阅读说明：本技术 制造固化膜的方法及其使用 (Method for producing cured film and use thereof ) 是由 关藤高志 中杉茂正 柳田浩志 平山拓 于 2020-04-24 设计创作，主要内容包括：本发明提供一种高膜密度、高膜硬度、高耐蚀刻性的固化膜的制造方法。一种制造固化膜的方法,包括(1)在基板的上方应用组合物(i)；(2)由组合物(i)形成含烃膜；以及(3)对含烃膜照射等离子体、电子束和/或离子,形成固化膜。该固化膜的使用。(The invention provides a method for producing a cured film having high film density, high film hardness, and high etching resistance. A method of making a cured film comprising (1) applying a composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating plasma, electron beam and/or ions to the hydrocarbon-containing film to form a cured film. Use of the cured film.)

1. A method of manufacturing a cured film, comprising the steps of:

(1) applying composition (i) over a substrate;

(2) Forming a hydrocarbon-containing film from composition (i); and

(3) irradiating plasma, electron beam and/or ions to the hydrocarbon-containing film to form a cured film;

with the proviso that composition (i) contains (a) a hydrocarbonaceous compound, and (B) a solvent;

(A) the hydrocarbon-containing compound contains a structural unit (A1) represented by the following formula (A1);

here, Ar₁₁Is by R₁₁Substituted or unsubstituted C_6-60A hydrocarbon of (A), but Ar₁₁Does not contain a fused aromatic ring;

R₁₁is C_1-20A linear, branched or cyclic alkyl, amino, or alkylamino group of (a);

R₁₂is I, Br or CN;

p₁₁p is a number of 0 to 5₁₂Q is a number of 0 to 1₁₁Q is a number of 0 to 5₁₂A number r of 0 to 1₁₁A number s of 0 to 5₁₁A number of 0 to 5;

p₁₁、q₁₁and r₁₁Not 0 at the same time in one structural unit.

2. The method for producing a cured film according to claim 1, wherein the aforementioned formula (a1) is the following formula (a1-1), (a1-2) and/or (a 1-3):

Ar₂₁is C_6-50The aromatic hydrocarbon (b) of (a),

R₂₁、R₂₂and R₂₃Are each independently C_6-50An aromatic hydrocarbon of (1), hydrogen, or a single bond bonded to other structural units,

n₂₁is an integer of 0 or 1;

here, Ar₂₁、R₂₁、R₂₂And R₂₃Does not contain a fused aromatic ring and, if desired,

R₁₂、p₁₁、p₁₂、q₁₁、q₁₂、r₁₁and s₁₁Are each independently the same as described above;

L₃₁and L₃₂Each independently is a single bond or phenylene,

n₃₁、n₃₂、m₃₁and m₃₂Each independently is a number from 0 to 6;

Here, R₁₂、p₁₁、p₁₂、q₁₁、q₁₂、r₁₁And s₁₁Are each independently the same as described above;

Ar₄₁is C_6-50The aromatic hydrocarbon (b) of (a),

R₄₁and R₄₂Are each independently C_1-10Alkyl radical, R₄₁And R₄₂It is also possible to form a hydrocarbon ring,

the carbon atom in position 41 is a quaternary carbon atom,

L₄₁is C_6-50Or a single bond bonded to other structural units,

here, R₁₂、p₁₁、p₁₂、q₁₁、q₁₂、r₁₁And s₁₁Are each independently the same as described above;

the hydrocarbon-containing compound (A) preferably has a molecular weight of 500 to 6,000.

3. The method for producing a cured film according to claim 1 or 2, wherein the aforementioned composition (i) further contains (C) a surfactant;

preferably composition (i) further comprises (D) an additive; and/or

Preferably, (D) the additive includes a crosslinking agent, a high carbon material, an acid generator, a radical generator, a photopolymerization initiator, a substrate adhesion enhancer, or a mixture thereof.

4. The method for producing a cured film according to any one of claims 1 to 3, wherein the solvent (B) comprises an organic solvent;

preferred organic solvents include hydrocarbon solvents, ether solvents, ester solvents, alcohol solvents, ketone solvents, or mixtures thereof.

5. The method for producing a cured film according to any one of claims 1 to 4, wherein the content of the (A) hydrocarbon-containing compound is 2 to 30% by mass based on the composition (i),

The content of the solvent (B) is 60 to 98 mass% based on the composition (i);

preferably, the content of the surfactant (C) is 0.01 to 10% by mass based on the hydrocarbon-containing compound (A); and/or

The content of the additive (D) is preferably 0.05 to 100% by mass based on the hydrocarbon-containing compound (A).

6. The method for producing a cured film according to any one of claims 1 to 5, wherein the hydrocarbon-containing compound (A) is a polymer, and the aldehyde derivative used in synthesizing the polymer is 0 to 30 mol% of the total of all elements used in the synthesis;

preferably, the aforementioned polymer is substantially free of secondary and tertiary carbon atoms in its main chain.

7. The method for producing a cured film according to any one of claims 1 to 6, wherein the step (3) includes the following conditions:

during plasma irradiation, the atmosphere is N₂、NF₃、H₂Fluorocarbon, rare gas, or a mixture of any of these gases, and/or an RF discharge power of 1,000 to 10,000W;

when the electron beam is irradiated, the accelerating voltage is 2kV to 200kV, and/or the irradiation amount is 100kGy to 5,000 kGy;

in the ion irradiation, the element species of the irradiated ions are hydrogen, boron, carbon, nitrogen, rare gas, or a mixture of any of these elements, the acceleration voltage is 3 to 1000kV, and/or the irradiation dose is 10 ¹³～10¹⁸ion/cm²。

8. The method for producing a cured film according to any one of claims 1 to 7, wherein the cured film formed in the step (3) has a film density increased by 5 to 75% and/or a film hardness increased by 50 to 500% as compared with the hydrocarbon-containing film formed in the step (2);

preferably, the intensity ratio R ═ I of the G band to the D band in raman spectroscopy of the cured film formed in step (3)_D/I_GMeasuring the wavelength of the laser light at 0.35-0.90 nm and 514.5 nm;

preferably, the hydrocarbon-containing film formed in step (2) is etched 5 to 200% more easily than the cured film formed in step (3); and/or

The surface resistivity of the cured film formed in the step (3) is preferably 10⁹～10¹⁶Omega □, more preferably 10¹²～10¹⁶Ω □, more preferably 10¹³～10¹⁶Ω□。

9. The method for producing a cured film according to any one of claims 1 to 8, wherein the step of forming a hydrocarbon-containing film from the composition (i) of the above (2) comprises at least any one of the following conditions:

heating at 80-800 ℃ for 30-180 seconds;

and (3) irradiating by using ultraviolet light of 10-380 nm.

10. The carbon-containing cured film has a film density of 1.3-3.2 g/cm³；

The film hardness is 1.5-20 GPa; and/or

Intensity ratio of G band to D band in Raman spectrum analysis, R ═ I_D/I_GIs 0.35-0.90, and the laser wavelength is 514.5 nm.

