Composition for hard mask
阅读说明：本技术 硬掩模用组合物 (Composition for hard mask ) 是由 金烔永 赵庸桓 崔汉永 于 2019-05-16 设计创作，主要内容包括：本发明涉及一种硬掩模用组合物,其包含下述化学式1所表示的聚合物和溶剂,下述化学式1中,R<Sub>1</Sub>为取代或非取代的碳原子数6～40的芳基、取代或非取代的碳原子数6～40的杂芳基、或者取代或非取代的碳原子数1～4的烷基,R<Sub>2</Sub>为氢、羟基、取代或非取代的碳原子数6～40的芳基、或者取代或非取代的碳原子数6～40的杂芳基,R<Sub>3</Sub>为取代或非取代的碳原子数6～40的芳基、或者取代或非取代的碳原子数6～40的杂芳基,从而能够形成具有优异的耐蚀刻性、涂布性和耐化学性的硬掩模层。化学式1<Image he="153" wi="242" file="1.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a composition for a hard mask, comprising a polymer represented by the following chemical formula 1 and a solvent, wherein in the following chemical formula 1, R 1 Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R 2 Is hydrogen, hydroxyl, substituted or unsubstituted aryl with 6-40 carbon atoms or substituted or unsubstituted heteroaryl with 6-40 carbon atoms, R 3 Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, thereby enabling the formation of a hard mask having excellent etching resistance, coating properties and chemical resistanceAnd (3) a layer. Chemical formula 1)
1. A composition for a hard mask, comprising a polymer represented by the following chemical formula 1 and a solvent,
chemical formula 1
In the chemical formula 1, R1Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
R2is hydrogen, hydroxyl, substituted or unsubstituted aryl with 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl with 6 to 40 carbon atoms,
R3is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms,
n is an integer of 1 to 100.
2. The composition for a hard mask according to claim 1, wherein the polymer represented by chemical formula 1 is a polymer produced by a condensation reaction of a first unit represented by chemical formula 2 or a synthetic equivalent thereof and a second unit represented by chemical formula 3 or a synthetic equivalent thereof,
chemical formula 2
In the chemical formula 2, R1Substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
R2is hydrogen, hydroxyl, substituted or unsubstituted aryl with 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl with 6 to 40 carbon atoms,
chemical formula 3
In the chemical formula 3, R3The aryl group is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms.
3. The composition for a hard mask according to claim 2, wherein the first unit cell represented by chemical formula 2 is any one selected from the group consisting of compounds represented by chemical formula 2-1 to chemical formula 2-4,
chemical formula 2-1
Chemical formula 2-2
Chemical formula 2-3
Chemical formula 2-4
4. The composition for a hard mask according to claim 2,
the second unit body represented by chemical formula 3 is any one selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-5,
chemical formula 3-1
Chemical formula 3-2
Chemical formula 3-3
Chemical formula 3-4
Chemical formula 3-5
In the chemical formulas 3-4 and 3-5, X is nitrogen (N), oxygen (O) or sulfur (S).
5. The composition for a hard mask as claimed in claim 1, wherein R is3Is any one selected from the group consisting of compounds represented by the following chemical formulas 4-1 to 4-5,
chemical formula 4-1
Chemical formula 4-2
Chemical formula 4-3
Chemical formula 4-4
Chemical formula 4-5
In the chemical formulas 4-4 and 4-5, X is nitrogen (N), oxygen (O) or sulfur (S).
6. The composition for a hard mask according to claim 1, comprising, based on the total weight of the composition:
5 to 25 wt% of a polymer represented by chemical formula 1; and
75-95 wt% of a solvent.
7. The composition for a hard mask according to claim 1, further comprising one or more selected from the group consisting of a crosslinking agent, a catalyst and a surfactant.
Technical Field
The present invention relates to a composition for a hard mask.
Background
In recent years, in highly integrated designs with miniaturization (ministry) and complication (complexity) of electronic devices, development of more improved materials and related processes has been accelerated. Thus, photolithography using conventional photoresists also requires new patterning materials and techniques.
In general, a predetermined pattern can be formed by applying a photoresist to a film to be etched to form a photoresist layer, forming a photoresist pattern through exposure and development processes, and partially removing the film to be etched using the photoresist pattern as an etching mask.
