CN111344634A - Hard mask composition and method for forming pattern - Google Patents
Hard mask composition and method for forming pattern Download PDFInfo
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- CN111344634A CN111344634A CN201880073203.XA CN201880073203A CN111344634A CN 111344634 A CN111344634 A CN 111344634A CN 201880073203 A CN201880073203 A CN 201880073203A CN 111344634 A CN111344634 A CN 111344634A
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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Abstract
The present invention discloses a hard mask composition and a method for forming a pattern using the same, the hard mask composition comprising: a polymer comprising a structural unit represented by chemical formula 1; and a solvent. [ chemical formula 1]
Chemical formula 1 is the same as defined in the specification.
Description
Technical Field
A hard mask composition and a method of forming a pattern using the same are disclosed.
Background
Recently, the semiconductor industry has developed to an ultra-fine technology having a pattern with a size of several nanometers to several tens of nanometers. Such ultra-fine techniques inherently require efficient lithography techniques.
Typical lithographic techniques include: providing a material layer on a semiconductor substrate; coating a photoresist layer thereon; exposing and developing the photoresist layer to provide a photoresist pattern; and etching the material layer using the photoresist pattern as a mask.
Currently, it is difficult to provide a fine pattern having an excellent profile only by the above-described typical lithography technique according to miniaturization of a pattern to be formed. Accordingly, a layer called a hard mask layer (hardmasklayer) may be formed between the material layer and the photoresist layer to provide a fine pattern.
The hard mask layer functions as an intermediate layer to transfer a fine pattern of photoresist to the material layer by a selective etching process. Therefore, the hard mask layer needs to have characteristics such as heat resistance and etching resistance in order to withstand multiple etching processes.
On the other hand, a spin-on coating (spin-on coating) method has been recently proposed instead of a Chemical Vapor Deposition (CVD) method for forming the hard mask layer. The spin coating method is not only easily performed but also improves gap-fill (gap-fill) characteristics and planarization characteristics. Herein, a gap filling characteristic of filling a pattern without a void is required because the fine pattern can be achieved by necessarily forming a plurality of patterns. In addition, when the substrate has a step (step) or when a pattern-dense area and a non-pattern area exist together on the wafer, it is necessary to planarize the surface of the hard mask layer through the underlayer.
There is a need for a hard mask material that satisfies the characteristics required for a hard mask layer.
Disclosure of Invention
Technical problem
One embodiment provides a hard mask composition having improved heat resistance and etching resistance while securing solubility.
Another embodiment provides a method of forming a pattern using the hard mask composition.
Technical solution
According to an embodiment, a hard mask composition includes a polymer including a structural unit represented by chemical formula 1 and a solvent.
[ chemical formula 1]
In the chemical formula 1, the first and second,
x is a polycyclic cyclic group containing at least three fused substituted or unsubstituted benzene rings, and
is a connection point.
In chemical formula 1, X may be a substituted or unsubstituted anthracene (anthracene) moiety, a substituted or unsubstituted phenanthrene (phenanthrene) moiety, a substituted or unsubstituted tetracene (tetracene) moiety
A (chrysene) moiety, a substituted or unsubstituted biphenylene (triphenylene) moiety, a substituted or unsubstituted pyrene (pyrene) moiety, a substituted or unsubstituted perylene (perylene) moiety, a substituted or unsubstituted benzoperylene (benzoperylene) moiety, or a substituted or unsubstituted coronene moiety.
The polymer may be obtained by the reaction of a substituted or unsubstituted diacetylene derivative with a substituted or unsubstituted dicyclopentadienone.
The substituted or unsubstituted diacetylene derivative may be represented by chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
x is a polycyclic cyclic group comprising at least three fused substituted or unsubstituted benzene rings, and may be a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstituted naphthacene moiety
A moiety, a substituted or unsubstituted triphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety.
The weight average molecular weight of the polymer may be in the range of 500 to 200,000.