11. The carbon-containing cured film according to claim 10, which is formed by irradiating plasma, electron beam and/or ion;

the surface resistivity of the carbon-containing cured film is preferably 10⁹～10¹⁶Ω□；

Preferably, the carbon-containing cured film is formed by irradiating plasma to the hydrocarbon-containing film; and/or

Preferably, the hydrocarbon-containing film is formed from a composition (i) comprising (a) a hydrocarbon-containing compound, and (B) a solvent;

(A) the hydrocarbon-containing compound comprises a structural unit (a1) represented by the following formula (a 1):

here, Ar₁₁Is by R₁₁Substituted or unsubstituted C_6-60A hydrocarbon of (A), but Ar₁₁Does not contain a fused aromatic ring;

R₁₁is C_1-20A linear, branched or cyclic alkyl, amino, or alkylamino group of (a);

R₁₂i, Br or CN;

p₁₁p is a number of 0 to 5₁₂Q is a number of 0 to 1₁₁Q is a number of 0 to 5₁₂A number r of 0 to 1₁₁A number s of 0 to 5₁₁A number of 0 to 5;

p₁₁、q₁₁and r₁₁Not 0 at the same time within 1 structural unit.

12. A method of producing a resist layer over the cured film of any one of claims 1 to 11.

13. A method for producing a resist pattern by exposing and developing the resist layer according to claim 12.

14. A method of manufacturing a device comprising the method of at least one of claims 1 to 9, 12 and 13.

Technical Field

The present invention relates to a method for producing a cured film and use thereof.

Background

In the manufacturing process of semiconductors, fine processing is generally performed by a photolithography technique using a photoresist (hereinafter also simply referred to as a resist). The fine processing comprises the following steps: a thin photoresist layer is formed on a semiconductor substrate such as a silicon wafer, a mask pattern corresponding to a target device pattern is covered on the layer, the layer is exposed to active light such as ultraviolet light through the mask pattern, the exposed layer is developed to obtain a photoresist pattern, and etching treatment of the substrate is performed using the obtained photoresist pattern as a protective film, thereby forming fine irregularities corresponding to the pattern.

In semiconductor manufacturing, the area of an IC chip is reduced by increasing the number of transistors per unit area, thereby continuously reducing the cost per transistor, but this method attempts finer processing by shortening the wavelength of ultraviolet rays irradiated on a photoresist.

The use of ultraviolet rays of a single wavelength (for example, a KrF light source 248nm) causes a problem of lowering the dimensional accuracy of the resist pattern due to the influence of standing waves. Therefore, in order to solve this problem, a method of providing an underlying antireflection film is widely studied. Such a lower antireflection film is required to have a high antireflection effect.

In order to realize further microfabrication, methods using ArF light sources (193nm) and EUV (13nm) have been widely studied. In this case, if the film thickness of the resist is too thick, the resist pattern may collapse or development residue is easily generated. Therefore, there is a problem that a sufficient protective film function cannot be obtained only by the resist.

Therefore, there is a method called multilayer, in which a new protective film is formed under a photoresist, a photoresist pattern is transferred to the lower film, and the substrate is etched using the lower film as a protective film.

There are various types of multilayer protective films, but an amorphous carbon film may be used as the protective film.

As a method for improving the function of the protective film of the carbon film by applying the solution and firing, a carbon film that can withstand firing at a general firing temperature exceeding 450 ℃ is applied, and firing at 600 ℃ is exemplified. The carbon concentration in the carbon film forming liquid solid substance can be increased to improve the function of the protective film, but the carbon film forming liquid solid substance is generally balanced with other properties such as solubility.

Under such a technical environment, patent document 1 is a technique for producing a cured film by irradiating a conductive polymer precursor such as polythiophene with plasma to polymerize the conductive polymer precursor in order to obtain a film having excellent heat resistance and moisture resistance.

Patent document 2 synthesizes a monocyclic hydrocarbon-bonded compound for the purpose of film formation, solvent solubility, and heat resistance, and provides the compound for use as an underlayer film, but does not describe plasma irradiation, electron beam irradiation, or ion irradiation during film formation.

Patent document 3 has studied a method for forming a resist underlayer film having excellent etching resistance.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5746670

Patent document 2: international publication WO2018/115043

Patent document 3: japanese patent laid-open publication No. 2016-

Disclosure of Invention

Problems to be solved by the invention

The inventors believe that there are more than one problems that need to be improved. Examples of these include:

the film density of the cured film is insufficient; the film hardness of the cured film is insufficient; the intensity ratio R ═ I in Raman spectrum analysis could not be obtained_D/I_GA cured film of 0.35 to 0.9; a cured film having a hard structure such as a diamond-like carbon structure cannot be obtained; the etching resistance of the film is insufficient; an insulating cured film cannot be obtained; in the composition species used, the solubility of the solute in the solvent is insufficient; the coatability of the composition is poor; the film is oxidized in the process of plasma and electron beam treatment; during the plasma and electron beam treatment, the film disappears due to excessive scattering of the solid components of the film.

The present inventors have focused on the possibility that a carbon film as a protective film in a photolithography process can improve the function of the protective film by increasing the film density. Therefore, it is considered useful to produce carbon films containing a large amount of sp3 carbon as diamond does. At the same time, it is considered useful that such components have high solubility.

As a result of the research, the present inventors have found a manufacturing method that can obtain a high-density film having a large amount of sp3 carbon by treating a film formed of a specific hydrocarbon-containing compound with energy such as plasma or electron beam.

The present invention has been made in view of the above technical background, and provides a method for producing a cured film, comprising (1) applying a composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating plasma, electron beam and/or ions to the hydrocarbon-containing film to form a cured film.

Means for solving the problems

The method for producing a cured film according to the present invention comprises the steps of:

(1) applying composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating plasma, electron beam and/or ions to the hydrocarbon-containing film to form a cured film; with the proviso that composition (i) comprises (a) a hydrocarbonaceous compound, and (B) a solvent; (A) the hydrocarbon-containing compound comprises a structural unit (A1) represented by the following formula (A1);

Here, Ar₁₁Is by R₁₁Substituted or unsubstituted C_6-60Hydrocarbons (however Ar)₁₁Does not contain a fused aromatic ring);

R₁₁is C_1-20A linear, branched or cyclic alkyl, amino, or alkylamino group of (a);

R₁₂i, Br or CN;

p₁₁p is a number of 0 to 5₁₂Q is a number of 0 to 1₁₁Is 0 to 5Number of (a), q₁₂A number r of 0 to 1₁₁A number s of 0 to 5₁₁A number of 0 to 5;

p₁₁、q₁₁and r₁₁Not 0 at the same time in one structural unit.

In addition, the invention provides a carbon-containing cured film, the film density is 1.3-3.2 g/cm³(ii) a The film hardness is 1.5-20 GPa; and/or the intensity ratio R ═ I of the G band to the D band in Raman spectroscopy (measurement at a laser wavelength of 514.5 nm)_D/I_G0.35 to 0.90.

The present invention also provides a method of producing a resist layer over the cured film. The present invention also provides a method for producing a resist pattern by exposing and developing the resist layer. The invention further provides a method of manufacturing a device comprising any of the methods described above.

ADVANTAGEOUS EFFECTS OF INVENTION

By using the method for producing a cured film of the present invention, one or more of the following effects can be obtained.

A cured film with high film density can be obtained; a cured film with high film hardness can be obtained; the intensity ratio R ═ I in Raman spectroscopic analysis can be obtained _D/I_G0.35 to 0.9 of a cured film. A cured film with a diamond-like carbon structure can be obtained; a film having high corrosion resistance can be obtained; an insulating cured film can be obtained; in the composition used, the solubility of the solute in the solvent is good; the coating property of the composition is high; the film can be prevented from being oxidized during plasma or electron beam treatment; prevent the film from being disappeared due to excessive scattering of the film solid component during the plasma or electron beam treatment.