In order to suppress the decrease in resolution due to light reflection in the exposure step, an anti-reflective coating (ARC) layer may be formed between the film to be etched and the photoresist layer. In this case, since the ARC layer is additionally etched, the consumption amount or etching amount of the photoresist layer or the photoresist pattern may increase. In addition, when the thickness of the film to be etched is increased or the amount of etching required for forming a desired pattern is increased, sufficient etching resistance of the photoresist layer or the photoresist pattern may not be secured.
Therefore, in order to transfer the photoresist fine pattern to a sufficient depth without collapse in the patterning process, an organic film called a hard mask layer (hardmark layer) can be formed as a hard intermediate film. Characteristics such as heat resistance and etching resistance are required for such a hard mask layer to be able to withstand during various etching processes, and it is necessary to be formed in a uniform thickness by a spin coating process.
Korean laid-open patent No. 10-2015-0031163 discloses an organic film composition for forming a hard mask layer. But is considered to be insufficient in etching resistance characteristics.
Disclosure of Invention
Problems to be solved
The purpose of the present invention is to provide a composition for a hard mask, which is used for forming a hard mask layer having excellent etching resistance, coating properties and chemical resistance.
Means for solving the problems
The invention provides a composition for a hard mask, which comprises a polymer represented by the following chemical formula 1 and a solvent.
[ chemical formula 1]
(in the above chemical formula 1, R1Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
R2is hydrogen, hydroxyl, substituted or unsubstituted aryl with 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl with 6 to 40 carbon atoms,
R3is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms,
n is an integer of 1 to 100. )
Effects of the invention
The polymer contained in the composition for a hard mask of the present invention may contain a constituent unit containing an indole derivative and a constituent unit containing a flexible aryl derivative. This promotes intermolecular interaction by oxidative coupling (oxidative coupling) reaction based on the high carbon content, and improves filling (packing) characteristics, resulting in improved etching resistance and heat resistance. In addition, by including a flexible aryl group, solubility can be increased, and coating characteristics such as flatness and gap-fill (gap-fill) characteristics can be improved. Therefore, when the composition for a hard mask of the present invention is used, a hard mask layer having improved etching resistance, heat resistance and coating properties can be formed.
Detailed Description
The present invention relates to a composition for a hard mask, which can form a hard mask layer having improved etching resistance, heat resistance and coating characteristics at the same time by including a polymer containing a repeating unit having a specific structure of chemical formula 1 and a solvent.
More specifically, the polymer of chemical formula 1 may be a polymer manufactured by a condensation reaction of a first unit body including an indole derivative and a second unit body including a flexible aryl derivative. From this, it was confirmed through experiments that the composition for a hard mask of the present invention can improve etching resistance and heat resistance by containing an indole derivative having a high carbon content, and can improve coating characteristics even with a high carbon content by containing a flexible aryl group to increase solubility, thereby completing the present invention.
Hereinafter, the composition for a hard mask according to the embodiment of the present invention will be described in detail. However, this is merely an example, and the present invention is not limited thereto.
In the present invention, when the compound, the repeating unit or the resin represented by the chemical formula has isomers, the compound, the repeating unit or the resin represented by the chemical formula represents the chemical formula including the isomers thereof.
In the present invention, the term "carbon content" refers to the ratio of the number of carbons per molecule of the compound to the total number of masses.
<Composition for hard mask>
The composition for a hard mask according to an exemplary embodiment of the present invention includes a polymer and a solvent.
Polymer and method of making same
The polymer includes a repeating unit represented by the following chemical formula 1:
[ chemical formula 1]
(in the above chemical formula 1, R1Substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
R2is hydrogen, hydroxyl, substituted or unsubstituted aryl with 6-40 carbon atoms, or substituted or unsubstituted carbon atomA heteroaryl group having a sub-number of 6 to 40,
R3substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms,
n is an integer of 1 to 100).
The term "substituted" in the above chemical formula 1 means being substituted with a substituent, each of which may be different or the same, and specific examples thereof include, but are not limited to, halogen atoms such as fluorine, chlorine and bromine, amino groups, hydroxyl groups, nitro groups, alkyl groups, aryl groups, cycloalkyl groups, aryloxy groups, alkylthio groups, arylthio groups, and the like.
