods are used: (i) a method in which a diphenol, a binaphthol or a dianthranol and a corresponding ketone are subjected to a polycondensation reaction in the presence of an acid catalyst to substitute the hydroxyl group of the obtained polyphenol with a mercapto group by the method described in j.am.chem.soc., vol.122, No.28,2000; (ii) a method in which a biphenylol, a binaphthol, or a dianthranol and a corresponding aldehyde are subjected to polycondensation in the presence of an acid catalyst to cause a substitution reaction of the methine moiety of the obtained triarylmethane or xanthene, and the hydroxyl group of the obtained polyphenol is substituted with a mercapto group by the method described in j.am.chem.soc., vol.122, No.28,2000.

Further, as (i) a method of subjecting diphenols, binaphthols or dianthranols and corresponding ketones to polycondensation reaction under an acid catalyst, there is a method comprising: (a) a method of carrying out in an organic solvent, (b) a method of carrying out in a water solvent, (c) a method of carrying out in a solvent-free solvent, and the like.

In the method of (i) (a) polycondensing a biphenol, a binaphthol, or a dianthranol with a corresponding ketone in an organic solvent under an acid catalyst, a biphenol, a binaphthol, or a dianthranol with a corresponding ketone is polycondensed under normal pressure under an acid catalyst to obtain the compound represented by the above formula (3). In addition, an acid-dissociable group may be introduced into the phenolic hydroxyl group of at least one of the compounds by a known method. Further, the reaction may be carried out under pressure, if necessary.

The compound represented by the formula (3) can be obtained by (i) polycondensing a biphenol, a binaphthol, or a dianthranol with a corresponding ketone in an acid catalyst in a water solvent or (c) in the absence of a solvent, by polycondensing a biphenol, a binaphthol, or a dianthranol with a corresponding ketone in an acid catalyst and a mercapto catalyst. In addition, an acid-dissociable group may be introduced into the phenolic hydroxyl group of at least one of the compounds by a known method. The reaction may be carried out under reduced pressure, normal pressure or increased pressure.

Examples of the diphenols include diphenols, methyl diphenols, and methoxy diphenols, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, when biphenol is used, it is more preferable in terms of stable supply of raw materials.

Examples of the binaphthols include binaphthol, methyl binaphthol, and methoxy binaphthol, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, binaphthol is more preferable in terms of increasing the carbon atom concentration and improving the heat resistance.

Examples of the dianthranol include dianthranol, methyl dianthranol, and methoxy dianthranol, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, dianthranol is more preferable in terms of increasing the carbon atom concentration and improving heat resistance.

Examples of the ketones include, but are not particularly limited to, acetone, methyl ethyl ketone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and the like. These can be used alone in 1 kind, or in combination of 2 or more. Among these, when acetophenone, diacetylbenzene, triacetylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are used, it is preferable in terms of providing high heat resistance, and when acetophenone, diacetylbenzene, triacetylbenzene, naphthylketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are used, it is more preferable in terms of providing high etching resistance.

When a ketone having an aromatic ring is used as the ketone, it is preferable to combine high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be suitably selected from known ones and used, and is not particularly limited. As such an acid catalyst, inorganic acids, organic acids, lewis acids, and solid acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid, lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid, and are not particularly limited thereto. Among these, organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as availability and ease of handling. The acid catalyst may be used alone in 1 kind or in combination of 2 or more kinds. The amount of the acid catalyst to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the raw material for reaction.

The mercapto catalyst used in the above reaction can be suitably selected from known ones and used without any particular limitation. As such a catalyst, alkyl mercaptans and mercapto carboxylic acids are widely known, and examples of the alkyl mercaptan include alkyl mercaptans having 1 to 12 carbon atoms, preferably n-octyl mercaptan, n-decyl mercaptan and n-dodecyl mercaptan, and examples of the mercapto carboxylic acid include 2-mercaptopropionic acid and 3-mercaptopropionic acid, but are not particularly limited thereto. Among them, n-octyl mercaptan, n-decyl mercaptan, and n-dodecyl mercaptan are preferable from the viewpoint of production. The mercapto catalyst may be used alone in 1 kind, or in combination of 2 or more kinds. The amount of the mercapto catalyst to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the raw material for reaction.

In the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction of the ketone used with the biphenol, the binaphthol, or the dianthradiol proceeds, and may be appropriately selected from known ones and used. Examples of the solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and a mixed solvent thereof. The solvent may be used alone in 1 kind, or in combination of 2 or more kinds.

The amount of the solvent to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the raw material for reaction. The reaction temperature in the reaction is not particularly limited, and is usually in the range of 10 to 200 ℃.

In order to obtain the compound represented by the formula (3) of the present embodiment, the reaction temperature is preferably high, specifically, preferably in the range of 60 to 200 ℃. The reaction method may be appropriately selected from known methods, and is not particularly limited, and the following methods may be used: adding biphenol, binaphthol or dianthradiol, ketone and catalyst; gradually dripping biphenol and binaphthol or dianthradiol and ketone in the presence of catalyst. After the completion of the polycondensation reaction, the obtained compound can be isolated by a conventional method, and is not particularly limited. For example, the target compound can be obtained by a general method such as raising the temperature of the reaction vessel to 130 to 230 ℃ and removing volatile components at about 1 to 50mmHg in order to remove unreacted raw materials, catalysts, and the like present in the system.

Preferable reaction conditions include a reaction at 50 to 150 ℃ for about 20 minutes to 100 hours under normal pressure using 1.0 mol to an excess of a diphenol, a binaphthol, or a dianthranediol, and 0.001 to 1 mol of an acid catalyst, based on 1 mol of a ketone.

After the reaction is completed, the target substance can be isolated by a known method. For example, the target compound represented by the formula (3) can be obtained by concentrating the reaction solution, precipitating the reaction product by adding pure water, cooling to room temperature, filtering and separating, filtering and drying the obtained solid, separating and purifying the solid from the by-product by column chromatography, distilling off the solvent, filtering, and drying.

As (ii) a method of substituting the methine moiety of triarylmethane or xanthene obtained by polycondensation of a biphenol, a binaphthol or a dianthranol with a corresponding aldehyde in the presence of an acid catalyst, there is a method of subjecting a biphenol, a binaphthol or a dianthranol with a corresponding aldehyde in the presence of an acid catalyst to polycondensation reaction to obtain R of the compound represented by the above formula (3)^YA compound (A) substituted with a hydrogen atom. After forming a compound (B) in which a hydroxyl group of the compound (A) is substituted with a protecting group by a protecting group introducing agent, the compound represented by the formula (3) is allowed to correspond to R^YPart of the hydrogen atoms are reacted with an alkylating agent in the presence of a base catalyst to introduce R corresponding to the compound represented by the formula (3)^YA partial alkyl group. Further, the protecting group substituted with a hydroxyl group in the compound (B) is deprotected to obtain the compound of formula (3). In addition, an acid-dissociable group may be introduced into the phenolic hydroxyl group of at least one of the compounds by a known method. Further, the reaction may be carried out under pressure, if necessary. The alkylating agent may be suitably selected from known ones and used, and is not particularly limited. Examples thereof include alkyl chloride, alkyl bromide, and alkyl iodide.

In the above production method, R is the equivalent of R in the compound represented by the above formula (3) for the compound (B)^YPart of the hydrogen atoms are introduced into the compound represented by the formula (3) corresponding to R^YPartial alkyl processes, except beforeIn addition to the method of reacting with an alkylating agent in the presence of a base catalyst in the above-mentioned production method, the compound (B) may be reacted with a halogenating agent so that R is the equivalent of the compound represented by the above-mentioned formula (3)^YThe above formula (3) can also be obtained by reacting an alkylating agent with a halogen atom substituted for a part of the hydrogen atoms. The alkylating agent may be suitably selected from known ones and used, and is not particularly limited. Examples thereof include Grignard reagents and alkyllithium.

Examples of the diphenols include diphenols, methyl diphenols, and methoxy diphenols, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, when biphenol is used, it is more preferable in terms of stable supply of raw materials.

Examples of the binaphthols include binaphthol, methyl binaphthol, and methoxy binaphthol, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, binaphthol is more preferable in terms of increasing the carbon atom concentration and improving the heat resistance.

Examples of the dianthranol include dianthranol, methyl dianthranol, and methoxy dianthranol, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, dianthranol is more preferable in terms of increasing the carbon atom concentration and improving heat resistance.

Examples of the aldehyde include, but are not particularly limited to, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phenylpropionaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenyl aldehyde, naphthalene formaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, pyrene formaldehyde, and furfural.

A method of introducing an acid-dissociable group into a phenolic hydroxyl group of at least one of the polyphenol compounds is known. For example, an acid-dissociable group may be introduced into a phenolic hydroxyl group of at least one of the compounds as follows. The compound for introducing an acid-dissociable group can be synthesized or easily obtained by a known method, and examples thereof include an active carboxylic acid derivative compound such as an acid chloride, an acid anhydride, and a bicarbonate, an alkyl halide, a vinyl alkyl ether, a dihydropyran, and a halogenated carboxylic acid alkyl ester, and are not particularly limited.

For example, the compound is dissolved or suspended in an aprotic solvent such as acetone, Tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. And then adding vinyl alkyl ether such as ethyl vinyl ether or dihydropyran, and reacting for 6-72 hours at 20-60 ℃ under normal pressure in the presence of an acid catalyst such as pyridinium p-toluenesulfonate. The reaction solution is neutralized with an alkali compound, distilled water is added to precipitate a white solid, and the separated white solid is washed with distilled water and dried to obtain a compound in which the hydrogen atom of the hydroxyl group is replaced with an acid dissociable group.

In addition, for example, the compound having a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, THF, propylene glycol monomethyl ether acetate, or the like. Then, an alkyl halide such as ethyl chloromethyl ether or an alkyl halocarboxylate such as methyl adamantyl bromoacetate is added and reacted at 20 to 110 ℃ for 6 to 72 hours under normal pressure in the presence of an alkali catalyst such as potassium carbonate. The reaction solution is neutralized with an acid such as hydrochloric acid, and after adding distilled water to precipitate a white solid, the separated white solid is washed with distilled water and dried to obtain a compound in which the hydrogen atom of the hydroxyl group is replaced with an acid dissociable group.

The timing of introducing the acid-dissociable group may be not only after the condensation reaction of the binaphthol and the ketone but also at the early stage of the condensation reaction. The resin may be produced after the production of the resin described later.

In the present embodiment, the acid-dissociable group is a characteristic group that is cleaved in the presence of an acid to generate a functional group that changes solubility, such as an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group, and the phenolic hydroxyl group and the carboxyl group are preferable, and the phenolic hydroxyl group is particularly preferable. The acid-dissociable group preferably has a property of causing a cleavage reaction in the presence of an acid in a chain manner, and is thus capable of realizing high-sensitivity/high-resolution patterning.

[ Process for producing Compound represented by formula (4) ]

The compound represented by the formula (4) used in the present embodiment can be synthesized by applying a known method, and the synthesis method is not particularly limited. For example, the following methods are used: (i) a method in which a phenol, a naphthol or an anthraphenol and a corresponding ketone are subjected to a polycondensation reaction in the presence of an acid catalyst to replace the phenolic hydroxyl group of the obtained polyphenol with a mercapto group by the method described in j.am.chem.soc., vol.122, No.28,2000; (ii) a method in which a phenol, a naphthol or an anthraphenol and a corresponding aldehyde are subjected to polycondensation in the presence of an acid catalyst to substitute the methine moiety of the triarylmethane or the xanthene obtained, and the phenolic hydroxyl group of the polyphenol obtained is substituted with a mercapto group by the method described in j.am.chem.soc., vol.122, No.28,2000.