Since these advantageous characteristics can be obtained, the cured film according to the present invention can be applied to the manufacturing process of a fine device, and is preferably applied to the manufacture of a semiconductor, and more preferably applied to the manufacture of DRAM, 3 DNAND. The cured film of the present invention is also effective as a hard mask SOC (spin on carbon) and a core material SOC.

Detailed Description

The embodiments of the present invention will be described in detail below.

Definition of

In this specification, the definitions and examples provided in this paragraph are followed unless otherwise stated.

The singular forms "a", "an" and "the" include plural forms and mean "at least one". Elements of a concept can be represented by a plurality of species, and when a quantity (e.g., mass% or mole%) is described, the quantity refers to the sum of the plurality of species.

"and/or" includes all combinations of elements, including also use alone.

When numerical ranges are expressed as "" to "" or "" they include both endpoints, the units being generic. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

“C_x-y”、“C_x-C_y"and" C_x"etc. describe refers to the number of carbons in a molecule or substituent. E.g. C_1～6The alkyl group means an alkyl chain having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

If the polymer has multiple types of repeating units, these repeating units will copolymerize. These copolymers may be any of alternating copolymers, random copolymers, block copolymers, graft copolymers, or mixtures thereof. When the polymer or resin is represented by the structural formula, n, m, etc. shown in parentheses represent the number of repetitions.

The units for temperature are given in degrees Celsius (Celsius). For example, 20 degrees means 20 degrees celsius.

The additive refers to the compound itself having this function (for example, in the case of a base generator, the compound itself generating a base). In some embodiments, the compound is dissolved or dispersed in a solvent and added to the composition. As an embodiment of the present invention, the composition of the present invention preferably contains such a solvent as (B) the solvent or other components.

The entire contents of international publication No. WO2018/115043, international patent application No. PCT/EP2018/079621 filed on 30.10.2018, international patent application No. PCT/EP2018/085147 filed on 17.12.2018, and european patent application No. 18199921.3 filed on 05.10.2018 are incorporated herein by reference and incorporated herein as part of the present specification.

Composition comprising a metal oxide and a metal oxide

The method for manufacturing a cured film according to the present invention includes the steps of:

(1) applying composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating plasma, electron beam and/or ions to the hydrocarbon-containing film to form a cured film.

The composition (i) contains (a) a hydrocarbon-containing compound containing a structural unit (a1) represented by formula (a1) described later and (B) a solvent. The hydrocarbon-containing compound (a) may contain the structural unit (a1) or may contain other structural units. (A) When the hydrocarbon-containing compound (a) contains another structural unit and the hydrocarbon-containing compound (a) is a polymer, it is a preferable embodiment that the structural unit (a1) is copolymerized with the other structural unit. In a preferred embodiment of the present invention, the hydrocarbon-containing compound (a) is substantially composed only of the constituent unit (a 1). However, terminal modifications are permissible.

Here, the hydrocarbon-containing film is preferably a resist underlayer film, more preferably BARC (underlayer anti-reflection film) or SOC, and still more preferably SOC. One embodiment of the present invention includes a hard mask SOC and a core material SOC.

(A) Hydrocarbon-containing compound

The hydrocarbon-containing compound (a) according to the present invention contains a structural unit (a1) represented by the following formula (a 1).

Ar₁₁Is by R₁₁Substituted or unsubstituted C_6-60The hydrocarbon of (1). But Ar is₁₁Does not contain a fused aromatic ring. As preferred Ar₁₁Examples thereof include 9, 9-diphenylfluorene, 9-phenylfluorene, phenyl and C_6-60Straight polyphenylene and C_6-60Branched chainPolyphenylene, which may each independently be R₁₁Substituted or unsubstituted.

R₁₁Is C_1-20A linear, branched or cyclic alkyl, amino, or alkylamino group. R₁₁Preferably C_1-10A linear, branched or cyclic alkyl group, or an alkylamino group. R₁₁More preferably C_1-3Straight chain alkyl group of (1), C_1-3Branched alkyl, cyclopentyl, cyclohexyl or dimethylamino.

(A) When the hydrocarbon-containing compound has a plurality of structural units (A1), R₁₁Can be used as a linking group in Ar₁₁And bonding the two. By substitution of one Ar₁₁R of (A) to (B)₁₁One or more than one; preferably one.

In one structural unit (A1), the radicals in parentheses (e.g., p)₁₁Groups in parentheses) may be substituted with R ₁₁And (4) bonding. In this case, R₁₁As a linking group with Ar₁₁Bonded to the group.

While not intended to limit or otherwise depart from the scope of the present invention, Ar is at least one member selected from the group consisting of₁₁Embodiments containing naphthyl groups (e.g., naphthols) are prone to oxidation or difficult to reconstitute cured films based on plasma, electron beam, and/or ion irradiation, and are therefore considered disadvantageous.

R₁₂I, Br or CN; preferably I or Br, more preferably I.

p₁₁Is a number of 0 to 5. Here, as an embodiment of the present invention, (a) the hydrocarbon-containing compound may have only one of 2 kinds (a1) as a structure. May be in the form of: ar (Ar)₁₁Are both phenyl, one Ar₁₁P of (a)₁₁1, another Ar₁₁P of (a)₁₁2. In this case, p as a whole₁₁1.5. In this specification, the same applies to numbers unless otherwise specified.

p₁₁Preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; more preferably 1. p is a radical of₁₁0 is also a preferred embodiment of the present invention.

p₁₂Is a number of 0 to 1(ii) a Preferably 0 or 1; more preferably 1.

q₁₁A number of 0 to 5; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; more preferably 1. q. q.s₁₁0 is also a preferred embodiment of the present invention.

q₁₂A number of 0 to 1; preferably 0 or 1; more preferably 1.

r₁₁A number of 0 to 5; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; more preferably 1. r is₁₁0 is also a preferred embodiment of the present invention.

s₁₁A number of 0 to 5; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; more preferably 1. s₁₁0 is also a preferred embodiment of the present invention.

p₁₁、q₁₁And r₁₁Not all of the 1 structural units are 0 at the same time.

The structural unit (A1) according to the present invention may be more specifically a structural unit (A1-1), (A1-2) and/or (A1-3) represented by the following formula (A1-1), (A1-2) and/or (A1-3). As will be described separately below.

As a preferred embodiment of the present invention, the structural unit (A1) is the structural unit (A1-1).

The structural unit (A1-1) is represented by the formula (A1-1).

Ar₂₁Is C_6-50The aromatic hydrocarbon of (1); preferably phenyl. Ar (Ar)₂₁The phenyl group can ensure solubility of the hydrocarbon-containing compound (a) in a solvent, and can be expected to have advantageous effects such as the ability to form a thick film.

R₂₁、R₂₂And R₂₃Are each independently C_6-50An aromatic hydrocarbon of (a), hydrogen, or a single bond bonded to other structural units; preferably phenyl, hydrogen, or a single bond to another structural unit; more preferably phenyl or a single bond to other structural units; further preferred is a phenyl group.

n₂₁Is an integer of 0 or 1; preferably 0.

Ar₂₁、R₂₁、R₂₂And R₂₃Does not contain a fused aromatic ring.

R₁₂、p₁₁、p₁₂、q₁₁、q₁₂、r₁₁And s₁₁The definitions and preferred embodiments of (a) are independently the same as above.

Although not intended to limit the present invention, specific examples of the (A) hydrocarbon-containing compound having the structural unit (A1-1) are listed below.