In chemical formula 1, the "heteroaryl group" refers to an aryl group containing one or more heteroatoms other than carbon atoms among atoms constituting a ring, and may be a saturated ring, an unsaturated ring, a monocyclic ring or a condensed ring, and the heteroatoms may be one or more atoms selected from oxygen, sulfur and nitrogen. Examples of the heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a triazolyl group, a thiadiazolyl group, an oxadiazolyl group, a quinolyl group, a benzofuranyl group, an indolyl group, a morpholinyl group, a pyrrolidinyl group, a piperidyl group, and a tetrahydrofuryl group.
The hard mask formed from the composition for a hard mask according to the present invention can exhibit excellent coating characteristics and excellent etching resistance by sufficiently ensuring solubility by including the polymer.
The polymer of the present invention can be produced by a condensation reaction of the first unit represented by chemical formula 2 or a synthetic equivalent thereof and the second unit represented by chemical formula 3 or a synthetic equivalent thereof.
[ chemical formula 2]
(in the above chemical formula 2, R1Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstitutedA substituted heteroaryl group having 6 to 40 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
R2the aryl group is hydrogen, hydroxyl, substituted or unsubstituted aryl group with 6-40 carbon atoms, or substituted or unsubstituted heteroaryl group with 6-40 carbon atoms. )
[ chemical formula 3]
(in the above chemical formula 3, R3The aryl group is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 40 carbon atoms. )
The first unit cell represented by chemical formula 2 may be any one selected from the group consisting of compounds represented by chemical formulas 2-1 to 2-4, for example.
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
The second unit cell represented by chemical formula 3 may be any one selected from the group consisting of compounds represented by chemical formulas 3-1 to 3-5, for example.
[ chemical formula 3-1]
[ chemical formula 3-2]
[ chemical formulas 3-3]
[ chemical formulas 3-4]
[ chemical formulas 3-5]
(in the above chemical formulas 3-4 and 3-5, X is nitrogen (N), oxygen (O) or sulfur (S))
As described above, the above-mentioned polymer of the present invention may comprise a first unit body containing an indole derivative. The intermolecular interaction by the oxidative coupling reaction can be promoted due to the high carbon content of the indole derivative, thereby improving the filling characteristics, and as a result, the etching resistance and heat resistance of the hard mask layer can be improved.
In addition, the above-mentioned polymer of the present invention may comprise a second unit body containing an aryl group. The solubility of the polymer is imparted by the flexible 3-valent carbon structure containing an aryl group, and the filling property is improved by increasing the carbon content depending on the kind of the aryl group contained, so that the etching resistance and the coating property of the hard mask layer can be simultaneously improved.
Further, the polymer of the present invention has a tertiary carbon structure rotatable between an indole derivative and an aryl group, and thus can improve flexibility of the polymer. Therefore, the polymer of the present invention can have excellent solubility even when the indole derivative and the aryl group having a high carbon content are contained, and thus can improve coating characteristics such as flatness and gap-filling characteristics of the hard mask layer.
The polymer represented by the above chemical formula 1 may be represented by R from the aspects of etch resistance and coating characteristics of the hard mask layer3Characterized in that the substituent is any one selected from the group consisting of the substituents represented by the following chemical formulae 4-1 to 4-5.
[ chemical formula 4-1]
[ chemical formula 4-2]
[ chemical formulas 4-3]
[ chemical formulas 4-4]
[ chemical formulas 4-5]
(in the above chemical formulas 4-4 and 4-5, X is nitrogen (N), oxygen (O) or sulfur (S))
Thus, R in the polymer represented by the above chemical formula 13When substituted with any one selected from the substituents represented by the above chemical formulae 4-1 to 4-5, the carbon content of the polymer can be increased and appropriate solubility can be secured.
According to an embodiment of the present invention, R is in the polymer of the above chemical formula 13In the case of a site-substituted bulky aryl or heteroaryl group, the etching resistance can be increased by increasing the carbon content, but the solubility and coating characteristics may be degradedThus by making R1The position (b) of (a) is substituted with an alkyl group having 1 to 4 carbon atoms, which has a small steric hindrance, and the solubility of the polymer can be suitably ensured, so that the etching resistance and the coating properties of the hard mask layer can be improved at the same time.
In addition, according to an embodiment of the present invention, the content of the polymer is not particularly limited as long as the object of the present invention can be achieved, and for example, may be 5 to 25% by weight, and preferably 5 to 15% by weight, based on the total weight of the composition. When the above range is satisfied, the above effects of the present invention can be exhibited most excellently.