The polymer may be included in an amount of 0.1 wt% to 30 wt% based on the total amount of the hard mask composition.
According to another embodiment, a method of forming a pattern includes: forming a material layer on a substrate; coating a hard mask composition comprising a polymer and a solvent on the material layer; performing a heat treatment on the hard mask composition to form a hard mask layer; forming a thin layer containing silicon on the hard mask layer; forming a photoresist layer on the thin layer containing silicon; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the silicon-containing thin layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer; and etching the exposed portion of the material layer.
The hard mask composition can be applied by spin coating.
The method may further include forming a bottom anti-reflective coating (BARC) layer before forming the photoresist layer.
Advantageous effects
The hard mask composition according to the embodiment exhibits improved heat resistance and etching resistance. Therefore, a hard mask thin layer having improved film density and etching resistance and satisfying flatness can be provided.
Drawings
Fig. 1 is a flow chart illustrating a method of forming a pattern according to an embodiment.
Detailed Description
Exemplary embodiments of the present disclosure will be described in detail below, and can be easily performed by those skilled in the art. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein.
In the present specification, when a definition is not otherwise provided, "substituted" may mean that a hydrogen atom of a compound is replaced with a substituent selected from the group consisting of: halogen atoms (F, Br, Cl or I), hydroxyl groups, nitro groups, cyano groups, amine groups, azide groups, amidino groups (amidinogroup), hydrazine groups (hydrazino group), hydrazone groups (hydrazono group), carbonyl groups, carbamoyl groups, thiol groups, ester groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C30 alkyl groups, C2 to C30 alkenyl groups, C2 to C30 alkynyl groups, C6 to C30 aryl groups, C7 to C30 aralkyl groups (arylakyl group), C1 to C30 alkoxy groups, C1 to C20 heteroalkyl groups (heteroarylakyl group), C3 to C20 heteroarylalkyl groups (heteroarylakyl group), C3 to C30 cycloalkyl groups, C3 to C15 cycloalkenyl groups, C2 to C15 cycloalkynyl groups, C6353 to C30 heterocycloalkyl groups (heterocycloalkyl groups), and combinations thereof.
In the present specification, when a definition is not otherwise provided, the term "hetero" (hetero) means that 1 to 3 hetero atoms selected from N, O, S and P are contained.
In the present specification, ""' refers to a connection point of a compound or a compound moiety (moiey), when no definition is otherwise provided.
Hereinafter, the hard mask composition according to the embodiment is described.
The hard mask composition according to an embodiment includes a polymer including a structural unit represented by chemical formula 1 and a solvent.
[ chemical formula 1]
In the chemical formula 1, the first and second,
x is a polycyclic cyclic group containing at least three fused substituted or unsubstituted benzene rings, and
is a connection point.
By including a polycyclic cyclic group in which at least three substituted or unsubstituted benzene rings are condensed in the X portion of the structural unit, the polymer can have improved etching resistance and heat resistance.
For example, in chemical formula 1, X may be an anthracene moiety, a phenanthrene moiety, a naphthacene moiety,
A moiety, a triphenylene moiety, a pyrene moiety, a perylene moiety, a benzoperylene moiety, or a coronene moiety, but is not limited thereto.
For example, in the anthracene moiety, the phenanthrene moiety, the naphthacene moiety,
At least one of the moieties, the triphenylene moieties, the pyrene moieties, the perylene moieties, the benzoperylene moieties, and the coronene moieties may be independently replaced with a hydroxyl, a halogen, a substituted or unsubstituted C1 to C30 alkoxy, a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof.
The polymer represented by chemical formula 1 may be synthesized by a Diels-Alder reaction (Diels-Alder reaction), and the polymer may be synthesized, for example, by reaction scheme 1.
[ Process 1]
Referring to scheme 1, the polymer is obtained by the reaction of a substituted or unsubstituted diacetylene derivative with a substituted or unsubstituted dicyclopentadienone (bischloropentadienone).
