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 2019-05-17 设计创作，主要内容包括：本发明提供一种硬掩模用组合物,更详细而言,通过包含含有化学式1所表示的重复单元的聚合物和溶剂,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。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的亚芳基、或者取代或非取代的碳原子数6～40的亚杂芳基,n为1～100的整数。化学式1<Image he="289" wi="700" file="DDA0002063084190000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention provides a composition for a hard mask, and more particularly, a composition for a hard mask, which comprises a polymer containing a repeating unit represented by chemical formula 1 and a solvent, thereby forming a hard mask layer having excellent etching resistance, coating properties, and chemical resistance. 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 arylene group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroarylene group having 6 to 40 carbon atoms, and n is an integer of 1 to 100. 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 arylene group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroarylene 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 with a second unit represented by chemical formula 3 or a synthetic equivalent thereof,
chemical formula 2
In the chemical formula 2, 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,
chemical formula 3
In the chemical formula 3, R3The substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or the substituted or unsubstituted heteroarylene 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, wherein the second unit cell represented by chemical formula 3 is any one selected from the group consisting of compounds represented by chemical formula 3-1 to chemical formula 3-6,
chemical formula 3-1
Chemical formula 3-2
Chemical formula 3-3
Chemical formula 3-4
In the chemical formula 3-4, X is nitrogen (N) or oxygen (O),
chemical formula 3-5
Chemical formula 3-6
5. The composition for a hard mask as claimed in claim 1, wherein R is3Is any one selected from the group 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 substituted or unsubstituted nitrogen (N) or oxygen (O).
6. The composition for a hard mask according to claim 1, wherein the composition for a hard mask comprises 5 to 25% by weight of the polymer represented by chemical formula 1 and 75 to 95% by weight of the solvent, based on the total weight of the composition.
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 on 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 used in forming a hard mask layer. However, it is considered that the improvement of the etching resistance is insufficient.
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 arylene group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroarylene group having 6 to 40 carbon atoms,
n is an integer of 1 to 100. )
Effects of the invention
The polymer of chemical formula 1 contained in the composition for a hard mask of the present invention may include a constitutional unit containing an indole derivative and a constitutional 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, coating characteristics such as solubility, flatness, and gap-fill (gap-fill) characteristics can be increased. 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.
In this specification, arylene means that there are two binding sites on the aryl group, i.e. a 2-valent group. They are applicable to the description of aryl groups, except that they are each a 2-valent group.
<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 chemical formula 1, R1Is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted aryl groupA heteroaryl group having 6 to 40 carbon atoms, 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, substituted or unsubstituted heteroaryl with 6 to 40 carbon atoms,
R3substituted or unsubstituted arylene having 6 to 40 carbon atoms, substituted or unsubstituted heteroarylene having 6 to 40 carbon atoms,
n is an integer of 1 to 100).
In the above chemical formula 1, "substituted" means substituted with a substituent, each of which may be different or the same, and specifically, a halogen atom such as fluorine, chlorine, bromine, etc., an amino group, a hydroxyl group, a nitro group, an alkyl group, an aryl group, a cycloalkyl group, an aryloxy group, an alkylthio group, an arylthio group, etc., but is not limited thereto.
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 unsubstituted heteroaryl group having 6 to 40 carbon atoms, or 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 substituted or unsubstituted arylene group having 6 to 40 carbon atoms, or the substituted or unsubstituted heteroarylene 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 3-6, for example.
[ chemical formula 3-1]
[ chemical formula 3-2]
[ chemical formulas 3-3]
[ chemical formulas 3-4]
In the above chemical formulas 3 to 4, X is nitrogen (N) or oxygen (O).
[ chemical formulas 3-5]
[ chemical formulas 3-6]
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 above polymer can be increased by the flexible property of the aryl group, thereby enabling to improve coating properties such as flatness and gap-filling property of the hard mask layer.
In addition, the polymer of the present invention has a secondary carbon structure rotatable between the indole derivative and the aryl group, and thus the flexibility of the polymer can be improved. 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 by being any one selected from the group represented by the following chemical formulas 4-1 to 4-5.
[ chemical formula 4-1]
[ chemical formula 4-2]
[ chemical formulas 4-3]
[ chemical formulas 4-4]
In the above chemical formula 4-4, X may be substituted or unsubstituted nitrogen (N) or oxygen (O).
[ chemical formulas 4-5]
In the above chemical formulas 4 to 5, X may be substituted or unsubstituted nitrogen (N) or oxygen (O).
The term "substituted" in the above chemical formulas 4-4 to 4-5 means substituted with a substituent, and the substituents may be different or the same, and specifically, examples thereof include, but are not limited to, halogen atoms such as fluorine, chlorine, bromine, etc., amino groups, hydroxyl groups, nitro groups, alkyl groups, aryl groups, cycloalkyl groups, aryloxy groups, alkylthio groups, arylthio groups, etc.
R in the polymer represented by the above chemical formula 13The substitution of the arylene group of chemical formula 4-1 to chemical formula 4-5 is preferable because the carbon content of the polymer can be increased and the solubility can be ensured.
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 used
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.
Synthesis example Synthesis of Polymer
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 13.8g (0.1mol) of the compound represented by chemical formula 3-1 in PGMEA100g, and dropwise added over 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 polymer was 1920, and the dispersity (Mw/Mn) was 1.4.
[ 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 18.8g (0.1mol) of the compound represented by chemical formula 3-2 was used as an aryl alcohol derivative. The weight average molecular weight (Mw) of the above polymer was 1730, and the dispersity (Mw/Mn) was 1.2.
[ 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 26.2g (0.1mol) of the compound represented by chemical formula 3-3 was used as the aryl alcohol derivative. The weight average molecular weight (Mw) of the above polymer was 1780, and the dispersity (Mw/Mn) was 1.5.
[ chemical formula A-3]
Synthesis example 4 (Polymer A' -1)
In a four-necked flask, 19.3g (0.1mol) of 2-phenylindole, 3.0g (0.1mol) of formaldehyde and 2.8g (0.015mol) of p-toluenesulfonic acid monohydrate were added to the flask, 100g of toluene was added thereto, the mixture was stirred, and the temperature was raised to 110 ℃ to dissolve the toluene, thereby starting polymerization. After 1 hour, the reaction mixture was cooled to room temperature, and 500g of methanol was added dropwise thereto to reprecipitate. The resulting solid compound was filtered, and the remaining solvent was removed by distillation 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 3000, and the dispersity (Mw/Mn) was 1.5.
[ chemical formula A' -1]
Synthesis example 5 (Polymer A' -2)
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 pH was adjusted to 7 neutral by using 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' -2). The weight average molecular weight (Mw) of the polymer was 3100, and the dispersity (Mw/Mn) was 1.8.
[ chemical formula A' -2]
Synthesis example 6 (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 14.4g (0.1mol) of 1-naphthol was used instead of the indole derivative. The weight average molecular weight (Mw) of the above polymer was 4720, and the dispersity (Mw/Mn) was 1.7.
[ chemical formula A' -3]
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