As a more preferred embodiment of the present invention, the structural unit (A1-1) is the structural unit (A1-1-1). The structural unit (A1-1-1) is represented by the formula (A1-1-1).

p₁₁、p₁₂、q₁₁、q₁₂、r₁₁And s₁₁The definitions and preferred examples of (a) are the same as those described above. But satisfies 1. ltoreq. p₁₁+q₁₁+r₁₁≤4。

The structural unit (A1-2) is represented by the formula (A1-2).

L₃₁And L₃₂Each independently is a single bond or phenylene; preferably a single bond.

n₃₁、n₃₂、m₃₁And m₃₂Each independently is a number from 0 to 6; preferably an integer of 0 to 3. n is₃₁+n₃₂Either 5 or 6 is a preferred embodiment. L is₃₁When it is a single bond, m₃₁＝1。L₃₂When it is a single bond, m₃₂＝1。

R₁₂、p₁₁、p₁₂、q₁₁、q₁₂、r₁₁And s₁₁The definitions and embodiments of (a) are the same as those described above.

Although not intended to limit the present invention, specific examples of the (A) hydrocarbon-containing compound having the structural unit (A1-2) are shown below.

The structural unit (A1-3) is represented by the formula (A1-3).

Ar₄₁Is C_6-50The aromatic hydrocarbon of (1); preferably phenyl.

R₄₁And R₄₂Are each independently C_1-10An alkyl group; preferably straight chain C_1-6An alkyl group.

R₄₁And R ₄₂A hydrocarbon ring may be formed; preferably forming a saturated hydrocarbon ring.

The carbon atom at position 41 is a quaternary carbon atom.

L₄₁Is C_6-50Or a single bond bonded to other structural units; preferably phenylene or a single bond to another structural unit; more preferably a single bond to other structural units.

R₁₂、p₁₁、p₁₂、q₁₁、q₁₂、r₁₁And s₁₁Are independently the same as described above

Although not intended to limit the present invention, specific examples of the (A) hydrocarbon-containing compound having the structural unit (A1-3) are shown below.

When the (a) hydrocarbon-containing compound of the present invention is a polymer, as a preferred embodiment of the present invention, the aldehyde derivative used in synthesizing the (a) hydrocarbon-containing compound is preferably 0 to 30 mol% (more preferably 0 to 15 mol%, further preferably 0 to 5 mol%, further preferably 0 mol%) based on the sum of all elements used for the synthesis. Examples of the aldehyde derivative include formaldehyde.

The use of ketone derivatives instead of aldehyde derivatives is a preferred embodiment of the present invention.

The polymer so synthesized may be characterized by a main chain containing no or little secondary and tertiary carbon atoms. As a preferred embodiment of the present invention, the aforementioned polymer is substantially free of secondary carbon atoms and tertiary carbon atoms in its main chain. While not being bound by theory, it is expected that this will increase the heat resistance of the formed film while ensuring the solubility of the polymer. However, for terminal modification, it is permissible to include secondary and tertiary carbon atoms at the terminals of the polymer.

In one embodiment of the present invention, the molecular weight of the hydrocarbon-containing compound (A) is 500 to 6,000, more preferably 500 to 4,000. When the (a) hydrocarbon-containing compound is a polymer, a weight average molecular weight (Mw) is used as the molecular weight. In the present invention, Mw may be measured by Gel Permeation Chromatography (GPC). In the same measurement, a 40 degrees C GPC column, 0.6mL/min elution solvent tetrahydrofuran, single dispersion of polystyrene as standard is the preferred example. The same applies below.

The hydrocarbon-containing compound (A) is preferably 2 to 30% by mass, more preferably 5 to 30% by mass, based on the composition (i); further preferably 5 to 25 mass%; further preferably 10 to 25 mass%.

(B) Solvent(s)

The composition (i) of the present invention comprises (B) a solvent. (B) The solvent is not particularly limited as long as it can dissolve the components to be mixed. (B) The solvent preferably comprises an organic solvent, and more preferably the aforementioned organic solvent comprises a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a mixture thereof.

Specific examples of the solvent (B) include water, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2, 4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, trimethylbenzene, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2, 6-dimethylheptanol-4, N-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3, 5-trimethylcyclohexanol, benzyl alcohol, benzylmethanol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1, 3-butanediol, pentanediol-2, 4, 2-methylpentanediol-2, 4, hexanediol-2, 5, heptanediol-2, 4, 2-ethylhexanediol-1, 3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, acetone, methyl ethyl ketone, methyl n-acetone, methyl n-butanone, diethyl ketone, methyl isobutyl ketone, methyl n-pentanone, ethyl n-butanone, methyl n-hexanone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2, 4-pentadecanedione, 2, 3-methyl-cyclohexanol, 3-pentanediol, 2, 4-methylpentanediol, 2, 5-trimethylcyclohexanol, benzyl alcohol, 2, 4-heptanediol, 2, 4-pentanediol, 2, 4-hexanediol, 2, 4-propanediol, and methyl-propanediol, and a mixture thereof, Acetonylacetone, diacetone alcohol, acetophenone, fennel ketone, diethyl ether, isopropyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1, 2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether, and mixtures thereof, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, anisole, diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate (n-butyl acetate, nBA), isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and mixtures thereof, Diethylene glycol mono N-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, N-butyl propionate, isoamyl propionate, diethyl oxalate, di-N-butyl oxalate, methyl lactate, Ethyl Lactate (EL), N-butyl lactate, N-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N-dimethylformamide, N-diethylformamide, acetamide, N-methylacetamide, N-propylmethyl ether acetate, N-butylmethyl ether acetate, N-ethylmethyl ether acetate, N-dimethylformamide, N-diethylformamide, N-ethylformamide, N-N-ethylformamide, N-methylacetamide, N-methyl acetamide, N-methylacetamide, N-propylmethyl acetamide, N-methyl acetamide, N-methyl acetamide, N-N-methyl acetamide, N-N-butyl ether acetate, N-butyl ether, N-methyl ether, N-butyl ether, N-ethyl acetate, N-butyl ether, N-ethyl phthalate, N-methyl ether, N-dimethyl-phthalate, N-methyl ether, N-phthalate, N-butyl ether acetate, N-dimethyl-phthalate, N-methyl ether acetate, N-phthalate, N-methyl-phthalate, N-1-methyl-phthalate, N-methyl-butyl acetate, N-methyl-phthalate, N-butyl acetate, N-phthalate, N-butyl ether acetate, N-2-methyl-butyl acetate, N-2-phthalate, N-methyl-N-methyl-2-methyl-phthalate, N-methyl-2-methyl-phthalate, N-methyl, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane and 1, 3-propane sultone. These solvents may be used alone or in combination of two or more.

It is a preferred embodiment of the present invention that (B) the solvent consists essentially of only those selected from the above-mentioned specific examples. However, it is permissible that the (B) solvent contains a small amount of a solvent for dissolving the solid components of the surfactant, the additive.

As the (B) solvent, PGMEA, PGME, anisole, EL, nBA, DBE or any mixture thereof is preferable; more preferably PGMEA, PGME or mixtures thereof; PGMEA is further preferred. In the case of mixing 2 types, the mass ratio of the 1 st solvent to the 2 nd solvent is preferably 95:5 to 5:95 (more preferably 90:10 to 10:90, still more preferably 80:20 to 20: 80).