Herein, the substituted or unsubstituted diacetylene derivative may be represented by, for example, chemical formula 2.
[ chemical formula 2]
In chemical formula 2, X is a polycyclic cyclic group including at least three fused substituted or unsubstituted benzene rings, and for example, X may be a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstituted naphthacene moiety
A moiety, a substituted or unsubstituted triphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety, but is not limited thereto.
The polymer may have a weight average molecular weight of about 500 to 200,000. More specifically, the polymer may have a weight average molecular weight of about 1,000 to 20,000. When the polymer has a weight average molecular weight within the range, the hard mask composition including the polymer may be optimized by adjusting the carbon content and the solubility in the solvent.
The solvent in the hardmask composition may be any solvent that is sufficiently soluble or dispersible for the polymer, and may include, for example, at least one selected from the group consisting of: propylene glycol, propylene glycol diacetate (propylene glycol diacetate), methoxypropylene glycol, diethylene glycol butyl ether (diethylene glycol butyl ether), tri (ethylene glycol) monomethyl ether (tri (ethylene glycol) monomethylether), propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate (ethyl lactate), gamma-butyrolactone (gamma-butyrolactone), N-dimethylformamide, N-dimethylacetamide, methylpyrrolidone (methyl pyrrolidone), acetylacetone, and ethyl3-ethoxypropionate (ethyl 3-ethylproprionate).
The polymer may be included in an amount of about 0.1 wt% to 50 wt%, about 0.1 wt% to 30 wt%, or about 0.1 wt% to 15 wt% based on the total amount of the hard mask composition. When polymers are included within the ranges, the thickness, surface roughness, and planarization of the hard mask layer can be controlled.
The hardmask composition may further comprise the following additives: surfactants, cross-linking agents, thermal acid generators, or plasticizers.
The surfactant may include, for example, a fluoroalkyl-based compound, an alkylbenzene sulfonate, an alkylpyridinium salt (alkyl pyridinium salt), polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.
The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent (cured urea-based) or a polymer-based crosslinking agent. Preferably, it may be a crosslinking agent having at least two crosslinking-forming substituents, such as compounds such as methoxy methylated glycoluril (methoxymethylated glycoluril), butoxy methylated glycoluril (butoxymethylated glycoluril), methoxy methylated melamine (methoxymethylated melamine), butoxy methylated benzoguanamine (butoxymethylated benzoguanamine), methoxy methylated urea (methoxymethylated urea), butoxy methylated benzoguanamine (butoxymethylated thiourea), methoxy methylated thiourea (methoxymethylated thiourea), or butoxy methylated thiourea (butoxymethylated thiourea).
The crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound including a crosslinking substituent including an aromatic ring (e.g., a benzene ring or a naphthalene ring) in a molecule.
The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid (pyridine p-toluene sulfonic acid), salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, etc., or/and 2,4,4,6-tetrabromocyclohexadienone (2,4,4, 6-tetrachlorocyclohexadienone), benzoin tosylate (benzoinsulate), 2-nitrobenzyl tosylate (2-nitrotoluene sulfonate), other alkyl organosulfonates, etc., but is not limited thereto.
The additive may be present in an amount of about 0.001 parts by weight to about 40 parts by weight based on 100 parts by weight of the hard mask composition. Within the range, the solubility can be improved without changing the optical properties of the hard mask composition.
According to another embodiment, an organic layer fabricated using the hard mask composition is provided. The organic layer may be formed, for example, by coating a hard mask composition on a substrate and heat-treating it to cure, and may include, for example, a hard mask layer for an electronic device, a planarization layer, a sacrificial layer, a filler, and the like.
According to another embodiment, an organic layer fabricated using the hard mask composition is provided.
Fig. 1 is a flow chart of a method of forming a pattern according to an embodiment.
