TWI679496B - Hardmask composition and method of forming patterns - Google Patents

Abstract

The invention discloses a hard mask composition and a method for forming a pattern using the hard mask composition. The hard mask composition includes a polymer including a structural unit represented by Chemical Formula 1 and a solvent. [Chemical Formula 1] X is a polycyclic cyclic group containing at least three fused substituted or unsubstituted benzene rings, and * is the point of attachment.

Description

Hard mask composition and method for forming pattern

The invention discloses a hard mask composition and a method for forming a pattern using the hard mask composition.

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 technology essentially requires effective lithography technology.

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 using the photoresist pattern as a mask The material layer is etched.

Currently, according to the miniaturization of a pattern to be formed, it is difficult to provide a fine pattern having an excellent outline only by the above-mentioned typical lithographic technique. Therefore, a layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern.

The hard cover curtain layer functions as an intermediate layer to transfer the fine pattern of photoresist to the material layer through 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 method has recently been proposed as an alternative A chemical vapor deposition (CVD) method is used to form the hard mask curtain layer. The spin coating method is not only easily performed, but also improves gap filling characteristics and planarization characteristics. Here, the gap-filling characteristic of filling a pattern without voids is required because the fine pattern can be achieved by forming a plurality of patterns as necessary. In addition, when the substrate has steps or when pattern-dense regions and non-patterned regions exist on the wafer together, it is necessary to planarize the surface of the hard mask layer through the bottom layer.

There is a need for a hard mask material that meets the required characteristics of a hard mask layer.

An embodiment provides a hard mask composition having improved heat resistance and etching resistance while ensuring solubility.

Another embodiment provides a method for forming a pattern using the hard mask composition.

According to an embodiment, a hard mask composition includes a polymer including a structural unit represented by Chemical Formula 1 and a solvent.

In Chemical Formula 1, X is a polycyclic ring containing at least three fused substituted or unsubstituted benzene rings Like base, and * is the connection point.

(chrysene)部分、經取代或未經取代的聯三伸苯(triphenylene)部分、經取代或未經取代的芘(pyrene)部分、經取代或未經取代的苝(perylene)部分、經取代或未經取代的苯並苝(benzoperylene)部分或者經取代或未經取代的蔻(coronene)部分。 In Chemical Formula 1, X may be a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstituted tetracene moiety, an Substituted or unsubstituted

(chrysene) moiety, substituted or unsubstituted triphenylene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted perylene moiety, substituted or An unsubstituted benzoperylene moiety or a substituted or unsubstituted coronene moiety.

The polymer can be obtained by reacting a substituted or unsubstituted diacetylene derivative with a substituted or unsubstituted biscyclopentadienone.

The substituted or unsubstituted butadiyne derivative may be represented by Chemical Formula 2.

部分、經取代或未經取代的聯三伸苯部分、經取代或未經取代的芘部分、經取代或未經取代的苝部分、經取代或未經取代的苯 並苝部分或者經取代或未經取代的蔻部分。 In Chemical Formula 2, X is a polycyclic cyclic group including at least three fused substituted or unsubstituted benzene rings, and may be a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted Phenanthrene moiety, substituted or unsubstituted fused tetraphenyl moiety, substituted or unsubstituted

Part, substituted or unsubstituted terphenylene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted benzofluorene moiety, or substituted or Unsubstituted Cardamom.

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% to 30% by weight based on the total amount of the hard mask composition.

According to another embodiment, a method for forming a pattern includes: forming a material layer on a substrate; coating a hard mask composition including a polymer and a solvent on the material layer; and heat-treating the hard mask composition to form Hard mask layer; forming a thin layer containing silicon on the hard mask layer; forming a photoresist layer on the silicon containing layer; exposing and developing the photoresist layer to form a photoresist pattern; using the photoresist pattern to select The silicon-containing thin layer and the hard cover curtain layer are removed to expose a part of the material layer; and the exposed part of the material layer is etched.

The hard mask composition can be applied by a spin coating method.

The method may further include forming a bottom antireflective coating (BARC) before forming the photoresist layer.