Further, as (i) a method of subjecting a phenol, a naphthol or an anthraphenol, and a corresponding ketone to polycondensation reaction in the presence of an acid catalyst, there is a method comprising: (a) a method of carrying out in an organic solvent, (b) a method of carrying out in a water solvent, (c) a method of carrying out in a solvent-free solvent, and the like.

The compound represented by the above formula (4) can be obtained by (i) (a) a method of polycondensing a phenol, a naphthol or an anthraphenol and a corresponding ketone in an organic solvent under an acid catalyst, and (ii) a method of polycondensing a phenol, a naphthol or an anthraphenol and a corresponding ketone under an acid catalyst under normal pressure. Further, the reaction may be carried out under pressure, if necessary. Further, an acid-dissociable group may be introduced into the phenolic hydroxyl group of at least one of the compounds by a known method.

The compound represented by the formula (4) can be obtained by (i) a polycondensation reaction of a phenol, a naphthol or an anthraphenol with a corresponding ketone in an acid catalyst in a water solvent or (c) a polycondensation reaction of a phenol, a naphthol or an anthraphenol with a corresponding ketone in an acid catalyst and a mercapto catalyst in the absence of a solvent. In addition, an acid-dissociable group may be introduced into the phenolic hydroxyl group of at least one of the compounds by a known method. The reaction may be carried out under reduced pressure, normal pressure, or increased pressure.

The naphthol is not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, and naphthalenediol, and when naphthalenediol is used, a xanthene structure can be easily formed, which is more preferable.

The phenol is not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, trimethylhydroquinone and the like.

Examples of the anthraphenols include, but are not particularly limited to, anthraphenol, methylanthracenol, and methoxyanthraphenol. These can be used alone in 1 kind, or in combination of 2 or more. Among these, the use of anthraphenols is more preferable in terms of increasing the carbon atom concentration and improving the heat resistance.

Examples of the ketones include, but are not particularly limited to, acetone, methyl ethyl ketone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and the like. These can be used alone in 1 kind, or in combination of 2 or more. Among these, when acetophenone, diacetylbenzene, triacetylbenzene, acetophenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are used, it is preferable in terms of providing high heat resistance, and when acetophenone, diacetylbenzene, triacetylbenzene, acetophenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoylnaphthalene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are used, it is more preferable in terms of providing high etching resistance.

When a ketone having an aromatic ring is used as the ketone, it is preferable to have both high heat resistance and high etching resistance.

The acid catalyst is not particularly limited, and may be suitably selected from known inorganic acids, organic acids, lewis acids, and solid acids. Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid. From the viewpoint of production, such as availability and ease of handling, hydrochloric acid or sulfuric acid is preferably used. Further, as the acid catalyst, 1 or 2 or more species may be used. The amount of the acid catalyst to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the raw material for reaction.

The mercapto catalyst used in the above reaction can be suitably selected from known ones and used without any particular limitation. As such a catalyst, alkyl mercaptans and mercapto carboxylic acids are widely known, and examples of the alkyl mercaptan include alkyl mercaptans having 1 to 12 carbon atoms, preferably n-octyl mercaptan, n-decyl mercaptan and n-dodecyl mercaptan, and examples of the mercapto carboxylic acid include 2-mercaptopropionic acid and 3-mercaptopropionic acid, but are not particularly limited thereto. Among them, n-octyl mercaptan, n-decyl mercaptan, and n-dodecyl mercaptan are preferable from the viewpoint of production. The mercapto catalyst may be used alone in 1 kind, or in combination of 2 or more kinds. The amount of the mercapto catalyst to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the raw material for reaction.

In the production of the compound represented by the formula (4), a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction of the ketone with the naphthol or the like proceeds, and for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used. The amount of the solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw material.

In the production of the polyphenol compound, the reaction temperature is not particularly limited, and may be suitably selected depending on the reactivity of the reaction raw material, and is preferably in the range of 10 to 200 ℃. In order to synthesize the compound represented by the formula (4) of the present embodiment with good selectivity, the effect is high at low temperature, and the range of 10 to 60 ℃ is more preferable.

The method for producing the compound represented by the formula (4) is not particularly limited, and examples thereof include the following methods: a method of simultaneously adding naphthol, etc., ketone and catalyst; gradually dripping naphthol and ketone in the presence of catalyst. After the polycondensation reaction is completed, the temperature of the reaction vessel may be raised to 130 to 230 ℃ and the volatile matter may be removed at about 1 to 50mmHg in order to remove unreacted raw materials, catalysts, and the like present in the system.

The amount of the raw materials for producing the compound represented by the formula (4) is not particularly limited, and for example, the reaction is carried out at 20 to 60 ℃ for about 20 minutes to 100 hours under normal pressure using 2 to an excess amount of naphthol or the like and 0.001 to 1 mole of an acid catalyst based on 1 mole of ketone.

In the production of the compound represented by the formula (4), after the completion of the reaction, the target compound is isolated by a known method. The method for separating the target compound is not particularly limited, and examples thereof include the following methods: concentrating the reaction solution, adding pure water to separate out a reaction product, cooling to room temperature, filtering and separating, filtering and drying the obtained solid, separating and purifying the solid and a byproduct through column chromatography, distilling the solvent to remove, filtering and drying to obtain the target compound.

As (ii) a method of substituting the methine moiety of triarylmethane or xanthene obtained by polycondensation of a phenol, a naphthol or an anthraphenol with a corresponding aldehyde in the presence of an acid catalyst, a method of subjecting a phenol, a naphthol or an anthraphenol with a corresponding aldehyde to polycondensation in the presence of an acid catalyst to obtain a compound represented by the above formula (4) wherein R is^YA compound (A') substituted with a hydrogen atom. After forming a compound (B ') in which a hydroxyl group of the compound (A') is substituted with a protecting group by a protecting group introducing agent, the compound represented by the formula (4) is reacted with R^YPart of the hydrogen atoms are reacted with an alkylating agent in the presence of a base catalyst to introduce R corresponding to the compound represented by the formula (4)^YA partial alkyl group. Further, the protecting group substituted with a hydroxyl group in the compound (B') is deprotected to obtain the compound of the formula (4). In addition, an acid-dissociable group may be introduced into the phenolic hydroxyl group of at least one of the compounds by a known method. Further, the reaction may be carried out under pressure, if necessary. The alkylating agent may be suitably selected from known ones and used, and is not particularly limited. Examples thereof include alkyl chloride, alkyl bromide, and alkyl iodide.

In the above production process, R is the equivalent of R in the compound represented by the above formula (4) for the compound (B')^YPart of the hydrogen atoms are introduced into the compound represented by the formula (4) corresponding to R^YA partial alkyl group production method, wherein the compound (B') is reacted with a halogenating agent to react the compound represented by the formula (4) with R in addition to the method of reacting the compound with an alkylating agent in the presence of a base catalyst in the above production method^YThe above formula (4) can also be obtained by reacting an alkylating agent with a halogen atom substituted for a part of the hydrogen atoms. The alkylating agent may be suitably selected from known ones and used, and is not particularly limited. Examples thereof include Grignard reagents and alkyllithium.

Examples of the phenol include, but are not particularly limited to, phenol, methylphenol, and methoxyphenol. These can be used alone in 1 kind, or in combination of 2 or more. Among these, the use of phenol is more preferable in terms of stable supply of the raw material.

Examples of the naphthol include naphthol, methylnaphthol, and methoxynaphthol, and are not particularly limited thereto. These can be used alone in 1 kind, or in combination of 2 or more. Among these, naphthol is more preferable in terms of increasing the carbon atom concentration and improving the heat resistance.

Examples of the anthraphenols include, but are not particularly limited to, anthraphenol, methylanthracenol, and methoxyanthraphenol. These can be used alone in 1 kind, or in combination of 2 or more. Among these, the use of anthraphenols is more preferable in terms of increasing the carbon atom concentration and improving the heat resistance.

Examples of the aldehyde include, but are not particularly limited to, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phenylpropionaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenyl aldehyde, naphthalene formaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, pyrene formaldehyde, and furfural.

A method of introducing an acid-dissociable group into a phenolic hydroxyl group of at least one of the polyphenol compounds is known. For example, an acid-dissociable group may be introduced into a phenolic hydroxyl group of at least one of the compounds as follows. The compound for introducing an acid-dissociable group can be synthesized or easily obtained by a known method, and examples thereof include an active carboxylic acid derivative compound such as an acid chloride, an acid anhydride, and a bicarbonate, an alkyl halide, a vinyl alkyl ether, a dihydropyran, and a halogenated carboxylic acid alkyl ester, and are not particularly limited.

For example, the compound is dissolved or suspended in an aprotic solvent such as acetone, Tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. And then adding vinyl alkyl ether such as ethyl vinyl ether or dihydropyran, and reacting for 6-72 hours at 20-60 ℃ under normal pressure in the presence of an acid catalyst such as pyridinium p-toluenesulfonate. The reaction solution is neutralized with an alkali compound, distilled water is added to precipitate a white solid, and then the separated white solid is washed with distilled water and dried, whereby a compound in which the hydrogen atom of the hydroxyl group is substituted with an acid dissociable group can be obtained.

In addition, for example, the compound having a hydroxyl group is dissolved or suspended in an aprotic solvent such as acetone, THF, propylene glycol monomethyl ether acetate, or the like. Then, an alkyl halide such as ethyl chloromethyl ether or the like or an alkyl halocarboxylate such as methyl adamantyl bromoacetate or the like is added and reacted at 20 to 110 ℃ for 6 to 72 hours under normal pressure in the presence of an alkali catalyst such as potassium carbonate or the like. The reaction solution is neutralized with an acid such as hydrochloric acid, and after adding distilled water to precipitate a white solid, the separated white solid is washed with distilled water and dried, whereby a compound in which the hydrogen atom of the hydroxyl group is replaced with an acid dissociable group can be obtained.

The timing of introducing the acid-dissociable group may be not only after the condensation reaction of the naphthol and the ketone but also at the early stage of the condensation reaction. The resin may be produced after the production of the resin described later.

In the present embodiment, the acid-dissociable group is a characteristic group that is cleaved in the presence of an acid to generate a functional group that changes solubility, such as an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group, and the phenolic hydroxyl group and the carboxyl group are preferable, and the phenolic hydroxyl group is particularly preferable. The acid-dissociable group preferably has a property of causing a cleavage reaction in the presence of an acid in a chain manner to thereby enable high-sensitivity/high-resolution patterning.

[ resin comprising Compound represented by formula (1) as a structural Unit ]

The compound represented by the formula (1) can be used as it is in a composition for forming a film for lithography or an optical member (hereinafter, also simply referred to as "composition"). In addition, a resin containing the compound represented by the above formula (1) as a structural unit may also be used. The resin is obtained, for example, by reacting a compound represented by the formula (1) with a compound having crosslinking reactivity.

Examples of the resin containing the compound represented by the formula (1) as a structural unit include resins having a structure represented by the following formula (5). That is, the composition in the present embodiment may contain a resin having a structure represented by the following formula (5).

(in the formula (5),

R^Y、R^Z、A、R^Tx and N are as defined in formula (1),

m is each independently an integer of 0 to 8,

l is an alkylene group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, an arylene group having 6 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, an alkyleneoxy group having 1 to 30 carbon atoms and optionally having a substituent and/or a hetero atom, or a single bond, the alkylene group, the arylene group, and the alkyleneoxy group optionally containing an ether bond, a thioether bond, a ketone bond, or an ester bond,

here, it is selected from A, R^Y、R^Z、R^TAt least 1 of X and L comprises a sulfur atom,

R^Tat least one of them contains a mercapto group, a hydroxyl group, or a group in which the hydrogen atom of the mercapto group or the hydroxyl group is substituted with an acid-crosslinkable group or an acid-dissociable group. )

Examples of the substituent for the alkylene group, the arylene group and the alkyleneoxy group include those mentioned above as substituents for the alkyl group, the aryl group and the alkoxy group.