A method of forming a pattern according to an embodiment includes: forming a material layer on a substrate (S1); coating a hard mask composition including a polymer and a solvent on the material layer (S2); performing a heat treatment on the hard mask composition to form a hard mask layer (S3); forming a thin layer containing silicon on the hard mask layer (S4); forming a photoresist layer on the silicon-containing thin layer (S5); exposing and developing the photoresist layer to form a photoresist pattern (S6); selectively removing the silicon-containing thin layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer (S7); and etching the exposed portion of the material layer (S8).
The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.
The material layer is a material to be finally patterned, for example, a metal layer such as an aluminum layer and a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as a silicon oxide layer and a silicon nitride layer. The material layer may be formed by a method such as a Chemical Vapor Deposition (CVD) process.
The hard mask composition is the same as described above and may be applied in solution by spin coating. Herein, the thickness of the hard mask composition is not particularly limited, but may be, for example, about 50 to 200,000 angstroms.
The hard mask composition may be heat treated, for example, at about 100 c to 700 c for about 10 seconds to 1 hour.
The silicon-containing thin layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and/or SiN.
The method may further include forming a bottom anti-reflective coating (BARC) layer on the silicon-containing thin layer before forming the photoresist layer.
The exposure may be performed on the photoresist layer using, for example, ArF, KrF, or EUV. After the exposure, a heat treatment may be performed at about 100 to 700 ℃.
An etching process may be performed on the exposed portions of the material layer by a dry etching process using an etching gas, which may be, for example, CHF3、CF4、Cl2、BCl3And mixed gases thereof, but not limited.
The etched material layer may be formed into a plurality of patterns, and the plurality of patterns may be metal patterns, semiconductor patterns, insulating patterns, etc., such as various patterns of semiconductor integrated circuit devices.
Modes for carrying out the invention
Hereinafter, the present disclosure is described in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited thereto.
Synthesis example
Synthesis example 1
Pyrene (12 g, 59.3 mmol) was put in a 1 l two-necked round bottom flask equipped with a condenser, 400 ml of acetic acid was added thereto in a dropwise manner (dropwise fast), and the mixture was heated at 90 ℃ to dissolve pyrene. Subsequently, the solution was cooled to 40 ℃, 40 ml of distilled water, iodine (15.07 g, 59.36 mmol) and KI (5.14 g, 24 mmol) were added thereto, and the mixture was stirred for 4 hours. Then, the brown solid generated therein was filtered, washed with dichloromethane and distilled water and recrystallized in hot toluene to obtain diiodopyrene. Subsequently, 2-methyl-but-3-yn-2-ol (2-methyl-but-3-yn-2-ol) (1 ml, 10.3 mmol) and 60 ml distilled diethylamine were placed in a Schlenk flask (Schlenk flash), cooled and degassed by freeze-pump-thaw method (freeze-pump-thawmethod), and then reacted under argon with diiodopyrene (2 g, 4.4 mmol), Pd [ PPh ], and3]2Cl2(68 mg) and CuI (0.12 mmol) were mixed. The obtained mixture was stirred at 50 ℃ for 20 hours, and after removing the solvent under vacuum, it was dried with dichloromethane to obtain an intermediate. Next, distilled toluene was added dropwise to the intermediate (500 mg, 1.34 mmol) and NaOH (480 mg, 12 mmol), and the mixture was refluxed and heated for 3 hours, filtered under heat and cooled to room temperature. After cooling, the organic layer therein was washed with water until pH 7, and then dried and recrystallized with hot toluene to obtain the compound represented by chemical formula 1 a.