The hard mask composition according to the examples exhibits improved heat resistance and etching resistance. Therefore, it is possible to provide a hard mask thin layer having improved film density and etching resistance and satisfying flatness.

S1, S2, S3, S4, S5, S6, S7, S8‧‧‧ steps

FIG. 1 is a flowchart illustrating a method of forming a pattern according to an embodiment.

The exemplary embodiments of the present disclosure will be described in detail below, and can be easily performed by those skilled in the art. However, this disclosure may be implemented in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

In this 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 a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, and a cyano group , Amine, azide, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid Or its salt, phosphoric acid or its salt, C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl group, C1 to C30 alkoxy Group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C3 to C30 heteroalkyl Cycloalkyl (heterocycloalkyl group) and combinations thereof.

In the present specification, when a definition is not provided separately, the term "hetero" means that it contains 1 to 3 heteroatoms selected from N, O, S, and P.

In this specification, when a definition is not provided separately, "*" means a point of attachment of a compound or a compound portion.

Hereinafter, the hard mask composition according to the embodiment will be explained.

The hard mask composition according to the embodiment includes a polymer and a solvent, and the polymer The compound contains a structural unit represented by Chemical Formula 1.

In Chemical Formula 1, X is a polycyclic cyclic group including at least three fused substituted or unsubstituted benzene rings, and * is a point of attachment.

By including a polycyclic cyclic group in which at least three substituted or unsubstituted benzene rings are fused in the X part of the structural unit, the polymer may have improved etching resistance and heat resistance.

部分、聯三伸苯部分、芘部分、苝部分、苯並苝部分或蔻部分，但並非僅限於此。 For example, in Chemical Formula 1, X may be an anthracene moiety, a phenanthrene moiety, a thick tetraphenyl moiety,

Part, bitriphenylene part, fluorene part, fluorene part, benzopyrene part, or metho part, but it is not limited to this.

部分、聯三伸苯部分、芘部分、苝部分、苯並苝部分及蔻部分中，至少一個氫可獨立地被羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜 烷基、經取代或未經取代的C2至C30雜芳基或其組合置換。 For example, in the anthracene part, the phenanthrene part, the fused tetraphenyl part,

At least one of the moieties, bitriphenylene moieties, fluorene moieties, fluorene moieties, benzofluorene moieties, and molybdenum moieties may be independently substituted by hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted Or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, Substituted or unsubstituted C1 to C30 heteroalkyl, 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, and the polymer may be synthesized, for example, by Reaction Scheme 1.

Referring to Scheme 1, the polymer is obtained by reacting a substituted or unsubstituted butadiyne derivative with a substituted or unsubstituted dicyclopentadienone.

Herein, the substituted or unsubstituted butadiyne derivative may be represented by, for example, Chemical Formula 2.

部分、經取代或未經取代的聯三伸苯部分、經取代或未經取代的芘部分、經取代或未經取代的苝部分、經取代或未經取代的苯並苝部分或者經取代或未經取代的蔻部分，但並非僅限於此。 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 Substituted phenanthrene moieties, substituted or unsubstituted fused tetraphenyl moieties, substituted or unsubstituted

Part, substituted or unsubstituted terphenylene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted benzofluorene moiety, or substituted or The unreplaced card part, but it is not limited to this.

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 can be optimized by adjusting the carbon content and solubility in a solvent.

The solvent in the hard mask 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, Methoxypropanediol, diethylene glycol, diethylene glycol butylether, tri (ethylene glycol) monomethylether, propylene glycol monomethyl ether, propylene glycol monomethyl ether ethyl Acid ester, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, N, N dimethylacetamide, methylpyrrole Ketones (methyl pyrrolidone), methyl pyrrolidinone (methyl pyrrolidinone), acetone and ethyl 3-ethoxypropionate (ethyl 3-ethoxypropionate).

The hard mask composition may be included in an amount of about 0.1% to 50% by weight, about 0.1% to 30% by weight, or about 0.1% to 15% by weight based on the total amount of the hard curtain composition. polymer. When the polymer is included in the range, the thickness, surface roughness, and planarization of the hard cover curtain layer can be controlled.

The hard mask composition may further include the following additives: a surfactant, a crosslinking agent, a thermal acid generator, or a plasticizer.