[ resin comprising a Compound represented by the formula (3) as a structural Unit ]

The compound represented by the formula (3) can be used as it is in a film-forming composition for lithography. In addition, a resin containing the compound represented by the above formula (3) as a structural unit may also be used. For example, it is also possible to use: a resin obtained by reacting a compound represented by the above formula (3) with a compound having crosslinking reactivity.

Examples of the resin containing the compound represented by the formula (3) as a structural unit include resins having a structure represented by the following formula (6). That is, the composition for forming a film for lithography according to the present embodiment may contain a resin having a structure represented by the following formula (6).

In the formula (6), L is a linear or branched alkylene group having 1 to 30 carbon atoms and optionally having a substituent, or a single bond. R⁰、R¹、R²～R⁵、m²～m⁵、p²～p⁵And n is the same as in the aforementioned formula (3), wherein m²～m⁵Not simultaneously becoming 0, R²～R⁵At least one of them is a mercapto group.

[ resin comprising a Compound represented by the formula (4) as a structural Unit ]

The compound represented by the formula (4) can be used as it is in a film-forming composition for lithography. In addition, a resin containing the compound represented by the above formula (4) as a structural unit may also be used. For example, it is also possible to use: a resin obtained by reacting a compound represented by the above formula (4) with a compound having crosslinking reactivity.

Examples of the resin containing the compound represented by the formula (4) as a structural unit include resins having a structure represented by the following formula (7). That is, the composition for forming a film for lithography according to the present embodiment may contain a resin having a structure represented by the following formula (7).

In the formula (7), L is a linear or branched alkylene group having 1 to 30 carbon atoms and optionally having a substituent, or a single bond.

R^0A、R^1A、R^2A、m^2A、n^A、q^AAnd X^AThe same as in the above formula (4),

n^Awhen n is an integer of 2 or more, n^A2]The internal structural formulae are optionally the same or different.

Wherein R is^2AAt least one of them is a mercapto group.

[ method for producing a resin containing the compound of the present embodiment as a structural unit ]

The resin in the present embodiment is obtained by reacting the compound of the present embodiment with a compound having crosslinking reactivity. As the compound having crosslinking reactivity, any known compound can be used without particular limitation as long as the compound of the present embodiment can be oligomerized or polymerized. Specific examples thereof include, but are not particularly limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin of the present embodiment include: a resin that is novolak-converted by a condensation reaction of the compound of the present embodiment of the formula described above with an aldehyde and/or ketone, which is a compound having crosslinking reactivity, or the like.

Examples of the aldehyde used in the novolak formation of the compound of the present embodiment include, but are not particularly limited to, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phenylpropionaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenyl aldehyde, naphthalene formaldehyde, anthracene formaldehyde, phenanthrene formaldehyde, pyrene formaldehyde, furfural, methylthiobenzaldehyde, thiophene formaldehyde, methylthiothiophene formaldehyde, formyltetrathiafulvalene, benzothiophene formaldehyde, and the like. From the viewpoint of improving the refractive index, methylthiobenzaldehyde, thiophenecarboxaldehyde, methylthiothiophenecarboxaldehyde, formyltetrathiafulvalene, and benzothiophenecarboxaldehyde into which a sulfur atom has been introduced are preferable. As the ketone, the aforementioned ketones can be mentioned. From the viewpoint of improving the refractive index, mercaptobenzoic acid, methylthioacetophenone, acetylthiophene, and acetylbenzothiophene into which a sulfur atom is introduced are more preferable. Among them, formaldehyde is preferred from the viewpoint of productivity.

These aldehydes and/or ketones may be used alone in 1 kind, or in combination with 2 or more kinds. The amount of the aldehyde and/or ketone to be used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, based on 1 mole of the compound of the present embodiment.

In the condensation reaction of the compound of the present embodiment with an aldehyde and/or a ketone, an acid catalyst may be used. The acid catalyst used herein can be suitably selected from known ones and used, and is not particularly limited. As such an acid catalyst, inorganic acids, organic acids, lewis acids, solid acids, and the like are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; examples of the metal salt include, but are not limited to, Lewis acids such as zinc chloride, aluminum chloride, ferric chloride and boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid and phosphomolybdic acid. Among them, from the viewpoint of production, organic acids and solid acids are preferable, and from the viewpoint of production such as availability and ease of handling, hydrochloric acid or sulfuric acid is preferable. The acid catalyst may be used alone in 1 kind or in combination of 2 or more kinds.

The amount of the acid catalyst to be used may be suitably set depending on the kind of the raw material and the catalyst to be used, the reaction conditions, and the like, and is not particularly limited, but is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the raw material for reaction. In the case of copolymerization with a compound having a non-conjugated double bond such as indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, biphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorbornane-2-ene, α -pinene, β -pinene, limonene, etc., the aldehyde is not necessarily required.

In the condensation reaction of the compound of the present embodiment with an aldehyde and/or a ketone, a reaction solvent may also be used. The reaction solvent in the polycondensation is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and a mixed solvent thereof. The solvent may be used alone in 1 kind or in combination of 2 or more kinds.

The amount of the solvent to be used is not particularly limited, and is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw material, although it may be suitably set depending on the kinds of the raw material and the catalyst to be used, the reaction conditions, and the like. The reaction temperature is not particularly limited, and is usually within a range of 10 to 200 ℃. The reaction method may be appropriately selected from known methods, and is not particularly limited, and the following methods may be mentioned: a method of simultaneously charging the compound of the present embodiment, an aldehyde and/or a ketone, and a catalyst; a method of gradually adding dropwise the compound, aldehyde and/or ketone of the present embodiment in the presence of a catalyst.

After the completion of the polycondensation reaction, the obtained resin can be isolated by a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, and the like present in the system, a novolak-formed resin as a target can be isolated by a general method such as raising the temperature of the reaction vessel to 130 to 230 ℃ and removing volatile components at about 1 to 50 mmHg.

Here, the resin of the present embodiment may be a homopolymer of the compound of the present embodiment, or may be a copolymer with another phenol. Examples of the phenols copolymerizable with this group include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, propylphenol, pyrogallol, thymol, and biphenol, but are not particularly limited thereto.

The resin of the present embodiment may be copolymerized with a polymerizable monomer other than the above-mentioned other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, naphthalene triol, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, biphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinylnorbornene, pinene, limonene and the like, and are not particularly limited thereto. The resin of the present embodiment may be a 2-or more-membered (for example, 2-to 4-membered) copolymer of the compound of the present embodiment and the phenol, may be a 2-or more-membered (for example, 2-to 4-membered) copolymer of the compound of the present embodiment and the comonomer, or may be a 3-or more-membered (for example, 3-to 4-membered) copolymer of the compound of the present embodiment and the phenol and the comonomer.

The molecular weight of the resin of the present embodiment is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30000, more preferably 750 to 20000. In addition, from the viewpoint of improving crosslinking efficiency and suppressing volatile components during baking, the degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the resin of the present embodiment is preferably within a range of 1 to 7. The Mw and Mn can be determined by the methods described in the examples described below.

The resin of the present embodiment is preferably high in solubility in a solvent from the viewpoint of, for example, easier application of a wet process. More specifically, when 1-methoxy-2-Propanol (PGME) and/or Propylene Glycol Monomethyl Ether Acetate (PGMEA) is used as a solvent for the resin, the solubility in the solvent is preferably 10 mass% or more. Here, the solubility for PGME and/or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) × 100 (mass%)". For example, when the resin 10g is dissolved in PGMEA90g, the solubility of the resin in PGMEA becomes "10 mass% or more", and when not dissolved, it becomes "less than 10 mass%".

The resin represented by the above formula (5) is preferably a compound represented by the following formula (5-1) from the viewpoint of solubility in an organic solvent.

In the formula (5-1),

R^Y、R^Za, X and N are as defined in formula (1),

R^3Aand R^4AIs defined in the formula (1-1),

l is defined in the formula (5),

here, theSelected from A, R^Y、R^Z、R^3A、R^4AAt least 1 of X and L comprises a sulfur atom,

m^6Aeach independently an integer of 0 to 5,

m^7Aeach independently an integer of 0 to 5.

[ method of purifying Compound and/or resin ]

The method for purifying a compound and/or a resin according to the present embodiment includes the steps of: a step of dissolving the compound or the resin of the present embodiment in a solvent to obtain a solution (S); and a step (first extraction step) of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound and/or the resin, wherein the solvent used in the step of obtaining the solution (S) contains a water-immiscible organic solvent.

In the first extraction step, the resin is preferably a resin obtained by a reaction between the compound of the present embodiment and a compound having a crosslinking reactivity. According to the purification method of the present embodiment, the content of various metals that may be contained as impurities in the above-described compound or resin having a specific structure can be reduced.

More specifically, in the purification method of the present embodiment, the extraction treatment may be performed by dissolving the compound and/or the resin in an organic solvent that is not miscible with water to obtain a solution (S), and further contacting the solution (S) with an acidic aqueous solution. Thus, the metal component contained in the solution (S) is transferred to the aqueous phase, and then the organic phase is separated from the aqueous phase, thereby obtaining a compound and/or a resin having a reduced metal content.

The compound and/or resin used in the purification method of the present embodiment may be used alone, or 2 or more kinds may be mixed. The compound and the resin may contain various surfactants, various acid crosslinking agents, various acid generators, various stabilizers, and the like.

The solvent that is not miscible with water at all and used in the purification method of the present embodiment is not particularly limited, and is preferably an organic solvent that can be safely used in a semiconductor production process, specifically, an organic solvent having a solubility in water at room temperature of less than 30%, more preferably less than 20%, and particularly preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times by mass based on the total amount of the compound and the resin used.

Specific examples of the solvent which is not miscible with water include those described in International publication WO 2015/080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, and methyl isobutyl ketone and ethyl acetate are still more preferable. Since the saturated solubility of the compound and the resin containing the compound as a constituent is high and the boiling point is low for methyl isobutyl ketone, ethyl acetate, and the like, the burden on the step of removing the solvent by distillation or drying in the industry can be reduced. These solvents may be used alone, or 2 or more of them may be used in combination.

The acidic aqueous solution used in the purification method of the present embodiment can be appropriately selected from aqueous solutions obtained by dissolving a generally known organic compound or inorganic compound in water. Examples thereof include those described in International publication WO 2015/080240. These acidic aqueous solutions may be used alone or in combination of 2 or more. Among these acidic aqueous solutions, 1 or more kinds of inorganic acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or 1 or more kinds of organic acid aqueous solutions selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid are preferable, aqueous solutions of carboxylic acids such as sulfuric acid, nitric acid, and acetic acid, oxalic acid, tartaric acid, and citric acid are more preferable, aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid are further preferable, and aqueous solutions of oxalic acid are still more preferable. It is considered that polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate to metal ions to produce a chelating effect, and thus metals tend to be removed more efficiently. The water used here is preferably water having a small metal content, for example, ion-exchanged water, for the purpose of the purification method of the present embodiment.

The pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, and is preferably adjusted in consideration of the influence on the above-mentioned compound and resin. The pH of the acidic aqueous solution is usually about 0 to 5, preferably about 0 to 3.