[ chemical formula 1a ]
Synthesis example 2
Dried triethylamine (50 ml), 9, 10-dibromoanthracene (5 g, 14.9 mmol), CuI (0.14 g, 0.75 mmol) and Pd [ PPh ]3]4(0.85 g, 0.75 mmol) was placed in a 200 ml flask and then degassed by freeze-pump-thaw. Subsequently, the process of the present invention,trimethylsilylacetylene (4.2 ml, 29.8 mmol) was added thereto in a dropwise manner, and the mixture was refluxed for 3 hours. After drying the solvent obtained therefrom, an extract was obtained therefrom using methylene chloride/distilled water and then subjected to column analysis (columned) and purification to obtain 9, 10-bis-trimethylsilylethyleneanthracene (9, 10-bis-trimethylallylanthracene). Next, 9, 10-bis-trimethylsilylacetyleneanthracene (0.6 g, 1.62 mmol), distilled dichloromethane (5 ml), anhydrous KF (0.94 g, 16.2 mmol), and distilled methanol (5 ml) were added thereto, and the obtained mixture was refluxed for 12 hours. The resultant was subjected to column analysis using methylene chloride to obtain a compound represented by chemical formula 2 a.
[ chemical formula 2a ]
Synthesis example 3
2, 6-dibromoanthracene (5 g, 14.9 mmol), CuI (0.5 g, 2.63 mmol) and Pd (PPh)3)2Cl2(0.5 g, 0.71 mmol) was dissolved in 125 ml Tetrahydrofuran (THF). The solution was degassed with nitrogen, trimethylsilylacetylene (10 ml, 72.5 mmol) and diisopropylamine (25 ml) were added dropwise thereto, and the mixture was heated and stirred at 60 ℃ for 7 hours. The resultant was subjected to column analysis using chloroform and dried to obtain a solid, and the solid was mixed with 3 g of K2CO3Dissolved together in a solution of methanol/THF (100 ml) mixed in a ratio of 1: 1. The obtained mixture was stirred at 50 ℃ for 30 minutes, extracted with distilled water and chloroform, and extracted with Na2SO4The organic layer obtained therefrom was dried and subjected to column analysis using hexane to obtain the compound represented by chemical formula 3 a.
[ chemical formula 3a ]
Synthesis example 4
Will be provided with
-2, 8-diylbis (trifluoromethane) sulfonate (5 g, 14.9 mmol), CuI (0.5 g, 2.63 mmol) and Pd (PPh)3)2Cl2(0.5 g, 0.71 mmol) was dissolved in 125 ml of THF. The solution was degassed with nitrogen, trimethylsilylacetylene (10 ml, 72.5 mmol) and diisopropylamine (25 ml) were added dropwise thereto, and the mixture was heated and stirred at 60 ℃ for 7 hours. The resultant was subjected to column analysis using chloroform and dried to obtain a solid, and the solid was mixed with 3 g of K2CO3Dissolved together in a solution of methanol/THF (100 ml) mixed in a ratio of 1: 1. The obtained solution was stirred at 50 ℃ for 30 minutes, extracted with distilled water and chloroform, and extracted with Na2SO4The organic layer obtained therefrom was dried and subjected to column analysis using hexane to obtain the compound represented by chemical formula 4 a.
[ chemical formula 4a ]
Comparative Synthesis example 1
Dimethylacetylene methanol (8.412 g, 100 mmol, 1 eq) was placed in a 500 ml two-neck round bottom flask equipped with a condenser, to which was added 1, 4-diiodobenzene (32.99 g, 100 mmol, 1 eq) dissolved in 100 g of benzene. Subsequently, diethylamine equivalent (51.198 g), 20 mol% (3.809) copper iodide and 3 mol% (2.1327 g) bis (triphenylphosphine) palladium (II) dichloride (bis (triphenylphosphine) palladium (II)) were added dropwise to the reaction mixture, and the mixture was refluxed at room temperature. The intermediate obtained therefrom was filtered, potassium hydroxide and methylbenzene were added thereto dropwise, and the mixture was refluxed to complete the reaction. Subsequently, the reaction was slowly cooled to room temperature to obtain the compound represented by chemical formula a.