The surfactant may include, but is not limited to, a fluoroalkyl-based compound, an alkylbenzene sulfonate, an alkyl pyridinium salt, a polyethylene glycol, or a quaternary ammonium salt.

The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent (substituted urea-based), or a polymer-based crosslinking agent. Preferably, it may be a cross-linking agent having at least two cross-linking substituents, for example, methoxymethylated glycoluril, butoxymethylated glycoluril ), Methoxymethylated melamine, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine Amine (butoxymethylated benzoguanamine), methoxymethylatedurea, butoxymethylatedurea, methoxymethylated thiourea, or butoxymethylated thiourea ( butoxymethylated thiourea).

The crosslinking agent may be a crosslinking agent having high heat resistance. The cross-linking agent having high heat resistance may be a cross-link including an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule Substituent compounds.

The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium 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-tetrabromocyclohexadienone), benzointosylate, 2 -2-nitrobenzyltosylate, other organic sulfonic acid alkyl esters, and the like, but not limited thereto.

The additive may be present in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the hard mask composition. Within this range, the solubility can be improved without changing the optical properties of the hard mask composition.

According to another embodiment, an organic layer manufactured 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, a planarization layer, a sacrificial layer, Fillers, etc.

According to another embodiment, an organic layer manufactured using the hard mask composition is provided.

FIG. 1 is a flowchart of a method for forming a pattern according to an embodiment.

A method for forming a pattern according to an embodiment includes: forming a material layer on a substrate (step S1); applying a hard mask composition containing a polymer and a solvent on the material layer (step S2); and applying a hard mask composition Heat treatment to form a hard cover curtain (step Step S3); forming a thin layer containing silicon on the hard mask layer (step S4); forming a photoresist layer on the thin layer containing silicon (step S5); exposing and developing the photoresist layer to form a photoresist pattern (Step S6); using a photoresist pattern to selectively remove the silicon-containing thin layer and the hard cover curtain layer to expose a portion of the material layer (Step S7); and etching the exposed portion of the material layer (Step 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 can be applied as a 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 heat treatment of the hard mask composition may be performed, 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) 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 ° C to 700 ° C.

The etching process may be performed on the exposed portion of the material layer by a dry etching process using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl _3, and a mixed gas thereof, but is not limited.

The etched material layer may be formed into a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, and the like, such as various patterns of a semiconductor integrated circuit device.

Hereinafter, the present disclosure will be described in more detail with reference to examples. However, these examples are exemplary, and the disclosure is not limited thereto.

Synthesis example

Synthesis Example 1

Plutonium (12 g, 59.3 mmol) was placed in a 1 liter two-necked round bottom flask equipped with a condenser, 400 ml of acetic acid was added thereto in a dropwise fashion, and the mixture was placed at 90 Heating was performed at ° C to dissolve the gadolinium. Subsequently, the solution was cooled to 40 ° C, 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. Next, the brown solid formed therein was filtered, washed with dichloromethane and distilled water, and recrystallized in hot toluene to obtain diiodine. Subsequently, 2-methyl-but-3-yn-2-ol (1 ml, 10.3 mmol) and 60 ml of distilled diethylamine It was placed in a Schlenk flask, cooled and degassed by the freeze-pump-thaw method, and then reacted with diiodine (2 g, 4.4 mmol), Pd [PPh ₃ ] ₂ Cl ₂ (68 mg), and CuI (0.12 mmol). The obtained mixture was stirred at 50 ° C 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. It was filtered under hot conditions and cooled to room temperature. After cooling, the organic layer therein was washed with water until the pH was 7, and then dried and recrystallized with hot toluene to obtain a compound represented by Chemical Formula 1a.