The weight average molecular weight of the polymer in one embodiment of the present invention is not particularly limited as long as the object of the present invention can be achieved, and may be, for example, 1000 to 8000, and preferably 1000 to 3000. When the above range is satisfied, the above effects of the present invention can be exhibited most excellently.
Solvent(s)
The solvent used in the composition for a hard mask according to the embodiment of the present invention is not particularly limited, and may contain an organic solvent having sufficient solubility for the polymer. For example, the solvent may include Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME), cyclohexanone, ethyl lactate, gamma-butyrolactone (GBL), acetylacetone (acetyl acetate), and the like.
The content of the solvent is not particularly limited, and may be the balance other than the polymer and the additional preparation described later. For example, the solvent may be contained in an amount of 75 to 95 wt%, preferably 85 to 95 wt%, based on the total weight of the composition for a hard mask. When the above range is satisfied, the effect of the present invention can be exhibited to be excellent.
Supplementary preparation
The composition for a hard mask according to an embodiment of the present invention may further include at least one of a crosslinking agent and a catalyst, as necessary. The crosslinking agent is not particularly limited as long as it can crosslink the repeating unit of the polymer by heating in a reaction in which a catalytic action is generated by the generated acid, and can react with the polymer so as to generate a catalytic action by the generated acid. As a representative example of such a crosslinking agent, any one selected from the group consisting of melamine, amino resin, glycoluril compound, and diepoxy compound can be used.
By further including the above-mentioned crosslinking agent, the curing characteristics of the composition for a hard mask can be further enhanced.
Specific examples of the crosslinking agent include etherified amino resins such as methylated or butylated melamine (specific examples include N-methoxymethyl-melamine or N-butoxymethyl-melamine) and methylated or butylated urea (urea) resin (specific examples include Cymel U-65 resin or UFR 80 resin), glycoluril derivatives represented by the following chemical formula 11 (specific examples include podderlink 1174), bis (hydroxymethyl) -p-cresol compounds represented by the chemical formula 12, and the like. Further, a bicyclo oxygen compound represented by the following chemical formula 13 and a melamine compound represented by the following chemical formula 14 may be used as the crosslinking agent.
[ chemical formula 11]
[ chemical formula 12]
[ chemical formula 13]
[ chemical formula 14]
As the catalyst, an acid catalyst or a basic catalyst can be used.
The acid catalyst may be a thermally activated acid catalyst. As an example of the acid catalyst, an organic acid such as p-toluenesulfonic acid monohydrate (p-toluene sulfonic acid monohydrate) can be used, and a Thermal Acid Generator (TAG) type compound having improved storage stability can be mentioned. As the thermal acid generator, for example, pyridine p-toluenesulfonate can be used as an acid generator compound capable of releasing an acid upon heat treatment
Other photosensitive catalysts known in the art of resist technology may be used as long as they are compatible with other components of the hardmask composition.
When the crosslinking agent is contained, the content of the crosslinking agent may be 1 to 30 parts by weight, preferably 5 to 20 parts by weight, and more preferably 5 to 10 parts by weight, based on 100 parts by weight of the polymer. When the catalyst is contained, the content of the catalyst may be 0.001 to 5 parts by weight, preferably 0.1 to 2 parts by weight, and more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polymer.
When the content of the crosslinking agent is within the above range, appropriate crosslinking characteristics can be obtained without changing the optical characteristics of the formed underlayer film.
When the catalyst content is within the above range, the acidity that affects the storage stability can be appropriately maintained while appropriate crosslinking characteristics are obtained.
Additive agent
The composition for a hard mask of the present invention may further contain an additive such as a surfactant, if necessary. As the surfactant, alkyl benzene sulfonate and alkyl pyridine can be usedSalts, polyethylene glycols, quaternary ammonium salts, and the like, but are not limited thereto. In this case, the content of the surfactant may be 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer.
When the content of the surfactant is in the above range, appropriate crosslinking characteristics can be obtained without changing the optical characteristics of the underlying film to be formed.
Hereinafter, in order to help understanding of the present invention, experimental examples including preferred examples and comparative examples are disclosed, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and various changes and modifications of the examples may be made within the scope and technical spirit of the present invention, which will be apparent to those skilled in the art, and such changes and modifications also fall within the scope of the appended claims.