[ chemical formula A ]
Comparative Synthesis example 2
A mixture of 4,4' -bis (trimethylsilyl) biphenyl (1.8 g, 5.19 mmol) and 30 ml of a mixture of diethyl ether/methanol mixed in a ratio of 1:1 was placed in a 50 ml spherical flask and then stirred. Subsequently, K was slowly added to this mixture while stirring2CO3(7.18 g, 51.93 mmol), and the resulting mixture was stirred and reacted at room temperature for 6 hours. After the reaction, the reaction was poured into 250 ml of distilled water, and the aqueous layer thereof was extracted three times with dichloromethane (125 ml each time). Using MgSO4The organic layer obtained therefrom is dehydrated, and the solvent therein is removed under vacuum and reduced pressure to obtain the compound represented by chemical formula B.
[ chemical formula B ]
Comparative Synthesis example 3
21.8 g (0.1 mol) of 1-hydroxypyrene, 14.5 g (0.1 mol) of 1-naphthol, 6 g (0.2 mol) of p-formaldehyde, 15.4 g (0.1 mol) of diethyl sulfate and 115 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were put into a 500-ml two-necked round bottom flask equipped with a condenser to obtain a polymer represented by the chemical formula C (MW: 1,500) by a synthetic process.
[ chemical formula C ]
Preparation of hard mask composition
Example 1
The compound represented by chemical formula 1a according to synthesis example 1 was dissolved in a mixed solvent of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and cyclohexanone (7:3(v/v)), and the solution was diluted with 4,4'- (1,4-phenylene) bis (2,3, 5-triphenylcyclopenta-2, 4-dienone) (4,4' - (1,4-phenylene) bis (2,3, 5-triphenylcylopeptan-2, 4-dienone)) at a molar ratio of 1:1, and then filtered with a 0.1 μm TEFLON (tetrafluoroethylene) filter to prepare a hard mask composition. The weight of the polymer is adjusted to be in the range of 5 wt% to 20 wt% based on the total weight of the hard mask composition, depending on the desired thickness.
Example 2
A hard mask composition was prepared according to the same method as example 1, except that the compound according to synthesis example 2 (chemical formula 2a) was used instead of the compound represented by synthesis example 1.
Example 3
A hard mask composition was prepared according to the same method as example 1, except that the compound according to synthesis example 3 (chemical formula 3a) was used instead of the compound represented by synthesis example 1.
Example 4
A hard mask composition was prepared according to the same method as example 1, except that the compound according to synthesis example 4 (chemical formula 4a) was used instead of the compound represented by synthesis example 1.
Comparative example 1
A hard mask composition was prepared according to the same method as example 1, except that the compound according to comparative synthesis example 1 (chemical formula a) was used instead of the compound represented by synthesis example 1.
Comparative example 2
A hard mask composition was prepared according to the same method as example 1, except that the compound according to comparative synthesis example 2 (chemical formula B) was used instead of the compound represented by synthesis example 1.
Comparative example 3
A hard mask composition was prepared by: the polymer (chemical formula C) according to comparative synthesis example 3 was dissolved in a mixed solvent of Propylene Glycol Monomethyl Ether Acetate (PGMEA) and cyclohexanone (7:3(v/v)), and the solution was filtered using a 0.1 μm teflon (tetrafluoroethylene) filter.
Evaluation of
Evaluation 1: etching resistance
Each of the hard mask compositions according to examples 1 to 4 and comparative examples 1 to 3 was spin-coated on a silicon wafer at a thickness of 4,000 angstroms and heat-treated on a hot plate at 240 ℃ for 30 minutes to form each thin film, respectively.
Subsequently, the thickness of each film was measured. Then, CHF is used3/CF4Mixed gas and N2/O2The mixed gases dry-etch the film for 100 seconds and 60 seconds, respectively, and measure the thickness thereof again. The thickness of the thin film before and after the dry etching and the etching time thereof are used to calculate the Bulk Etch Rate (BER) according to the calculation equation 1.