In relation to other layers and films, (B) the solvent contains substantially no water is an embodiment. For example, the amount of water in the entire solvent (B) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably 0.001% by mass or less. (B) The solvent contains no water (0 mass%) is also a preferred embodiment.

The solvent (B) is preferably 60 to 98 mass% based on the composition (i); more preferably 60 to 95 mass%; further preferably 70 to 95 mass%; more preferably 70 to 90% by mass.

(C) Surface active agent

The composition (i) according to the present invention may further contain (C) a surfactant.

The coating property can be improved by containing a surfactant.

In the present invention, the (C) surfactant means a compound itself having the above-mentioned function. The compound may be dissolved or dispersed in a solvent and contained in the composition, but such a solvent is preferably contained in the composition as the (B) solvent or other component. Hereinafter, the same applies to various additives that may be contained in the composition.

Examples of the surfactant that can be used in the present invention include (I) an anionic surfactant, (II) a cationic surfactant, and (III) a nonionic surfactant. More specifically preferred are (I) alkyl sulfonates, alkyl benzene sulfonic acids, and alkyl benzene sulfonates, (II) chlorinated dodecylpyridines and lauryl methyl ammonium chloride, and (III) polyoxyethylene octyl ethers, polyoxyethylene lauryl ethers, and polyoxyethylene acetylene glycol ethers, fluorosurfactants, such as Fluorad (sumitomo 3M), megafac (dic), Surflon (asahi nitro) or organosilicone surfactants (e.g. KP341, shin-Etsu chemical industry).

Preferably, the surfactant (C) is 0.01 to 10% by mass based on the hydrocarbon-containing compound (A); more preferably 0.05 to 10 mass%; further preferably 0.05 to 5 mass%; more preferably 0.05 to 1 mass%.

(D) Additive agent

The compositions (i) according to the invention may also further comprise (D) additives. (D) The additive is a component other than (A), (B) and (C). Preferably (D) the additive comprises a crosslinking agent, a high carbon material, an acid generator, a radical generator, a photopolymerization initiator, a substrate adhesion enhancer or a mixture thereof. More preferably, (D) the additive includes a crosslinking agent, an acid generator, a radical generator, a photopolymerization initiator, a substrate adhesion enhancer, or a mixture thereof. As a more preferable additive (D), a crosslinking agent is exemplified. In another embodiment of the present invention, a high carbon material is used as the additive (D).

The crosslinking agent is useful for the following purposes: the hydrocarbon-containing film of the present invention has improved film-forming properties, eliminates intermixing with an upper layer film (e.g., a silicon-containing intermediate layer and a resist), and eliminates diffusion of low-molecular components into the upper layer film.

Examples of the crosslinking agent include a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one group selected from a hydroxymethyl group, an alkoxymethyl group and an acyloxymethyl group, an epoxy compound, a thioepoxy compound, an isocyanate compound, an azide compound, an alkenyl ether group and other compounds containing a double bond. They can also be used as additives and can also be introduced as side groups into the polymer side chains. Furthermore, hydroxyl group-containing compounds can also be used as crosslinking agents.

Of the above compounds, examples of the epoxy compound include tris (2, 3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethyleneethane triglycidyl ether. Specific examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound of hexamethylolmelamine in which 1 to 6 methylol groups are methylolated, a mixture thereof, and a compound of hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound of hexamethylolmelamine in which 1 to 6 methylol groups are acyloxymethylated, or a mixture thereof. The guanamine compound includes tetramethylol guanamine, tetramethoxymethyl guanamine, a compound in which 1 to 4 methylol groups of the tetramethylol guanamine are methylolated, and a mixture thereof, tetramethoxyethyl guanamine, tetraalkoxyguanamine, a compound in which 1 to 4 methylol groups of the tetramethylol guanamine are acyloxymethylated, and a mixture thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyol glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are methylolated, a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethyl groups, and a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylols of tetramethylol urea are methoxymethylated, a mixture thereof, and tetramethoxyethyl urea.

Examples of the compound having an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1, 2-propylene glycol divinyl ether, 1, 4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1, 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

The molecular weight of the crosslinking agent is preferably 100 to 480, more preferably 200 to 400, and further preferably 300 to 380.

Although the present invention is not intended to be limited, specific examples of the crosslinking agent include the following.

The high carbon material is a molecule containing many carbon atoms per molecule, and is a solid component remaining in the hydrocarbon-containing membrane of the present invention. By adding a high carbon material, the etching resistance can be improved. The high carbon material itself does not necessarily have to be capable of forming a film as long as it can form a hydrocarbon-containing film together with the (a) hydrocarbon-containing compound.

Although not intended to limit the present invention, specific examples of the high carbon material include isoanthrone violet, 2, 7-bis (1-pyrenyl) -9,9' -spirobis [ 9H-fluorene ]9, 9-bis [4- [ di (2-naphthyl) amino group]Phenyl radical]Fluorene, 9-bis [4- [ N- (1-naphthyl) anilino group]Phenyl radical]Fluorene, 3,4,9, 10-perylene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic diimide, benzanthrone, perylene, coronene, 5, 12-naphthonaphtho quinone, 6, 13-pentabenzoquinone, fullerene C₆₀、C₆₀MC₁₂(C₆₀Condensation of N-methylpyrrolidine) -m-C₁₂Phenyl), ICBA (indene-C)₆₀Bis adduct), N, 2-diphenyl [60 ]]Fullerene pyrrolidine, PCBM (phenyl-C61-methyl butyrate), PCBB (phenyl-C61-butyl butyrate), N-phenyl-2-hexyl [ 60%]Fullerene pyrrolidine, and the like.

In the present invention, the additive (D) is preferably 0.05 to 100% by mass based on the hydrocarbon-containing compound (A); more preferably 0.05 to 25 mass%; further preferably 0.05 to 20 mass%; more preferably 0.05 to 15 mass%; more preferably, the content is 0.05 to 10% by mass.

Method for producing cured film

The method for producing a cured film of the present invention includes the following steps.

(1) Applying composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating plasma, electron beam and/or ions to the hydrocarbon-containing film to form a cured film.

In the present invention, as a method of applying the composition (i), there can be mentioned a coating method using a spin coater, a coater or the like. The composition (i) of the present invention facilitates embedding of a pattern on a substrate. The substrate and composition (i) are preferably in direct contact with the upper part of the substrate, but may also be coated by other films.

The method for forming a hydrocarbon-containing film from the composition (i) includes ultraviolet irradiation and/or heating, and preferably heating.

PreferablyThe conditions of ultraviolet irradiation were: using ultraviolet rays with a wavelength of 10 to 380nm (more preferably 10 to 200nm) at a wavelength of 100 to 10,000mJ/cm²The cumulative irradiation amount of (3) is irradiated with light.

Air is suitable as an atmosphere for ultraviolet irradiation and heating. The oxygen concentration may also be reduced to prevent oxidation of the present composition (i) and/or the hydrocarbon-containing membrane of the present invention. For example, by introducing an inert gas (N)₂Ar, He, or a mixture thereof) may be set to 1,000ppm or less (preferably 100ppm or less).

When the hydrocarbon-containing film is formed by heating, the heating conditions may be appropriately selected from the range of 80 to 800 ℃ (preferably 200 to 700 ℃, more preferably 300 to 600 ℃) and 30 to 180 seconds (preferably 30 to 120 seconds) for the heating time. While not being bound by theory, it is believed that by performing high temperature heating, crosslinking of groups such as acetylene groups that crosslink between polymers can be promoted well, which helps increase the density of the cured film.