The amount of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, and is preferably adjusted from the viewpoint of reducing the number of times of extraction for removing metals and from the viewpoint of ensuring the operability in consideration of the entire amount of liquid. From the above viewpoint, the amount of the acidic aqueous solution to be used is preferably 10 to 200 mass%, more preferably 20 to 100 mass%, based on 100 mass% of the solution (S).

In the purification method of the present embodiment, the acidic aqueous solution is brought into contact with the solution (S), whereby the metal component can be extracted from the compound or the resin in the solution (S).

In the purification method of the present embodiment, the solution (S) preferably further contains an organic solvent which is optionally miscible with water. When the solution (S) contains an organic solvent which is freely miscible with water, the amount of the compound and/or the resin charged can be increased, the liquid-separating property can be improved, and the purification can be performed with high pot efficiency. The method of adding the organic solvent which is optionally miscible with water is not particularly limited. For example, the organic solvent may be added to the solution containing the organic solvent, the water or the acidic aqueous solution, or the solution containing the organic solvent may be added after contacting the solution with the water or the acidic aqueous solution. Among these, a method of adding the organic solvent to a solution containing an organic solvent in advance is preferable from the viewpoint of workability in operation and easiness in controlling the amount of charged material.

The organic solvent that is optionally miscible with water used in the purification method of the present embodiment is not particularly limited, and is preferably an organic solvent that can be safely used in a semiconductor production process. The amount of the organic solvent which is optionally miscible with water is not particularly limited as long as the solution phase and the aqueous phase are separated from each other, and is preferably 0.1 to 100 times by mass, more preferably 0.1 to 50 times by mass, and still more preferably 0.1 to 20 times by mass, based on the total amount of the compound and the resin used.

Specific examples of the organic solvent which is optionally miscible with water and used in the purification method of the present embodiment include those described in international publication No. WO 2015/080240. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents may be used alone, or 2 or more of them may be used in combination.

The temperature for the extraction is usually 20 to 90 ℃, preferably 30 to 80 ℃. The extraction operation is performed by, for example, sufficiently mixing the components by stirring and then leaving the mixture to stand. Thereby, the metal component contained in the solution (S) migrates into the aqueous phase. In addition, the acidity of the solution is reduced by this operation, and deterioration of the compound and/or the resin can be suppressed.

The mixed solution is allowed to stand to separate into a solution phase containing the compound and/or the resin and the organic solvent and an aqueous phase, and the solution phase is recovered by decantation or the like. The time for the standing is not particularly limited, and is preferably adjusted from the viewpoint of better separation of the aqueous phase from the solution phase containing the organic solvent. The time for standing is usually 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. The extraction treatment may be performed only 1 time, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.

The purification method of the present embodiment preferably further includes, after the first extraction step: and a step (second extraction step) of further extracting impurities in the compound or the resin by bringing a solution phase containing the compound or the resin into contact with water. Specifically, for example, after the first extraction step is performed using an acidic aqueous solution, the recovered solution phase containing the compound and/or resin and the organic solvent is preferably subjected to extraction treatment with water. The extraction treatment with water is not particularly limited, and can be performed, for example, by sufficiently mixing the solution phase and water with stirring or the like, and then leaving the resulting mixed solution to stand. Since the mixed solution after standing is separated into a solution phase containing a compound and/or a resin and a solvent and an aqueous phase, the solution phase can be recovered by decantation or the like.

The water used here is preferably water containing a small amount of metal, for example, ion-exchanged water, for the purpose of the present embodiment. The extraction treatment can be carried out only 1 time, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times. Conditions such as the ratio of both used in the extraction treatment, temperature, and time are not particularly limited, and the same may be applied to the contact treatment with the acidic aqueous solution as in the case of the previous contact treatment.

The water mixed in the solution containing the compound and/or the resin and the solvent thus obtained can be easily removed by performing an operation such as distillation under reduced pressure. If necessary, a solvent may be added to the solution to adjust the concentration of the compound and/or the resin to an arbitrary concentration.

The method for separating the compound and/or the resin from the obtained solution containing the compound and/or the resin and the solvent is not particularly limited, and the separation can be performed by a known method such as removal under reduced pressure, separation by reprecipitation, or a combination thereof. If necessary, known treatments such as a concentration operation, a filtration operation, a centrifugation operation, and a drying operation may be performed.

[ film-Forming composition for lithography ]

The composition for forming a film for lithography according to the present embodiment contains the compound and/or the resin according to the present embodiment.

[ composition for Forming a film for lithography for use in a chemically amplified resist ]

The composition for forming a film for lithography for use as a chemical amplification resist (hereinafter also referred to as "resist composition") according to the present embodiment contains the compound and/or the resin according to the present embodiment as a resist base material.

The resist composition in this embodiment preferably contains a solvent. The solvent is not particularly limited, and examples thereof include: ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as Propylene Glycol Monomethyl Ether (PGME) and propylene glycol monoethyl ether; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-pentyl lactate; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, Cyclopentanone (CPN), and Cyclohexanone (CHN); amides such as N, N-dimethylformamide, N-methylacetamide, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ -lactone. These solvents may be used alone, or 2 or more of them may be used in combination.

The solvent used in the present embodiment is preferably a safe solvent, more preferably at least 1 selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and still more preferably at least one selected from PGMEA, PGME, and CHN.

In the present embodiment, the amounts of the solid component and the solvent are not particularly limited, and are preferably 1 to 80% by mass of the solid component and 20 to 99% by mass of the solvent, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, further preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component and 90 to 98% by mass of the solvent, based on 100% by mass of the total mass of the solid component and the solvent.

The resist composition of the present embodiment may contain at least one selected from the group consisting of an acid generator (C), an acid crosslinking agent (G), an acid diffusion controller (E), and another component (F) as another solid component. In the present specification, the term "solid component" refers to a component other than a solvent.

Here, as the acid generator (C), the acid crosslinking agent (G), the acid diffusion controller (E), and the other component (F), known ones can be used, and those described in, for example, international publication No. 2013/024778 are preferable.

The acid crosslinking agent (G) preferably further contains a compound that reacts with a mercapto group, and the compound that reacts with a mercapto group is not particularly limited, and examples thereof include an epoxy group-containing compound, an episulfide group-containing compound, and an isocyanate group-containing compound. These compounds may be used alone or in combination of 2 or more.

The epoxy group-containing compound is not limited, and it can be used: bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins and alicyclic epoxy resins, phenol novolac type epoxy resins, heterocycle-containing epoxy resins, hydrogenated bisphenol a type epoxy resins, hydrogenated bisphenol F type epoxy resins, aliphatic epoxy resins, spiro ring-containing epoxy resins, and the like.

The episulfide group-containing compound is a compound obtained by substituting an oxygen atom of an epoxy compound with a sulfur atom, and can be obtained by, for example, reacting the epoxy compound described above with thiocyanate, thiourea, or the like as a vulcanizing agent.

As the isocyanate group-containing compound, compounds generally used for polyurethanes, polyisocyanurates, and the like can be used. Such polyisocyanates are not limited, and include, for example: aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, modified products thereof, isocyanate-terminated prepolymers, and the like.

[ compounding ratio of respective ingredients ]

The content of the compound and/or resin used as the resist base material in the resist composition of the present embodiment is not particularly limited, but is preferably 1 to 100% by mass of the total mass of the solid components (including the total of the solid components of the optionally used components such as the resist base material, the acid generator (C), the acid crosslinking agent (G), the acid diffusion controller (E), and the other component (F), the same applies hereinafter), more preferably 50 to 99.4% by mass, still more preferably 55 to 90% by mass, still more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. When the content of the compound and/or the resin used as the resist base material is within the above range, the resolution tends to be further improved, and the Line Edge Roughness (LER) tends to be further reduced.

When both the compound and the resin are contained as the resist base material, the content is the total amount of the two components.

[ other component (F) ]

In the resist composition of the present embodiment, as components other than the resist base material, the acid generator (C), the acid crosslinking agent (G), and the acid diffusion controlling agent (E), 1 or 2 or more kinds of various additives such as a dissolution accelerator, a dissolution controlling agent, a sensitizer, a surfactant, an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof, a thermal and/or photo-curing catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a photo-curing resin, a dye, a pigment, a thickener, a lubricant, a defoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant, a nonionic surfactant, and the like may be added as necessary within a range not to impair the object of the present invention. In the present specification, the other component (F) may be referred to as an arbitrary component (F).

In the resist composition of the present embodiment, the resist base material (hereinafter, also referred to as "component (a)"), the acid generator (C), the acid crosslinking agent (G), the acid diffusion controlling agent (E), and the content of the optional component (F) (component (a)/acid generator (C)/acid crosslinking agent (G)/acid diffusion controlling agent (E)/optional component (F)) are in mass% based on solid matter,

Preferably 1 to 100/0 to 49/0 to 49/0 to 49/0 to 99,

More preferably 50 to 99.4/0.001 to 49/0.5 to 49/0.001 to 49/0 to 49,

Further preferably 55 to 90/1 to 40/0.5 to 40/0.01 to 10/0 to 5,

Further preferably 60 to 80/3 to 30/1 to 30/0.01 to 5/0 to 1,

Particularly preferably 60 to 70/10 to 25/2 to 20/0.01 to 3/0.

The compounding ratio of each component may be selected from ranges such that the total thereof becomes 100 mass%. When the blending ratio of each component is in the above range, the properties such as sensitivity, resolution, and developability tend to be excellent.

The resist composition of the present embodiment is generally prepared as follows: when used, the components are dissolved in a solvent to form a homogeneous solution, and then filtered, if necessary, with a filter having a pore size of about 0.2 μm or so, for example.

The resist composition of the present embodiment may contain other resins than the resin of the present embodiment within a range not to impair the object of the present invention. The other resin is not particularly limited, and examples thereof include: novolac resins, polyvinyl phenols, polyacrylic acids, epoxy resins, polyvinyl alcohols, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, vinyl phenol, or maleimide compounds as monomer units, or derivatives thereof, and the like. The content of the other resin is not particularly limited, and may be appropriately adjusted depending on the kind of the component (a) to be used, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 0 part by mass, relative to 100 parts by mass of the component (a).

[ Properties of resist composition, etc. ]

Using the resist composition of this embodiment, an amorphous film can be formed by spin coating. The resist composition of the present embodiment can be applied to a general semiconductor manufacturing process. Any one of the positive resist pattern and the negative resist pattern may be separately prepared according to the kind of the compound and/or the resin and/or the kind of the developer used in the present embodiment.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin coating the resist composition of the present embodiment in a developer at 23 ℃ is preferably highThe following, more preferablyFurther preferred isThe dissolution rate isIn the following case, the resist tends to be insoluble in a developer and to be easily formed. In addition, the dissolution rate isIn the above case, the resolution may be improved. In addition, this is presumed to be because: the change in solubility of the compound and/or the resin of the present embodiment before and after exposure increases the contrast at the interface between the exposed portion dissolved in the developer and the unexposed portion insoluble in the developer. In addition, the effect of reducing LER and reducing defects was also observed.

In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment in a developer at 23 ℃ is preferably set

The above. A dissolution rate ofIn the above case, the compound is easily dissolved in a developer and is suitable for a resist. In addition, the dissolution rate is

In the above case, the resolution may be improved. Push awayThis was measured because: the microscopic surface portion of the compound and/or resin of the present embodiment dissolves, and lowers LER. In addition, a defect reduction effect was also observed.

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ℃ for a predetermined time and measuring the film thickness before and after the immersion by a known method such as visual observation, ellipsometry, or QCM.