[ calculation equation 1]
(initial film thickness-film thickness after etching)/etching time (Angstrom/sec)
The results are shown in Table 1.
[ Table 1]
Referring to table 1, each of the thin films respectively formed of the hard mask compositions according to examples 1 to 4 shows sufficient etch resistance against an etching gas and shows improved bulk etching characteristics, compared to each of the thin films respectively formed of the hard mask compositions according to comparative examples 1 to 3.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (9)
1. A hard mask composition comprising:
a polymer including a structural unit represented by chemical formula 1; and
a solvent, a water-soluble organic solvent,
[ chemical formula 1]
Wherein, in chemical formula 1,
x is a polycyclic cyclic group comprising at least three fused substituted or unsubstituted benzene rings, and
is a connection point.
2. The hard mask composition as claimed in claim 1, wherein in chemical formula 1, X is substituted or unsubstituted anthracene moiety, substituted or unsubstituted phenanthrene moiety, substituted or unsubstituted tetracene moiety
A moiety, a substituted or unsubstituted triphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety.
3. The hard mask composition of claim 1 wherein the polymer is obtained by the reaction of a substituted or unsubstituted diacetylene derivative with a substituted or unsubstituted dicyclopentadiene ketone.
4. The hard mask composition of claim 3 wherein the substituted or unsubstituted diacetylene derivative is represented by formula 2:
[ chemical formula 2]
Wherein, in chemical formula 2,
x is a polycyclic cyclic group comprising at least three fused substituted or unsubstituted benzene rings, and is a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstituted naphthacene moiety
A moiety, a substituted or unsubstituted triphenylene moiety, a substituted or unsubstituted pyrene moiety, a substituted or unsubstituted perylene moiety, a substituted or unsubstituted benzoperylene moiety, or a substituted or unsubstituted coronene moiety.
5. The hard mask composition of claim 1 wherein the weight average molecular weight of the polymer is in the range of 500 to 200,000.
6. The hard mask composition of claim 1 comprising the polymer in an amount of 0.1 to 30 wt% based on the total amount of the hard mask composition.
7. A method of forming a pattern, comprising:
providing a layer of material on a substrate;
coating a hard mask composition comprising the polymer and the solvent according to any one of claims 1 to 6 on the material layer;
heat-treating the hard mask composition to form a hard mask layer;
forming a thin layer containing silicon on the hard mask layer;
forming a photoresist layer on the thin layer containing silicon;
exposing and developing the photoresist layer to form a photoresist pattern;
selectively removing the silicon-containing thin layer and the hard mask layer using the photoresist pattern to expose a portion of the material layer; and
the exposed portions of the material layer are etched.
8. The method of claim 7, wherein the hard mask composition is applied by spin coating.
9. The method of forming a pattern according to claim 7, wherein the method further comprises:
before forming the photoresist layer, a bottom anti-reflective coating (BARC) layer is formed.
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| KR10-2017-0160979 | 2017-11-28 | ||
| KR1020170160979A KR102113659B1 (en) | 2017-11-28 | 2017-11-28 | Hardmask composition, and method of forming patterns |
| PCT/KR2018/007364 WO2019107690A1 (en) | 2017-11-28 | 2018-06-28 | Hard mask composition and pattern forming method |
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| CN111344634A true CN111344634A (en) | 2020-06-26 |
| CN111344634B CN111344634B (en) | 2023-03-24 |
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| KR (1) | KR102113659B1 (en) |
| CN (1) | CN111344634B (en) |
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| Publication number | Publication date |
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| CN111344634B (en) | 2023-03-24 |
| TWI679496B (en) | 2019-12-11 |
| KR20190062013A (en) | 2019-06-05 |
| KR102113659B1 (en) | 2020-05-21 |
| WO2019107690A1 (en) | 2019-06-06 |
| TW201932979A (en) | 2019-08-16 |
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