The heating may be carried out in multiple steps (step baking). The hydrocarbon-containing film may be formed by heating alone, but is preferably combined with ultraviolet irradiation.

The hydrocarbon-containing film is irradiated with plasma, electron beam, and/or ions to form a cured film. While not being bound by theory, it is believed that these irradiations dissociate and re-bond the chemical bonds of the hydrocarbon-containing film and reconstitute into a cured film having a diamond-like carbon structure, thereby contributing to an increase in hardness, density.

As an embodiment of the present invention, it is also included that the composition (i) is irradiated with plasma, electron beam and/or ion immediately after coating, thereby forming a cured film. That is, the present invention also includes an embodiment in which the above-described steps (2) and (3) are performed almost simultaneously in one operation (step).

The plasma irradiation may be performed by a known method. For example, patent No. 5746670 (patent document), "Improvement of the wigging profile of spin-on carbon mask by H₂plasma stream "(j.vac.sci.technol.b 26(1), Jan/Feb2008, p67-71, non-patent literature).

The RF discharge power may be selected from 1,000 to 10,000W, and more preferably 1,000 to 5,000W.

As the gas atmosphere, N is mentioned₂、NF₃、H₂Rare gases, fluorocarbons; preferable examples thereof include Ar, Ne and NF₃、H₂、CF₄、CHF₃、CH₂F₂、CH₃F、C₄F₆、C₄F₈And the like. These gases may be mixed with 2 or more kinds of gases. Using a catalyst containing no O ₂The gas atmosphere of (2) can also expect the effects of the present invention, and is an advantageous point of the present invention.

The time can be selected from 10-240 seconds.

The pressure may be appropriately selected.

The electron beam irradiation may be performed by a known method. Examples thereof include a method described in "technology of an electron beam irradiation apparatus and its use" (7.7.2012, SEI technical review, No. 181, p50-57, non-patent document).

The accelerating voltage can be selected from 2 to 200 kV.

The irradiation dose can be selected from 100 to 5,000 kGy.

The electron beam irradiation is preferably performed while heating. In this case, the temperature may be selected from 80 to 800 ℃ (preferably 200 to 700 ℃, more preferably 300 to 600 ℃).

The ion irradiation may be performed by a known method. Examples thereof include "Raman spectroscopy and microhardness of ion-implanted a-C: the method described in H-films (Ceramics int.26(1),2000, p29-32, non-patent document). One preferred embodiment of the ion irradiation of the present invention is ion implantation.

The element species of the irradiated ions include hydrogen, boron, carbon, nitrogen, and a rare gas; preferably boron, carbon, nitrogen, neon, argon, etc.; more preferably carbon, nitrogen or the like. These gases may be mixed with 2 or more kinds of gases.

The accelerating voltage can be selected from 3 to 1000 kV. The acceleration voltage is more preferably 5 to 750kV, and still more preferably 10 to 500 kV.

The irradiation dose can be from 10¹³～10¹⁸ion/cm²To select. The irradiation dose is more preferably 5X 10¹³～5×10¹⁷ion/cm²More preferably 10¹⁴～10¹⁷ion/cm²。

The ion irradiation may also be performed while heating the device chamber. In this case, the temperature may be 500 ℃ or lower. In the case of heating after plasma irradiation and electron beam irradiation, the heating temperature may be appropriately selected from the range of 80 to 800 ℃ (preferably 200 to 700 ℃, more preferably 300 to 600 ℃), and the heating time may be appropriately selected from the range of 30 to 180 seconds (preferably 30 to 120 seconds). Although not being bound by theory, it is thought that dangling bonds may be bonded by heating at a high temperature after plasma and electron beam irradiation, and the density of the cured film may be increased.

As the irradiation apparatus, Tactras Vigus, EB-Engine (Hamamatsu photonics), EXCEED2300AH (Nissan ion machine) can be used. The effects of the present invention can be exerted by selecting a device and setting conditions.

In one embodiment of the present invention, the cured film formed in the step (3) has an advantageous effect of increasing the film density by 5 to 75% and/or increasing the film hardness by 50 to 500% as compared with the hydrocarbon-containing film formed in the step (2).

In addition, the intensity ratio R of the G band to the D band in raman spectroscopy (measurement of the laser wavelength 514.5 nm) of the cured film formed in the step (3) is I_D/I_GCan be 0.35 to 0.90. Without being bound by theory, it is believed that it is possible to have a diamond-like carbon structure.

Further, it is considered that the hydrocarbon-containing film formed in the step (2) is more easily etched by 5 to 200% (preferably 5 to 100%, more preferably 5 to 50%, and further preferably 10 to 50%) than the cured film formed in the step (3) (the latter cured film has higher etching resistance).

The surface resistivity of the cured film formed in the step (3) is preferably 10⁹～10¹⁶Omega □ (more preferably 10)¹²～10¹⁶Ω □, more preferably 10¹³～10¹⁶Ω □). That is, (A) containsThe hydrocarbon compound is not a conductive polymer precursor, and the cured film of the present invention is not a conductive polymer film.

As one embodiment of the present invention, a carbon-containing cured film having the following features is provided.

The film density is 1.3 to 3.2g/cm³；

The film hardness is 1.5-20 GPa; and/or

Intensity ratio of G band to D band in Raman spectrum analysis (measurement of laser wavelength 514.5 nm) is represented by R ═ I_D/I_G0.35 to 0.90.

Preferably, the carbon-containing cured film is formed by plasma, electron beam and/or ion irradiation. More preferably, the film has a surface resistivity of 10 ⁹～10¹⁶Ω □ (Ohm square). As a composition for forming such a carbon-containing cured film, use of the aforementioned composition (i) is a more preferred embodiment of the present invention.

As a film known as SOC, there is a film described in The roll of underwlarers in EUVL (Journal of Photopolamer Science and Technology Vol.31, Number 2, p209-214,2018), but The film density is not more than 1.05 to 1.32g/cm³Left and right.

The film density of the cured film or the carbon-containing cured film is preferably 1.3 to 3.2g/cm³(more preferably 1.4 to 3.2 g/cm)³More preferably 1.5 to 2.8g/cm³). It is considered that the high film density of the cured film contributes to the increase in etching resistance. Further, if the stress of the cured film is too strong, stress is applied to the substrate, which is considered to be disadvantageous.

The film density can be measured, for example, by the methods described in examples, and can be adjusted by appropriately combining known methods.

The film of the present invention preferably has a film hardness of 1.5 to 20GPa (more preferably 1.7 to 20GPa, still more preferably 2.0 to 15GPa, and still more preferably 2.0 to 10 GPa).

The measurement of the film hardness can be carried out by, for example, the methods described in examples, and can be adjusted by appropriately combining known methods.

The films of the present invention are preferably subjected to Raman spectroscopy (laser wavelength 514) 5nm measurement) of the intensity ratio of the G band to the D band, R ═ I_D/I_GIs 0.35 to 0.90 (more preferably 0.40 to 0.90, still more preferably 0.40 to 0.80, still more preferably 0.45 to 0.70).

The raman spectroscopy can be adjusted by using, for example, the methods described in examples, and appropriately combining known methods (for example, japanese patent No. 3914179 (patent document)).

< method for producing resist film, resist pattern >

A resist film may also be produced over the cured film produced by the method of the present invention.

The method of manufacturing the resist film of the present invention includes:

(4) applying a resist composition over the cured film;

(5) the resist composition is heated to form a resist layer.