In the case of a positive resist pattern, the dissolution rate of the exposed portion of the amorphous film formed by spin coating the resist composition of the present embodiment by radiation such as KrF excimer laser, ultra-violet ray, electron beam, or X-ray in a developing solution at 23 ℃The above. A dissolution rate of

In the above case, the compound is easily soluble in a developer and is suitable for a resist. In addition, the dissolution rate is

In the above case, the resolution may be improved. This is presumably because the microscopic surface portion of the compound and/or resin of the present embodiment dissolves, and the LER is reduced. But also the effect of reducing defects.

In the case of a negative resist pattern, the dissolution rate of the exposed portion of the amorphous film formed by spin-coating the resist composition of the present embodiment by radiation such as KrF excimer laser, ultra-violet ray, electron beam, or X-ray in a developer at 23 ℃

The following, more preferably

Further, the method can be used for preparing a novel materialPreferably, it isA dissolution rate of

In the following case, the resist tends to be insoluble in a developer and to be easily formed. In addition, the dissolution rate isIn the above case, the resolution may be improved. This is presumably because the change in solubility of the compound and/or the resin according to the present embodiment before and after exposure increases the contrast of the interface between the unexposed portion dissolved in the developer and the exposed portion not dissolved in the developer. Further, the reduction of LER and the reduction of defects were observed.

[ composition for Forming a film for lithography for use in a non-chemically amplified resist ]

The component (a) contained in the composition for forming a film for lithography for use as a non-chemically amplified resist of the present embodiment (hereinafter, also referred to as "radiation-sensitive composition") is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and is useful as a substrate for a positive resist which becomes a compound easily soluble in a developer by irradiating with g-ray, h-ray, i-ray, KrF excimer laser, ArF excimer laser, ultra-ultraviolet ray, electron beam, or X-ray. The properties of the component (a) are not greatly changed by g-rays, h-rays, i-rays, KrF excimer laser, ArF excimer laser, ultra ultraviolet rays, electron beams or X-rays, but the diazonaphthoquinone photoactive compound (B) which is hardly soluble in a developer is changed to a compound which is easily soluble in a developer, and thus a resist pattern can be formed by a developing process.

Since the component (a) contained in the radiation-sensitive composition of the present embodiment is a relatively low molecular weight compound, the roughness of the resulting resist pattern is very small. In the formula (1), R is selected from the group consisting of^T、A、R^Y、R^ZAt least 1 of the group of (a) is preferably a group containing an iodine atom.The radiation-sensitive composition of the present embodiment, if containing the component (a) containing an iodine atom, has an increased ability to absorb radiation such as electron beams, Extreme Ultraviolet (EUV) and X-rays, and as a result, has improved sensitivity.

The glass transition temperature of the component (a) contained in the radiation-sensitive composition of the present embodiment is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, further preferably 140 ℃ or higher, and particularly preferably 150 ℃ or higher. The upper limit of the glass transition temperature of the component (A) is not particularly limited, and is, for example, 400 ℃. Since the glass transition temperature of the component (a) is in the above range, heat resistance capable of maintaining a pattern shape in a semiconductor lithography process tends to improve performance such as high resolution.

The crystallization heat release as determined by differential scanning calorimetry analysis of the glass transition temperature of the component (a) contained in the radiation-sensitive composition of the present embodiment is preferably less than 20J/g. The (crystallization temperature) - (glass transition temperature) is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 130 ℃ or higher. When the crystallization heat release is less than 20J/g or (crystallization temperature) - (glass transition temperature) is within the above range, an amorphous film is easily formed by spin-coating the radiation-sensitive composition, and the film-forming property required for the resist can be maintained over a long period of time, and the resolution tends to be improved.

In the present embodiment, the crystallization heat release amount, crystallization temperature and glass transition temperature can be determined by differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu corporation. About 10mg of the sample was charged into an aluminum non-sealed container and heated to a temperature higher than the melting point in a nitrogen gas flow (50 mL/min) at a temperature rising rate of 20 ℃/min. After quenching, the temperature was again raised to the melting point or higher in a nitrogen gas flow (30 mL/min) at a temperature raising rate of 20 ℃ per minute. Further, after quenching, the temperature was again raised to 400 ℃ in a nitrogen gas flow (30 mL/min) at a temperature raising rate of 20 ℃ per minute. The temperature at the midpoint of the height difference of the base line of the stepwise change (when the specific heat becomes half) was defined as the glass transition temperature (Tg), and the temperature of the exothermic peak appearing thereafter was defined as the crystallization temperature. The heat release was determined from the area of the region surrounded by the heat release peak and the base line as the crystallization heat release.

The component (a) contained in the radiation-sensitive composition of the present embodiment is preferably: the sublimation property is low at normal pressure and at 100 ℃ or lower, preferably 120 ℃ or lower, more preferably 130 ℃ or lower, still more preferably 140 ℃ or lower, and particularly preferably 150 ℃ or lower. Low sublimability means: in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, and particularly preferably 0.1% or less. By reducing the sublimation property, contamination of the exposure apparatus due to exhaust gas during exposure can be prevented. In addition, a pattern shape with low roughness and good quality can be obtained.

The component (a) contained in the radiation-sensitive composition of the present embodiment is preferably dissolved by 1 mass% or more, more preferably dissolved by 5 mass% or more, further preferably dissolved by 10 mass% or more, particularly preferably dissolved by 20 mass% or more at 23 ℃ in a solvent selected from the group consisting of Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME), Cyclohexanone (CHN), Cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and showing the highest dissolving ability for the component (a), and particularly preferably dissolved by 20 mass% or more at 23 ℃ in a solvent selected from the group consisting of PGMEA, PGME, and CHN, and showing the highest dissolving ability for the component (a). By satisfying the above conditions, the semiconductor device can be easily used in a semiconductor manufacturing process in actual production.

[ diazonaphthoquinone photoactive Compound (B) ]

The diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition of the present embodiment is a diazonaphthoquinone material including a polymer-based and a non-polymer-based diazonaphthoquinone photoactive compound, and is not particularly limited as long as it is a material generally used as a photosensitive component (sensitizer) in a positive resist composition, and 1 kind or 2 or more kinds can be optionally used.

As the component (B), a compound obtained by reacting naphthoquinone diazide sulfonyl chloride, benzoquinone diazide sulfonyl chloride or the like with a low molecular weight compound or a high molecular weight compound having a functional group capable of undergoing a condensation reaction with these acid chlorides is preferable. Here, the functional group capable of condensing with an acid chloride is not particularly limited, and examples thereof include: hydroxyl group, amino group and the like, and particularly preferred is hydroxyl group. The compound capable of condensing with an acid chloride and containing a hydroxyl group is not particularly limited, and examples thereof include: hydroxybenzophenones such as hydroquinone, resorcinol, 2, 4-dihydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,4,4 '-trihydroxybenzophenone, 2,3,4, 4' -tetrahydroxybenzophenone, 2 ', 3,4, 6' -pentahydroxybenzophenone; hydroxyphenyl alkanes such as bis (2, 4-dihydroxyphenyl) methane, bis (2,3, 4-trihydroxyphenyl) methane, and bis (2, 4-dihydroxyphenyl) propane; hydroxytriphenylmethanes such as 4,4 ', 3 ', 4 ' -tetrahydroxy-3, 5,3 ', 5 ' -tetramethyltriphenylmethane, and 4,4 ', 2 ', 3 ', 4 ' -pentahydroxy-3, 5,3 ', 5 ' -tetramethyltriphenylmethane.

Examples of the acid chlorides such as naphthoquinone diazide sulfonyl chloride and benzoquinone diazide sulfonyl chloride include: 1, 2-naphthoquinonediazide-5-sulfonyl chloride, 1, 2-naphthoquinonediazide-4-sulfonyl chloride and the like are preferable.

The radiation-sensitive composition of the present embodiment is preferably prepared, for example, by dissolving each component in a solvent to prepare a homogeneous solution at the time of use, and then filtering the solution with, for example, a filter having a pore size of about 0.2 μm or so, if necessary.

[ Properties of radiation-sensitive composition ]

An amorphous film can be formed by spin coating using the radiation-sensitive composition of the present embodiment. The radiation-sensitive composition of the present embodiment can be used in a general semiconductor production process. Either one of the positive resist pattern and the negative resist pattern may be separately prepared depending on the kind of the developing solution used.

In the case of a positive resist pattern, the amorphous film formed by spin coating the radiation-sensitive composition of the present embodiment preferably has a dissolution rate in a developer at 23 ℃

The following, more preferably

Further preferred isA dissolution rate ofIn the following case, the resist tends to be insoluble in a developer and to be easily formed. In addition, the dissolution rate isIn the above case, the resolution may be improved. This is presumably because the change in solubility of the compound and/or the resin according to the present embodiment before and after exposure increases the contrast at the interface between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer. Further, the reduction of LER and the reduction of defects were observed.

In the case of a negative resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment preferably has a dissolution rate in a developer at 23 ℃The above. A dissolution rate of

In the above case, the compound is easily soluble in a developer and is suitable for a resist. In addition, the dissolution rate isIn the above case, the resolution may be improved. This is presumably because the microscopic surface portion of the compound and/or resin of the present embodiment dissolves, and the LER is reduced. But also the reduction of defects

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ℃ for a predetermined time and measuring the film thickness before and after the immersion by a known method such as visual observation, ellipsometry, or QCM.

In the case of a positive resist pattern, the dissolution rate of the exposed portion of the amorphous film formed by spin coating the radiation-sensitive composition of the present embodiment in a developer at 23 ℃ after irradiation with radiation such as KrF excimer laser, ultra-violet ray, electron beam, or X-ray, or after heating at 20 to 500 ℃ is preferably set to be high

Above, more preferablyFurther preferred isA dissolution rate ofIn the above case, the compound is easily soluble in a developer and is suitable for a resist. In addition, the dissolution rate is

In the following cases, the resolution may be improved. This is presumably because the microscopic surface portion of the compound and/or resin of the present embodiment dissolves, and the LER is reduced. Moreover, the effect of reducing defects is also seen.

In the case of a negative resist pattern, an amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is exposed to light after being irradiated with radiation such as KrF excimer laser, ultra-violet light, electron beam, or X-ray, or after being heated at 20 to 500 ℃The portion (A) preferably has a dissolution rate at 23 ℃ in the developer

The following, more preferably

Further preferred is

A dissolution rate ofIn the following case, the resist tends to be insoluble in a developer and to be easily formed. In addition, the dissolution rate isIn the above case, the resolution may be improved. This is presumably because the change in solubility of the compound and/or the resin according to the present embodiment before and after exposure increases the contrast of the interface between the unexposed portion dissolved in the developer and the exposed portion not dissolved in the developer. Further, the effect of reducing LER and the effect of reducing defects can be seen.

[ compounding ratio of respective ingredients ]

In the radiation-sensitive composition of the present embodiment, the content of the component (a) is preferably 1 to 100% by mass, more preferably 1 to 99% by mass, further preferably 5 to 95% by mass, further preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass, based on the total weight of the solid components (including the sum of the components (a), the diazonaphthoquinone photoactive compound (B), and the other components (D), which are optionally used. When the content of the component (a) in the radiation-sensitive composition of the present embodiment is within the above range, a pattern having high sensitivity and small roughness tends to be obtained.

In the radiation-sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass, based on the total weight of the solid content. When the content of the diazonaphthoquinone photoactive compound (B) in the radiation-sensitive composition of the present embodiment is within the above range, a pattern having high sensitivity and small roughness tends to be obtained.