< example >
Synthesis example: synthesis of polymers
Synthesis example 1 (Polymer A-1)
A1L three-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel was placed in an oil container, 19.3g (0.1mol) of the compound represented by the chemical formula 2-1 was charged into the reactor and dissolved in 200g of propylene glycol monomethyl ether acetate (PGEMA). Thereafter, 0.19g (0.002mol) of sulfuric acid was added. The dropping funnel was filled with a solution prepared by dissolving 26.9g (0.1mol) of the compound represented by chemical formula 3-1 in PGMEA100g, and dropwise added for 2 hours while maintaining the temperature inside the reactor at 120 ℃. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 12 hours, then 0.45g (0.003mol) of triethanolamine as a neutralizing agent was added to the reactor and further stirred at room temperature for 1 hour, and the reaction mixture obtained by cooling to room temperature was added dropwise while stirring back to a round-bottomed flask containing a distilled water/methanol mixed solution in a mass ratio of 3: 7. A solid product formed on the bottom of the flask was obtained by using a high-speed stirrer and distilled at 80 ℃ under reduced pressure for 1 hour to obtain a polymer represented by the following chemical formula (A-1). The weight average molecular weight (Mw) of the above polymer was 2000, and the dispersity (Mw/Mn) was 1.5.
[ chemical formula A-1]
Synthesis example 2 (Polymer A-2)
A polymer represented by the following chemical formula (A-2) was obtained in the same manner as in Synthesis example 1, except that 26.9g (0.1mol) of the indole derivative of chemical formula 2-2 and 15.6g (0.1mol) of the aryl aldehyde derivative of chemical formula 3-2 were used. The weight average molecular weight (Mw) of the above polymer was 1840, and the dispersity (Mw/Mn) was 1.25.
[ chemical formula A-2]
Synthesis example 3 (Polymer A-3)
A polymer represented by the following chemical formula (A-3) was obtained in the same manner as in Synthesis example 1, except that 14.5g (0.1mol) of the indole derivative of chemical formula 2-3 and 23.0g (0.1mol) of the aryl aldehyde derivative of chemical formula 3-3 were used. The weight average molecular weight (Mw) of the above polymer was 1650, and the dispersity (Mw/Mn) was 1.21.
[ chemical formula A-3]
Synthesis example 4 (Polymer A' -1)
To a flask were added 11.7g (0.1mol) of indole, 25.3g (0.1mol) of 2, 6-naphthalenedicarboxylic dichloride and 300g of 1, 2-dichloroethane, and 13.3g (0.1mol) of aluminum chloride was slowly added dropwise at normal temperature, followed by stirring at 60 ℃ for 8 hours. After the reaction was completed, the solid compound formed by reverse dropwise addition of methanol was filtered and dried. In a solution prepared by dissolving 6.0g (0.02mol) of the solid compound obtained in this step in 100g of tetrahydrofuran, 7.6g (0.2mol) of an aqueous sodium borohydride solution was slowly added dropwise, and the mixture was stirred at 50 ℃ for 11 hours. After completion of the reaction, the reaction mixture was adjusted to pH 7 neutrality with a 5% hydrogen chloride solution, and the resulting solid compound was filtered and dried to obtain a polymer represented by the following chemical formula (A' -1). The weight average molecular weight (Mw) of the polymer was 3100, and the dispersity (Mw/Mn) was 1.8.
[ chemical formula A' -1]
Synthesis example 5 (Polymer A' -2)
In a 1L flask, 11.7g (0.1mol) of indole, 23.0g (0.1mol) of 1-pyrenecarboxaldehyde, 24.5g (0.1mol) of triphenylamine, and 19.0g (0.1mol) of p-toluenesulfonic acid monohydrate were dissolved in 300g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and stirred at 120 ℃. When the reaction was completed, a small amount of Ethyl Acetate (EA) and tetrahydrofuran were added, and then the acid catalyst was removed using distilled water. Thereafter, the solid compound formed using tetrahydrofuran and hexane was filtered and dried to obtain a polymer represented by the following chemical formula (a' -2). The weight average molecular weight (Mw) of the above polymer was 1780, and the dispersity (Mw/Mn) was 1.5.
[ chemical formula A' -2]
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