Further, the present invention can also produce a resist pattern from the aforementioned resist film. The method of manufacturing a resist pattern of the present invention includes:

(6) exposing the resist layer;

optionally, (7) subjecting the resist layer to post-exposure heating; and

(8) the resist layer is developed.

For clarity, numerals in parentheses indicate order. For example, the step (4) is performed before the step (5).

Hereinafter, one embodiment of a method for producing a resist film or a resist pattern of the present invention will be described.

The resist composition is applied over a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc.) by an appropriate method. Here, in the present invention, the upper portion includes a case where the upper portion is directly formed and a case where the upper portion is formed with another layer interposed therebetween. For example, a planarizing film or a resist underlayer film may be formed directly above the substrate, and a resist composition may be applied directly above the planarizing film or the resist underlayer film. The application method is not particularly limited, and a coating method by a spinner and a coater can be exemplified. After coating, a resist layer is formed by heating. (5) The heating of (2) is performed by a hot plate, for example. The heating temperature is preferably 60 to 140 ℃, and more preferably 90 to 110 ℃. The temperature here is a heating atmosphere, for example, a heating surface temperature of a hot plate. The heating time is preferably 30 to 900 seconds, and more preferably 60 to 300 seconds. The heating is preferably performed in the atmosphere or nitrogen atmosphere.

The film thickness of the resist layer can be appropriately selected according to the purpose. The thickness of the resist layer may be made larger than 1 μm.

The resist layer is exposed through a predetermined mask. The wavelength of the light used for exposure is not particularly limited, and exposure is preferably performed with light having a wavelength of 190 to 440nm (more preferably 240 to 370 nm). Specifically, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), i-line (wavelength 365nm), h-line (wavelength 405nm), g-line (436nm), and the like can be used. The wavelength is more preferably 240 to 440nm, still more preferably 360 to 440nm, and still more preferably 365 nm. These wavelengths are allowed to be within a range of ± 1%.

After exposure, post-exposure heating (post-exposure baking, hereinafter sometimes referred to as PEB) may be optionally performed. (7) The heating of (2) is performed by a hot plate, for example. The temperature of heating after exposure is preferably 80-160 ℃, more preferably 105-115 ℃, and the heating time is 30-600 seconds, preferably 60-200 seconds. The heating is preferably performed in the atmosphere or nitrogen atmosphere.

After PEB, development was performed using a developer. As the developing method, a method conventionally used for developing a photoresist, for example, a spin-on immersion developing method, a dip developing method, or a swing dip developing method can be used. The developer may be an aqueous solution containing an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium silicate, an organic amine such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, or triethylamine, or a quaternary amine such as tetramethylammonium hydroxide (TMAH), and preferably a 2.38 mass% aqueous TMAH solution. A surfactant may also be added to the developer. The temperature of the developing solution is preferably 5-50 ℃, more preferably 25-40 ℃, and the developing time is preferably 10-300 seconds, more preferably 30-60 seconds. After development, washing or rinsing may be carried out, if necessary.

As one embodiment of the present invention, various substrates as a base may be patterned using the manufactured resist pattern as a mask. The substrate may be processed directly using the resist pattern as a mask, or may be processed via an intermediate layer. For example, the resist underlayer film may be patterned using the resist pattern as a mask, and the substrate may be patterned using the resist underlayer film as a mask. The processing may be performed by a known method, and a dry etching method, a wet etching method, an ion implantation method, a metal plating method, or the like may be used. Electrodes and the like may also be wired on the patterned substrate.

Substrate

In the present invention, examples of the substrate include a semiconductor wafer, a glass substrate for a liquid crystal display device, a glass substrate for an organic EL display device, a glass substrate for a plasma display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for an optical disk, a glass substrate for a photomask, a substrate for a solar cell, and the like. The substrate may be a raw substrate (e.g., a bare wafer) or a processed substrate (e.g., a pattern substrate). The substrate may be formed by stacking a plurality of layers. Preferably the surface of the substrate is a semiconductor. The semiconductor may be composed of an oxide, a nitride, a metal, or any combination thereof. Preferably, the substrate surface is selected from the group consisting of Si, Ge, SiGe, Si₃N₄、TaN、SiO₂、TiO₂、Al₂O₃、SiON、HfO₂、T₂O₅、HfSiO₄、Y₂O₃、GaN、TiN、TaN、Si₃N₄NbN, Cu, Ta, W, Hf, Al.

Device with a metal layer

Devices can be fabricated by further processing the substrates of the present invention. Examples of the device include a semiconductor device, a liquid crystal display device, an organic EL display device, a plasma display device, and a solar cell device. The device is preferably a semiconductor. These processes may be performed by known methods. After forming the device, the substrate may be cut into chips, connected to a lead frame, and encapsulated with resin as necessary. One example of such a packaged product is a semiconductor.

The present invention will be described below with reference to examples. The present invention is not limited to these examples.

< Synthesis of P0 >

A reactor equipped with a stirrer, a Liebig condenser, a heating device, a nitrogen inlet tube and a temperature control device was prepared. To a reactor, 9-fluorenone (200 parts, tokyo chemical industry), 9-bis (4-hydroxyphenyl) fluorene (2333 parts, Osaka Gas Chemicals) and dichloromethane (10430 parts) were added, and the mixture was kept at 40 ℃ under nitrogen atmosphere with stirring. Then, trifluoromethanesulfonic acid (92 parts, mitsubishi material electronics chemistry) and 3-mercaptopropionic acid (6 parts, tokyo chemical industry) dissolved in dichloromethane (200 parts) were slowly added to the reactor, maintained at 40 ℃ and stirred, and allowed to react for 4 hours. After completion of the reaction, the solution was returned to room temperature, water was added to the reaction solution, and excess 9, 9-bis (4-hydroxyphenyl) fluorene was removed by filtration and washed with dichloromethane. The trifluoromethanesulfonic acid was removed by washing the dichloromethane solution thoroughly with water. Then, methylene chloride was distilled off at 40 ℃ and 10mmHg to obtain P0(2111 parts). When the molecular weight was measured by GPC (tetrahydrofuran), the number average molecular weight Mn was 533Da, the weight average molecular weight Mw was 674Da, and the molecular weight distribution (Mw/Mn) was 1.26.

< Synthesis example 1: synthesis of P1

A reactor equipped with a stirrer, a Liebig condenser, a heating device, a nitrogen inlet and a temperature control device was prepared. P0(350 parts), potassium carbonate (562 parts) and acetone (1414 parts) were added to the reactor, and the mixture was kept at 56 ℃ under nitrogen with stirring. Allyl bromide (500 parts, tokyo chemical industries) was then slowly added to the reactor, maintained at 56 ℃ and stirred, and allowed to react for 3 hours. After completion of the reaction, the solution was returned to room temperature, excess potassium carbonate and salt were removed by filtration, and the precipitate was washed with acetone. Then, acetone was distilled off at 40 ℃ under 10 mmHg. The resulting solid was dissolved in ethyl acetate (3000 parts), and the ethyl acetate solution was washed sufficiently with water to remove metal impurities. Ethyl acetate was distilled off at 40 ℃ under 10mmHg, and the resulting solid was dissolved in acetone (600 parts). The acetone solution was then added to n-heptane (6000 parts), and the solid was filtered and dried at 100 ℃ under 10mmHg to give P1(345 parts). When the molecular weight was measured by GPC (tetrahydrofuran), the number average molecular weight Mn was 671Da, the weight average molecular weight Mw was 833Da, and the molecular weight distribution (Mw/Mn) was 1.32.