[ other component (D) ]

In the radiation-sensitive composition of the present embodiment, as components other than the component (a) and the diazonaphthoquinone photoactive compound (B), various additives such as 1 or 2 or more kinds of acid generators, acid crosslinking agents, acid diffusion control agents, dissolution accelerators, dissolution control agents, sensitizers, surfactants, oxoacids of organic carboxylic acids or phosphorus or derivatives thereof, thermal and/or photo-curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photo-curing resins, dyes, pigments, thickeners, lubricants, defoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants and the like may be added as necessary within a range not to impair the object of the present invention. In the present specification, the other component (D) may be referred to as an arbitrary component (D).

In the radiation-sensitive composition of the present embodiment, the blending ratio of each component (a)/naphthoquinone diazide photoactive compound (B)/optional component (D)) is calculated as mass% based on the solid content,

preferably 1 to 99/99 to 1/0 to 98,

More preferably 5 to 95/95 to 5/0 to 49,

More preferably 10 to 90/90 to 10/0 to 10,

More preferably 20 to 80/80 to 20/0 to 5,

Particularly preferably 25 to 75/75 to 25/0.

The compounding ratio of each component may be selected from ranges such that the total thereof becomes 100 mass%. When the blending ratio of each component of the radiation-sensitive composition of the present embodiment is in the above range, the composition tends to have excellent performance such as sensitivity and resolution in addition to roughness.

The radiation-sensitive composition of the present embodiment may contain other resins than those of the present embodiment within a range not interfering with the object of the present invention. Examples of such other resins include novolak resins, polyvinyl phenols, polyacrylic acids, polyvinyl alcohols, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as a monomer unit, or derivatives thereof. The amount of these resins to be blended may be appropriately adjusted depending on the kind of the component (a) to be used, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 0 part by mass, relative to 100 parts by mass of the component (a).

In the radiation-sensitive composition of the present embodiment, an acid crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, an acid generator, and a basic compound, which are exemplified in the "film-forming composition for lithography for a lower-layer film" described later, can be used within a range not to impair the object of the present invention.

[ method for Forming resist Pattern or insulating film ]

The method for forming a resist pattern in the present embodiment includes the steps of: after a photoresist layer is formed on a substrate using the resist composition or radiation-sensitive composition of the present embodiment, a predetermined region of the photoresist layer is irradiated with radiation and developed. The insulating film can be formed by the same method as the method for forming the resist pattern.

More specifically, the method comprises the following steps: a step of forming a resist film on a substrate using the resist composition or the radiation-sensitive composition of the present embodiment; exposing the formed resist film; and a step of forming a resist pattern by developing the resist film. The resist pattern in this embodiment mode can also be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, a resist film is formed by applying a resist composition or a radiation-sensitive composition onto a conventionally known substrate by an application means such as spin coating, cast coating, or roll coating. The conventionally known substrate is not particularly limited, and examples thereof include: a substrate for electronic components, a substrate having a predetermined wiring pattern formed thereon, and the like. More specifically, there may be mentioned: silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. Examples of the wiring pattern material include: copper, aluminum, nickel, gold, etc. Further, an inorganic and/or organic film may be provided on the substrate as needed. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be cited. As the organic film, an organic anti-reflection film (organic BARC) can be mentioned. A surface treatment with hexamethylenedisilazane or the like may be performed on the substrate.

Next, the substrate coated with the resist composition or the radiation-sensitive composition is heated as necessary. The heating conditions vary depending on the compounding composition of the resist composition or the radiation-sensitive composition, and the like, and are preferably 20 to 250 ℃ and more preferably 20 to 150 ℃. Heating is preferable because the adhesion of the resist to the substrate tends to be improved. Next, the resist film is exposed to a desired pattern using any one of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, Extreme Ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like may be appropriately selected depending on the compounding composition of the resist composition or the radiation-sensitive composition. In the present embodiment, in order to stably form a fine pattern with high accuracy in exposure, it is preferable to heat the pattern after irradiation with radiation. The heating conditions vary depending on the compounding composition of the resist composition or the radiation-sensitive composition, and the like, and are preferably 20 to 250 ℃ and more preferably 20 to 150 ℃.

Next, the exposed resist film is developed with a developer to form a predetermined resist pattern. As the developer, a solvent having a solubility parameter (SP value) close to that of the compound or the resin of the present embodiment is preferably selected. For example, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent, a hydrocarbon solvent, or an aqueous alkali solution described in international publication No. WO2013/024778 can be used.

The solvent may be mixed in plural, or may be mixed with a solvent other than the above-mentioned solvents or water within the range of performance. Among these, in order to sufficiently exhibit the effects of the present invention, the water content of the entire developer is preferably less than 70% by mass, more preferably less than 50% by mass, still more preferably less than 30% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. That is, the content of the organic solvent with respect to the developer is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, further preferably 70% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer.

From the viewpoint of improving the resist properties such as resolution and roughness of the resist pattern, a developer containing at least 1 solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is particularly preferable.

The vapor pressure of the developer is preferably 5kPa or less, more preferably 3kPa or less, and still more preferably 2kPa or less at 20 ℃. When the vapor pressure of the developer is 5kPa or less, evaporation of the developer on the substrate or in the developing cup can be suppressed, and temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface tends to be improved.

Specific examples of the developer having a vapor pressure of 5kPa or less at 20 ℃ include those described in international publication No. WO 2013/024778.

Specific examples of the developer having a vapor pressure of 2kPa or less at 20 ℃ include those described in international publication No. WO 2013/024778.

An appropriate amount of a surfactant may be added to the developer as required. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or silicon-based surfactant can be used. Examples of the fluorine-based and/or silicon-based surfactant include: the surfactant described in Japanese patent laid-open Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, 5405720, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511 and 5824451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, and is preferably a fluorine-based surfactant or a silicon-based surfactant.

The amount of the surfactant to be used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass based on the total amount of the developer.

As the developing method, for example, there can be applied: a method of immersing the substrate in a tank filled with a developing solution for a constant time (immersion method); a method of carrying a developing solution on a substrate surface by using surface tension and standing for a constant time (paddle method); a method of spraying a developing solution onto a substrate surface (spraying method); a method (dynamic dispensing method) in which the developing solution is continuously applied to a substrate rotating at a constant speed while scanning the developing solution applying nozzle at a constant speed. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

After the step of performing the development, the step of stopping the development may be performed while replacing the solvent with another solvent.

After development, the method preferably includes a step of washing with a rinse solution containing an organic solvent.

The rinse solution used in the post-development rinse step is not particularly limited as long as it does not dissolve the resist pattern cured by crosslinking, and a solution containing a general organic solvent or water may be used. As the rinse liquid, a rinse liquid containing at least 1 organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is preferably used. More preferably, after development, the step of washing the substrate with a rinse solution containing at least 1 organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents is performed. Further, it is more preferable to perform a step of washing with a washing liquid containing an alcohol-based solvent or an ester-based solvent after development. Further, it is more preferable to perform a step of washing with a washing liquid containing 1-membered alcohol after development. Particularly, it is preferable to perform a step of washing with a washing liquid containing 1-membered alcohol having 5 or more carbon atoms after development. The time for rinsing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Examples of the 1-membered alcohol used in the rinsing step after development include linear, branched and cyclic 1-membered alcohols, and examples thereof include those described in international publication No. WO 2013/024778. Particularly preferred 1-membered alcohols having 5 or more carbon atoms include: 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The above-mentioned components may be mixed in plural, or may be mixed with an organic solvent other than the above-mentioned components.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. By setting the water content in the rinse liquid to 10 mass% or less, more favorable development characteristics tend to be obtained.

The vapor pressure of the rinse liquid used after the development is preferably 0.05kPa or more and 5kPa or less, more preferably 0.1kPa or more and 5kPa or less, and still more preferably 0.12kPa or more and 3kPa or less at 20 ℃. By setting the vapor pressure of the rinse liquid to 0.05kPa or more and 5kPa or less, the temperature uniformity in the wafer surface is further improved, and furthermore, the swelling due to the permeation of the rinse liquid is further suppressed, and the dimensional uniformity in the wafer surface tends to be further improved.

An appropriate amount of a surfactant may be added to the rinse solution.

In the rinsing step, the wafer subjected to the development is subjected to a cleaning process using a rinse liquid containing the organic solvent. The method of the cleaning treatment is not particularly limited, and for example, the following methods can be applied: a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (spin coating method); a method of immersing the substrate in a tank filled with a rinse liquid for a constant time (immersion method); among them, it is preferable to carry out a cleaning treatment by a spin coating method, and after the cleaning, remove the rinse liquid from the substrate by rotating the substrate at a rotation speed of 2000 to 4000 rpm.

After the resist pattern was formed, a patterned wiring substrate was obtained by etching. The etching method can be performed by a known method such as dry etching using a plasma gas, wet etching using an alkali solution, a copper chloride solution, an iron chloride solution, or the like.

The plating may be performed after the resist pattern is formed. Examples of the plating method include: copper plating, solder plating, nickel plating, gold plating, and the like.

The residual resist pattern after etching can be stripped with an organic solvent. Examples of the organic solvent include: PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like. Examples of the peeling method include a dipping method and a spraying method. The wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate or may have a small-diameter through hole.

The wiring board in this embodiment can also be formed by a lift-off method, which is a method of evaporating metal in a vacuum after the resist pattern is formed and then dissolving the resist pattern in a solution.

[ film-forming composition for lithography for use as a bottom-layer film ]

The film-forming composition for lithography (hereinafter, also referred to as "underlayer film-forming material") for use as a surface underlayer film in the present embodiment contains the compound and/or the resin of the present embodiment. In the present embodiment, the amount of the substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, even more preferably 50 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 100% by mass, of the solid content of the underlayer coating forming material, from the viewpoints of coatability and quality stability.

The composition for forming a film for lithography for use as a layer-down facing film in the present embodiment can also be used as an optical member-forming composition. The optical member-forming composition is, for example, coated or cast on a substrate, whereby an optical member-forming film can be formed.

The lower layer film forming material of the present embodiment can be used for a wet process and is excellent in heat resistance and etching resistance. Further, since the above-described materials are used as the material for forming the lower layer film of the present embodiment, deterioration of the film at the time of high-temperature baking is suppressed, and the lower layer film having excellent etching resistance to oxygen plasma etching and the like can be formed. Further, the lower layer film-forming material of the present embodiment is also excellent in adhesion to the resist layer, and therefore, an excellent resist pattern can be obtained. The lower layer film-forming material of the present embodiment may include a conventionally known lower layer film-forming material for lithography, and the like, as long as the effects of the present invention are not impaired.

[ solvent ]

The lower layer film-forming material in the present embodiment may contain a solvent. The solvent used for the lower layer film-forming material is not particularly limited as long as it dissolves at least the above-mentioned substance, and a known solvent can be suitably used.

Specific examples of the solvent are not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester-based solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, and 1-ethoxy-2-propanol; and aromatic hydrocarbons such as toluene, xylene, and anisole. These solvents may be used alone in 1 kind or in combination of 2 or more kinds.

Among the above solvents, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole are particularly preferable from the viewpoint of safety.

The content of the solvent is not particularly limited, and is preferably 100 to 10000 parts by mass, more preferably 200 to 5000 parts by mass, and still more preferably 200 to 1000 parts by mass, per 100 parts by mass of the compound and/or the resin of the present embodiment, from the viewpoint of solubility and film formation.

[ acid crosslinking agent ]

The lower layer film-forming material in the present embodiment may contain an acid crosslinking agent as necessary from the viewpoint of suppressing mixing or the like. The acid crosslinking agent is not particularly limited, and for example, one described in international publication No. 2013/024779 can be used.

Specific examples of the acid crosslinking agent that can be used in the present embodiment include, but are not particularly limited to, phenol compounds, epoxy compounds, cyanate ester compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, azide compounds, and the like. These crosslinking agents may be used alone in 1 kind, or in combination of 2 or more kinds. Among them, a benzoxazine compound, an epoxy compound, or a cyanate ester compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improvement of etching resistance.

As the above-mentioned phenol compound, a known one can be used. Examples of the phenols include, in addition to phenol, alkylphenols such as cresol and xylenol, polyphenols such as hydroquinone, polycyclic phenols such as naphthol and naphthalenediol, bisphenols such as bisphenol a and bisphenol F, and polyfunctional phenol compounds such as phenol novolak and phenol aralkyl resins. Among them, aralkyl type phenol resins are preferable from the viewpoint of heat resistance and solubility.

The epoxy compound may be a known epoxy compound, and may be selected from those having 2 or more epoxy groups in 1 molecule. Examples thereof include 2-membered phenol type epoxides such as bisphenol A, bisphenol F, 3 ', 5, 5' -tetramethyl-bisphenol F, bisphenol S, bisphenol fluorene, 2,2 '-biphenol, 3', 5,5 '-tetramethyl-4, 4' -dihydroxybiphenyl, resorcinol and naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,2, 2-tetrakis (4-hydroxyphenyl) ethane, tris (2, 3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, phenol novolac, o-cresol novolac or other 3-or more-membered phenol type epoxides, dicyclopentadiene and phenol copolycondensation resins, phenol aralkyl type epoxides synthesized from phenols and p-xylene dichloride or the like, phenol aralkyl type epoxides, Epoxy compounds of biphenyl aralkyl type phenol resins synthesized from phenols and bischloromethylbiphenyl, and epoxy compounds of naphthol aralkyl type resins synthesized from naphthols and p-xylene dichloride. These epoxy resins may be used alone, or 2 or more kinds may be used in combination. Among them, from the viewpoint of heat resistance and solubility, epoxy resins solid at room temperature such as epoxy resins obtained from phenol aralkyl resins and biphenyl aralkyl resins are preferable.

The cyanate ester compound is not particularly limited as long as it has 2 or more cyanate groups in 1 molecule, and known ones can be used. In the present embodiment, a preferable cyanate ester compound includes a compound having 2 or more hydroxyl groups in 1 molecule, in which a hydroxyl group is substituted with a cyanate group. The cyanate ester compound preferably has an aromatic group, and a structure in which a cyanate group is directly bonded to an aromatic group can be suitably used. Examples of the cyanate ester compound include compounds obtained by substituting hydroxyl groups of bisphenol a, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac, cresol novolac, dicyclopentadiene novolac, tetramethylbisphenol F, bisphenol a novolac, brominated bisphenol a, brominated phenol novolac, 3-functional phenol, 4-functional phenol, naphthalene-type phenol, biphenyl-type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus-containing phenol, and the like with cyanate groups. These cyanate ester compounds may be used alone or in a suitable combination of 2 or more. The cyanate ester compound may be in any form of a monomer, an oligomer, and a resin.

Examples of the amino compound include m-phenylenediamine, p-phenylenediamine, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfide, 3 ' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 4-diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfide, 3 ' -bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminopheno, Bis [4- (4-aminophenoxy) phenyl]Sulfone, 2-bis [4- (4-aminophenoxy) phenyl]Propane, 2-bis [4- (3-aminophenoxy) phenyl]Propane, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl]Ether, bis [4- (3-aminophenoxy) phenyl]Ether, 9-bis (4-aminophenyl) fluorene, 9-bis (4-amino-3-chlorophenyl) fluorene, 9-bis (4-amino-3-fluorophenyl) fluorene, o-tolidine, m-tolidine, 4 ' -diaminobenzanilide, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2- (4-aminophenyl) -6-aminobenzoxazole, and the like. Further, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylpropane, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl ] benzene, bis]Sulfone, 2-bis [4- (4-aminophenoxy) phenyl]Propane, 2-bis [4- (3-aminophenoxy) phenyl]Propane, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl]Ether, bis [4- (3-aminophenoxy) phenyl]Aromatic amines such as ether, diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, and diaminodicyclohexylpropaneDiamino bicyclo [2.2.1]Heptane, bis (aminomethyl) -bicyclo [2.2.1]Heptane, 3(4),8(9) -bis (aminomethyl) tricyclo [5.2.1.0^2,6]Alicyclic amines such as decane, 1, 3-bisaminomethylcyclohexane and isophoronediamine, and aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine and triethylenetetramine.

Examples of the benzoxazine compound include P-d type benzoxazines obtained from bifunctional diamines and monofunctional phenols, and F-a type benzoxazines obtained from monofunctional diamines and bifunctional phenols.

Specific examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound obtained by methoxymethylation of 1 to 6 methylol groups of hexamethylolmelamine or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound obtained by acyloxymethyl group of 1 to 6 methylol groups of hexamethylolmelamine or a mixture thereof, and the like.

Specific examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylol guanamine, or a mixture thereof, tetramethoxyethyl guanamine, tetraalkoxyguanamine, a compound obtained by acyloxymethyl-methylation of 1 to 4 methylol groups of tetramethylol guanamine, or a mixture thereof.

Specific examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyol, tetramethoxymethyl glycoluril, 1 to 4 methoxymethylated methylol compounds of tetramethylol glycoluril, mixtures thereof, 1 to 4 acyloxymethyl methylol compounds of tetramethylol glycoluril, mixtures thereof, and the like.

Specific examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.

In addition, in the present embodiment, an acid crosslinking agent having at least 1 allyl group can be used from the viewpoint of improvement of crosslinkability. Specific examples of the acid crosslinking agent having at least 1 allyl group include 2, 2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, allylphenols such as bis (3-allyl-4-hydroxyphenyl) sulfide and bis (3-allyl-4-hydroxyphenyl) ether, 2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3-allyl-4-cyanatophenyl) propane, and the like, Allyl cyanates such as bis (3-allyl-4-cyanatophenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide, bis (3-allyl-4-cyanatophenyl) ether, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, but not limited thereto. They may be used alone or in a mixture of 2 or more. Among these, allylphenols such as 2, 2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, and bis (3-allyl-4-hydroxyphenyl) ether are preferable from the viewpoint of excellent compatibility with the bismaleimide compound and/or the addition polymerization type maleimide resin.

The content of the acid crosslinking agent in the lower layer film-forming material is not particularly limited, but is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 10 to 40 parts by mass, based on 100 parts by mass of the compound and/or the resin of the present embodiment. When the content of the acid crosslinking agent is in the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, and the antireflection effect and the film formability after crosslinking tend to be improved.

[ crosslinking Accelerator ]

As the lower layer film-forming material of the present embodiment, there may be used, as required: and a crosslinking accelerator for accelerating crosslinking and curing reactions.

The crosslinking accelerator is not particularly limited as long as it can accelerate crosslinking and curing reactions, and examples thereof include amines, imidazoles, organophosphines, and lewis acids. These crosslinking accelerators may be used alone in 1 kind or in combination of 2 or more kinds. Of these, imidazoles and organophosphines are preferred, and imidazoles are more preferred from the viewpoint of lowering the crosslinking temperature.

The crosslinking accelerator is not limited to the following, and examples thereof include tertiary amines such as 1, 8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and 2,4, 5-triphenylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetra-substituted phosphonium and tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate and the like; tetraphenylboron salts such as 2-ethyl-4-methylimidazolium tetraphenylboron and N-methylmorpholine tetraphenylboron.

The amount of the crosslinking accelerator to be blended is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, from the viewpoint of easiness of control and economy, in general, when the compound and/or the resin of the present embodiment is 100 parts by mass.

[ radical polymerization initiator ]

The lower layer film-forming material of the present embodiment may contain a radical polymerization initiator as necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or a thermal polymerization initiator that initiates radical polymerization by heat.

The radical polymerization initiator is not particularly limited, and conventionally used ones can be suitably used. Examples thereof include ketone-based photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methylpropan-1-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like, Methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetoacetic ester peroxide, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) -cyclohexane, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) -2-methylcyclohexane, 1-bis (t-butylperoxy) -cyclohexane, 1-bis (t-butylperoxy) cyclododecane, 1-bis (t-butylperoxy) butane, 2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, methyl-n-butyl-ethyl ketone peroxide, p-butyl-ethyl methyl-ethyl-ketone peroxide, p-butyl-ethyl, Diisopropylbenzene hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexylhydroperoxide, tert-butylhydroperoxide, α' -bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5, 5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, cumene hydroperoxide, tert-butylhydroperoxide, di-tert-butylperoxy, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-, Diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α' -bis (neodecanoylperoxy) diisopropylbenzene, cumyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy isobutyrate, t-butylperoxy maleate, t-butylperoxy-3, 5, 5-trimethylhexanoate, t-butylperoxy laurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxy acetate, t-butylperoxy-m-toluoylbenzoate, methyl ethyl hexanoate, ethyl hexano, Organic peroxide-based polymerization initiators such as t-butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, 2, 5-dimethyl-2, 5-bis (m-toluoylperoxy) hexane, t-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3 ', 4, 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2, 3-dimethyl-2, 3-diphenylbutane.

Further, there may be mentioned 2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile, 1- [ (1-cyano-1-methylethyl) azo ] formamide, 1 ' -azobis (cyclohexane-1-carbonitrile), 2 ' -azobis (2-methylbutyronitrile), 2 ' -azobisisobutyronitrile, 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2-methylpropionamidine) dihydrochloride, 2 ' -azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2 ' -azobis [ N- (4-chlorophenyl) -2-methylpropionamidine ] dihydrochloride, 2,2 '-azobis [ N- (4-hydroxyphenyl) -2-methylpropionamidine ] dihydrochloride, 2' -azobis [ 2-methyl-N- (phenylmethyl) propionamidine ] dihydrochloride, 2 '-azobis [ 2-methyl-N- (2-propenyl) propionamidine ] dihydrochloride, 2' -azobis [ N- (2-hydroxyethyl) -2-methylpropionamidine ] dihydrochloride, 2 '-azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis [2- (4,5,6, 7-tetrahydro-1H-1, 3-diazepin-2-yl) propane ] dihydrochloride, 2 ' -azobis [2- (3,4,5, 6-tetrahydropyrimidin-2-yl) propane ] dihydrochloride, 2 ' -azobis [2- (5-hydroxy-3, 4,5, 6-tetrahydropyrimidin-2-yl) propane ] dihydrochloride, 2 ' -azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl ] propane ] dihydrochloride, 2 ' -azobis [2- (2-imidazolin-2-yl) propane ], 2 ' -azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide ], 2 '-azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl ] propionamide ], 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2 '-azobis (2-methylpropionamide), 2' -azobis (2,4, 4-trimethylpentane), azo polymerization initiators such as 2,2 ' -azobis (2-methylpropane), dimethyl-2, 2-azobis (2-methylpropionate), 4 ' -azobis (4-cyanovaleric acid), and 2,2 ' -azobis [2- (hydroxymethyl) propionitrile ]. As the radical polymerization initiator in the present embodiment, 1 kind of them may be used alone, or 2 or more kinds may be used in combination, or other known polymerization initiators may be further used in combination.

The content of the radical polymerization initiator may be an amount required for a stoichiometric amount, and is preferably 0.05 to 25 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the compound and/or the resin of the present embodiment. When the content of the radical polymerization initiator is 0.05 parts by mass or more, curing tends to be prevented from becoming insufficient, while when the content of the radical polymerization initiator is 25 parts by mass or less, long-term storage stability of the lower layer film-forming material at room temperature tends to be prevented from being impaired.