< Synthesis example 2: synthesis of P2

A reactor equipped with a stirrer, a Liebig condenser, a heating device, a nitrogen inlet and a temperature control device was prepared. P0(200 parts), potassium carbonate (323 parts) and acetone (616 parts) were added to the reactor, and the mixture was kept at 56 ℃ under nitrogen with stirring. Then, 3-bromo-1-propyne (278 parts) was slowly added to the reactor, maintained at 56 ℃ with stirring, and allowed to react for 3 hours. After completion of the reaction, the solution was returned to room temperature, excess potassium carbonate and salt were removed by filtration, and the precipitate was washed with acetone. Then, acetone was distilled off at 40 ℃ under 10 mmHg. The resulting solid was dissolved in ethyl acetate (820 parts), and the ethyl acetate solution was sufficiently washed with water to remove metal impurities. After ethyl acetate was distilled off at 40 ℃ and 10mmHg, the obtained solid (185 parts) was dissolved in acetone (185 parts). Then, methanol (1850 parts) was added to the acetone solution, and the solid was filtered and dried at 100 ℃ under 10mmHg to give P2(76 parts). When the molecular weight was measured by GPC (tetrahydrofuran), Mn was 789Da, Mw was 1054Da, and Mw/Mn was 1.34.

Preparation example 1 of composition 1

P1(13.9 parts) and Megafac R-41(0.1 part, DIC) were added to propylene glycol 1-monomethyl ether 2-acetate (PGMEA) (86 parts) and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The resulting mixture was filtered through a 0.2 μm fluororesin filter (Merck Millipore, SLFG025NS) to obtain composition 1.

Preparation example 2 of composition 2

P2(11.9 parts) and Megafac R-41(0.1 part) were added to PGMEA (88 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

Composition 2 was obtained by filtration through a 0.2 μm fluororesin filter.

Preparation example 3 of composition 3

P3(13.9 parts) and Megafac R-41(0.1 part) having the following structures were added to PGMEA (86 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

Composition 3 was obtained by filtration through a 0.2 μm fluororesin filter.

Preparation example 4 of composition 4

P4(14.9 parts) and Megafac R-41(0.1 part) having the structures shown below were added to PGMEA (85 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 4.

Preparation example 5 of composition 5

P5(14.9 parts) and Megafac R-41(0.1 part) having the structures shown below were added to PGMEA (85 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The resulting mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 5.

Preparation example 6 of composition 6

P6(13.9 parts) and Megafac R-41(0.1 part) having the following structures were added to PGMEA (86 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 6.

Preparation example 7 of composition 7

P0(24.9 parts) and Megafac R-41(0.1 part) described above were added to PGMEA (75 parts), and the mixture was stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 7.

Preparation example 8 of composition 8

P7(12.9 parts) having the structure shown below, P8(1 part) having the structure shown below, and Megafac R-41(0.1 part) were added to PGMEA (87 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 8.

Preparation of composition 9 example 9

P2(8.9 parts), P9(5 parts) having the structure shown below, and Megafac R-41(0.1 part) were added to PGMEA (85 parts), and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 9.

Preparation example 10 of composition 10

P2(2.9 parts) and Megafac R-41(0.1 part) were added to PGMEA (97 parts) and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The resulting mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 10.

Preparation of composition 11 example 11

P2(3.9 parts) and Megafac R-41(0.1 part) were added to PGMEA (96 parts) and stirred at room temperature for 1 hour. Complete dissolution of the solute was confirmed visually.

The resulting mixture was filtered through a 0.2 μm fluororesin filter to obtain composition 11.

Formation of hydrocarbon-containing films

Each composition was coated on a silicon bare wafer using CLEAN TRACK ACT 12(Tokyo Electron) at a speed of 1,500 rpm. The wafer was baked at 250 ℃ for 60 seconds under an air atmosphere, and further baked at 450 ℃ for 120 seconds under a nitrogen atmosphere. Thereby obtaining a hydrocarbon-containing film from the composition.

Formation of cured film (in the case of plasma treatment)

The wafer on which the above hydrocarbon-containing film was formed was subjected to plasma treatment for 2 minutes using Tactras Vigus (Tokyo Electron).

Formation of cured film (in the case of Electron Beam treatment)

The wafer on which the above hydrocarbon-containing film was formed was heated to 400 ℃ with EB-engine (hamamatsu photonics) while being subjected to electron beam irradiation of 1 MGy.

Formation of cured film (in the case of ion irradiation treatment)

Subjecting the wafer having the hydrocarbon-containing film formed thereon to an acceleration voltage of 10kV¹⁶ion/cm²Carbon ion irradiation.

Measurement of film thickness

A wafer cross section was prepared, and SEM photograph was taken using JSM-7100F (Japan Electron microscope) to measure the film thickness.

Determination of film Density

Using a fully automated multifunctional X-ray diffraction apparatus SmartLab (science) by high resolution X-ray reflectance measurements, the anticathode: cu and power: 45kV × 200mA, analytical range: 0.2 to 3.0 °, measurement step 0.002 ° simulation curve was fitted to the obtained X-ray reflectance curve to calculate the film density.

Measurement of film hardness

The film hardness was calculated using an ENT-2100 indentation hardness tester (eioiix) at indentation loads of 10 μ N, 100 measurement times, and 100ms step intervals.

_{D G}Determination of I/I

I in Raman spectroscopy was measured at a Laser wavelength of 514.5nm using a Triple Raman Laser Spectrometer (Triple Raman Laser Spectrometer) RAMATOR T64000(Horiba Jobin Yvon)_D/I_G。

Will appear at about 900-1800 cm-¹The broad peak of the compound is divided into 1590cm-¹Nearby G band, and 1350cm-¹Nearby D band, 1100cm-¹The intensity of the D band and the G band is calculated for the nearby bands. Thereby calculating I_D/I_G。

Determination of etching resistance

Using an etching apparatus NE-5000N (ULVAC), a chamber pressure of 0.17mT, an RF power of 200W, and a gas flow rate CF were measured₄(50sccm)、Ar(35sccm)、O₂Dry etching was performed for 30 seconds (4 sccm).

The film thickness before etching and the film thickness after etching were measured as described in the above "measurement of film thickness", and the difference between before and after the measurement was obtained to calculate the amount of decrease in film thickness per unit time.

Evaluation results

The evaluation results are shown in table 1 below.

TABLE 1

In the above-mentioned table, the following,

in the compositions 1 to 9, "before treatment" means the result of evaluation of the hydrocarbon-containing film before plasma treatment, and "after treatment" means the result of evaluation of the cured film after plasma treatment.

For the composition 10, "before treatment" means the result of evaluation of the hydrocarbon-containing film before electron beam irradiation, and "after treatment" means the result of evaluation of the cured film after electron beam irradiation.

In the composition 11, "before treatment" means the result of evaluation of the hydrocarbon-containing film before ion irradiation, and "after treatment" means the result of evaluation of the cured film after ion beam irradiation.

Comparative example evaluation of etching resistance of Hydrocarbon-containing film

The etching resistance of the hydrocarbon-containing film before the plasma treatment of composition 2 was measured in the same manner as described above. The etching resistance was 204 nm/min.

When the etching resistance of the hydrocarbon-containing film (before plasma treatment) obtained from composition 2 and the etching resistance of the cured film (after plasma treatment) were compared, the former was easily etched by about 24%.