[ acid generators ]

The lower layer film-forming material in the present embodiment may contain an acid generator as necessary from the viewpoint of further promoting the crosslinking reaction by heat, and the like. As the acid generator, a substance that generates an acid by thermal decomposition, a substance that generates an acid by light irradiation, and the like are known, and any of them can be used. As the acid generator, for example, the one described in international publication No. 2013/024779 can be used.

The content of the acid generator in the lower layer film-forming material is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, per 100 parts by mass of the compound and/or the resin of the present embodiment. When the content of the acid generator is in the above range, the amount of acid generated increases, the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist tends to be suppressed.

[ basic Compound ]

The lower layer film-forming material in the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound functions as a quencher for an acid, and is used for preventing a crosslinking reaction from proceeding by a trace amount of an acid generated from the acid generator. Such a basic compound is not particularly limited, and examples thereof include those described in international publication No. 2013/024779.

The content of the basic compound in the lower layer film-forming material is not particularly limited, but is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the compound and/or the resin of the present embodiment. When the content of the basic compound is in the above range, the storage stability tends to be improved without excessively impairing the crosslinking reaction.

[ other additives ]

The lower layer film-forming material in the present embodiment may contain other resins and/or compounds for the purpose of imparting curability by heat or light and controlling absorbance. Examples of such other resins and/or compounds include: naphthol resins, xylene resins, naphthol modified resins, phenol modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylate esters, dimethacrylate esters, trimethacrylate esters, tetramethacrylate esters, vinylnaphthalene, polyacenaphthylene and the like containing naphthalene rings, phenanthrenequinone, fluorene and the like containing biphenyl rings, thiophene, indene and the like containing hetero rings having hetero atoms or resins containing no aromatic rings; alicyclic structure-containing resins and compounds such as rosin-based resins, cyclodextrins, adamantane (poly) alcohols, tricyclodecane (poly) alcohols, and derivatives thereof, and the like, are not particularly limited thereto. Further, the lower layer film-forming material in the present embodiment may contain a known additive. The known additives are not limited to the following, and examples thereof include: a thermal and/or photo-curing catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a photo-curing resin, a dye, a pigment, a thickener, a lubricant, an antifoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant, a nonionic surfactant, and the like.

[ methods for Forming underlayer film for lithography and multilayer resist Pattern ]

The underlayer film for lithography in this embodiment is formed of the underlayer film forming material.

The resist pattern forming method of the present embodiment includes the steps of: an underlayer film is formed on a substrate using the above composition, at least 1 photoresist layer is formed on the underlayer film, and then a predetermined region of the photoresist layer is irradiated with radiation to develop the photoresist layer. More specifically, the method comprises the following steps: a step (a-1) of forming an underlayer film on a substrate using the underlayer film forming material of the present embodiment; a step (A-2) of forming at least 1 photoresist layer on the underlayer film; and a step (A-3) of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer after the step (A-2).

Further, the circuit pattern forming method of the present embodiment includes the steps of: forming an underlayer film on a substrate using the composition, forming an interlayer film on the underlayer film using a resist interlayer film material, and forming at least 1 photoresist layer on the interlayer film;

a step of forming a resist pattern by irradiating a predetermined region of the photoresist layer with radiation and developing the resist pattern; and the combination of (a) and (b),

and a step of forming a pattern on the substrate by etching the substrate with the lower layer film pattern obtained by etching the lower layer film with the intermediate layer film pattern obtained by etching the intermediate layer film with the resist pattern as an etching mask.

More specifically, the method comprises the following steps: a step (B-1) of forming an underlayer film on a substrate using the underlayer film forming material of the present embodiment; a step (B-2) of forming an intermediate layer film on the underlayer film by using a resist intermediate layer film material containing silicon atoms; a step (B-3) of forming at least 1 photoresist layer on the intermediate layer film; a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer to form a resist pattern; and (B-5) etching the intermediate layer film using the resist pattern as a mask after the step (B-4), etching the underlying layer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained underlying layer film pattern as an etching mask, thereby forming a pattern on the substrate.

The lower layer film for lithography in the present embodiment is not particularly limited in its forming method as long as it is formed from the lower layer film forming material of the present embodiment, and a known method can be applied. For example, the underlayer film material of the present embodiment may be applied to a substrate by a known coating method such as spin coating or screen printing, or a printing method, and then the organic solvent may be evaporated and removed, followed by crosslinking and curing by a known method, thereby forming the underlayer film for lithography of the present embodiment. Examples of the crosslinking method include a method of thermal curing, photo curing and the like. The organic solvent is evaporated and removed, whereby an underlayer film can be formed.

In the formation of the lower layer film, baking is preferably performed in order to suppress the occurrence of a mixing phenomenon with the upper layer resist and to promote a crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ℃, and more preferably 200 to 400 ℃. The baking time is not particularly limited, and is preferably within a range of 10 to 300 seconds. The thickness of the underlayer film is not particularly limited, and may be appropriately selected depending on the required performance, but is usually preferably about 30 to 20000nm, more preferably 50 to 15000 nm.

After the formation of the underlayer film on the substrate, in the case of a 2-layer process, a silicon-containing resist layer or a single-layer resist made of a normal hydrocarbon can be formed on the underlayer film. In the case of a 3-layer process, a silicon-containing intermediate layer may be fabricated on the underlying film, and a single-layer resist layer that does not contain silicon may be fabricated on the silicon-containing intermediate layer. In these cases, the photoresist material used for forming the resist layer may be appropriately selected from known materials and used, and is not particularly limited.

As the silicon-containing resist material for the 2-layer process, a positive type resist material is preferably used from the viewpoint of oxygen etching resistance, which uses a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative as a base polymer, and further contains an organic solvent, an acid generator, a basic compound if necessary, and the like. Here, as the polymer containing a silicon atom, a known polymer used in such a resist material can be used.

As a silicon-containing intermediate layer for a 3-layer process, a polysilsesquioxane based intermediate layer is preferably used. By providing the intermediate layer with an effect as an antireflection film, reflection tends to be effectively suppressed. For example, in a 193nm exposure process, when a material containing a large amount of aromatic groups and having high substrate etching resistance is used as an underlayer film, the k value tends to be high and the substrate reflection tends to be high, and the substrate reflection can be made 0.5% or less by suppressing the reflection by the intermediate layer. The intermediate layer having such an antireflection effect is not limited to the following, and polysilsesquioxane in which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced for 193nm exposure and crosslinked by an acid or heat is preferably used.

In addition, an intermediate layer formed by a Chemical Vapor Deposition (CVD) method may also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, a SiON film is known. In general, the formation of the intermediate layer by a wet process such as spin coating or screen printing is more convenient and has an advantage in cost than the CVD method. The upper layer resist in the 3-layer process may be either a positive or negative resist, and the same resist as a commonly used single layer resist may be used.

Further, the underlayer coating in the present embodiment can also be used as an antireflection coating for a normal single-layer resist or as an underlayer material for suppressing pattern collapse. The underlayer coating of the present embodiment is excellent in etching resistance for underlayer processing, and therefore can be expected to function as a hard mask for underlayer processing.

In forming a resist layer using the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the underlayer film. After the resist material is applied by a spin coating method or the like, a prebaking is usually performed, and the prebaking is preferably performed at 80 to 180 ℃ for 10 to 300 seconds. Then, exposure, post-exposure baking (PEB), and development were performed according to a conventional method, whereby a resist pattern was obtained. The thickness of the resist film is not particularly limited, but is preferably 30 to 500nm, more preferably 50 to 400 nm.

The exposure light may be appropriately selected and used according to the photoresist material used. The exposure light is usually a high-energy radiation having a wavelength of 300nm or less, and specific examples thereof include: 248nm, 193nm and 157nm excimer laser, 3-20 nm soft X-ray, electron beam, X-ray and the like.

The resist pattern formed by the above method becomes a resist pattern in which pattern collapse is suppressed by the lower layer film. Therefore, by using the lower layer film in this embodiment mode, a finer pattern can be obtained, and the exposure amount necessary for obtaining the resist pattern can be reduced.

Next, the resulting resist pattern is used as a mask to perform etching. As the etching of the lower layer film in the 2-layer process, gas etching is preferably used. As the gas etching, etching using oxygen is suitable. On the basis of oxygen, inactive gas such as He and Ar, CO and CO can be added₂、NH₃、SO₂、N₂、NO₂、H₂A gas. Alternatively, only CO or CO may be used without using oxygen₂、NH₃、N₂、NO₂、H₂The gas is used to perform gas etching. In particular, the latter gas can be preferably used for the purpose of side wall protection against undercut of the pattern side wall.

On the other hand, in the etching of the intermediate layer in the 3-layer process, gas etching is also preferably used. As the gas etching, the same gas etching as that described in the 2-layer process can be applied. In particular, the intermediate layer in the 3-layer process is preferably processed using a freon gas and using the resist pattern as a mask. Then, for example, oxygen etching is performed using the intermediate layer pattern as a mask as described above, whereby the lower layer film can be processed.

Here, when the inorganic hard mask intermediate layer film is formed as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, and for example, the methods described in Japanese patent laid-open Nos. 2002-334869 and WO2004/066377 can be used. The photoresist film may be formed directly on the intermediate layer film, or an organic anti-reflection film (BARC) may be formed on the intermediate layer film by spin coating, and a photoresist film may be formed thereon.

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By providing the resist interlayer film with an effect as an antireflection film, reflection tends to be effectively suppressed. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, and for example, materials described in japanese patent laid-open nos. 2007 & 226170 and 2007 & 226204 can be used.

In addition, the subsequent etching of the substrate can also be carried out by conventional methods, for example, the substrate is SiO₂In the case of SiN, etching mainly with a freon gas is possible, and etching mainly with a chlorine-based or bromine-based gas is possible as long as the substrate is p-Si, Al, or W. When a substrate is etched with a freon gas, a silicon-containing resist in a 2-layer resist process and a silicon-containing intermediate layer in a 3-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is peeled off separately, and generally, dry etching peeling with a freon-based gas is performed after the substrate processing.

The lower layer film in the present embodiment is characterized by excellent etching resistance of the substrate, and a known substrate can be appropriately selected and used as the substrate, and examples thereof include, but are not particularly limited to, Si, α -Si, p-Si, and SiO₂SiN, SiON, W, TiN, Al, etc. The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such a film to be processed include: si, SiO₂The thickness of the substrate or film to be processed is not particularly limited, and is usually preferably about 50 to 10000nm, more preferably 75 to 5000 nm.

The permanent resist film coated with the composition of the present embodiment is suitable as a permanent film remaining in the final product after a resist pattern is formed as necessary. Specific examples of the permanent film include a solder resist layer, an encapsulating material, an underfill material, an encapsulating adhesive layer for a circuit element and the like, and an adhesive layer for an integrated circuit element and a circuit board in a semiconductor device, and a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer and the like in a thin display. In particular, the permanent film formed from the composition of the present embodiment has an extremely excellent advantage of being excellent in heat resistance and moisture resistance and also having little contamination due to a sublimed component. In particular, a display material has high sensitivity, high heat resistance, and high moisture absorption reliability, which are accompanied by less image quality deterioration due to important contamination.

When the composition of the present embodiment is used for a permanent resist film, various additives such as other resins, surfactants, dyes, fillers, acid crosslinking agents, and dissolution accelerators may be added in addition to the curing agent as needed, and dissolved in an organic solvent to form a composition for a permanent resist film.

The composition for forming a resist film and the composition for a permanent resist film in the present embodiment can be prepared by mixing the above components and mixing them with a stirrer or the like. When the composition for a resist underlayer film or the composition for a permanent resist film in the present embodiment contains a filler or a pigment, it can be prepared by dispersing or mixing the components using a dispersing device such as a dissolver, a homogenizer, or a triple roll mill.