Synthesis Example 2

50 ml of dried triethylamine, 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) Mol) was placed in a 200 ml flask and then degassed in a freeze-aspirate-thaw manner. Subsequently, trimethylsilylacetylene (4.2 ml, 29.8 mmol) was added thereto dropwise, and the mixture was refluxed for 3 hours. After drying the solvent obtained therefrom, an extract was obtained therefrom using dichloromethane / distilled water and then subjected to column analysis and purification to obtain 9,10-bis-trimethylsilylacetylene Anthracene (9,10-bis-trimethylsilylethynylanthracene). Next, 9,10-bis-trimethylsilylacetylanthracene (0.6 g, 1.62 mmol), distilled dichloromethane (5 ml), and anhydrous KF (0.94 g, 16.2 mmol) were added thereto. ) And distilled methanol (5 ml), and the obtained mixture was refluxed for 12 hours. The resultant was subjected to column analysis using dichloromethane to obtain a compound represented by Chemical Formula 2a.

Synthesis Example 3

Dissolve 2,6-dibromoanthracene (5 g, 14.9 mmol), CuI (0.5 g, 2.63 mmol) and Pd (PPh ₃ ) ₂ Cl ₂ (0.5 g, 0.71 mmol) in 125 ml Tetrahydrofuran (THF). This solution was degassed with nitrogen, and trimethylsilylacetylene (10 ml, 72.5 mmol) and diisopropylamine (25 ml) were added dropwise thereto, and the mixture was heated at 60 ° C. It was heated and stirred for 7 hours. The product was subjected to column analysis with chloroform and dried to obtain a solid, and the solid was dissolved together with 3 g of K ₂ CO ₃ in a methanol / THF solution (100 ml) mixed at a ratio of 1: 1. in. The obtained mixture was stirred at 50 ° C. for 30 minutes, and extracted with distilled water and chloroform. The organic layer obtained therefrom was dried with Na ₂ SO ₄ and subjected to column analysis with hexane. A compound represented by Chemical Formula 3a is obtained.

Synthesis Example 4

-2,8-二基雙(三氟甲烷)磺酸鹽(Chrysene-2,8-diyl bis(trifluoromethan)sulfonate)(5克，14.9毫莫耳)、CuI(0.5克，2.63毫莫耳)及Pd(PPh₃)₂Cl₂(0.5克，0.71毫莫耳)溶解於125毫升THF中。利用氮氣對此溶液進行了除氣，向其中以滴入的方式加了三甲基矽烷基乙炔(10毫升、72.5毫莫耳)及二異丙胺(25毫升)，且將此混合物在60℃下進行了加熱並攪拌了7小時。利用氯仿對生成物進行了管柱分析並進行了乾燥以獲得固體，且將所述固體與3克K₂CO₃一起溶解於以1：1的比率混合的甲醇/THF的溶液(100毫升)中。將所獲得的溶液在50℃下攪拌了30分鐘，並利用蒸餾水及氯仿進行了萃取，且利用Na₂SO₄對自其獲得的有機層進行了乾燥並利用己烷進行了管柱分析，以獲得由化學式4a表示的化合物。 will

-2,8-diyl bis (trifluoromethane) sulfonate (Chrysene-2,8-diyl bis (trifluoromethan) sulfonate) (5 g, 14.9 mmol), CuI (0.5 g, 2.63 mmol) And Pd (PPh ₃ ) ₂ Cl ₂ (0.5 g, 0.71 mmol) were dissolved in 125 ml of THF. This solution was degassed with nitrogen, and trimethylsilylacetylene (10 ml, 72.5 mmol) and diisopropylamine (25 ml) were added dropwise thereto, and the mixture was heated at 60 ° C. It was heated and stirred for 7 hours. The product was subjected to column analysis with chloroform and dried to obtain a solid, and the solid was dissolved together with 3 g of K ₂ CO ₃ in a methanol / THF solution (100 ml) mixed at a ratio of 1: 1. in. The obtained solution was stirred at 50 ° C. for 30 minutes, and extracted with distilled water and chloroform. The organic layer obtained therefrom was dried with Na ₂ SO ₄ and subjected to column analysis with hexane. A compound represented by Chemical Formula 4a is obtained.

Comparative Synthesis Example 1

Dimethylacetylenemethanol (8.412 g, 100 mmol, 1 equivalent) was placed in a 500 ml two-necked round bottom flask equipped with a condenser, and dissolved was added thereto 1,4-diiodobenzene in 100 grams of benzene (32.99 grams, 100 millimoles, 1 equivalent). Subsequently, diethylamine equivalent (51.198 g), 20 mole% (3.809) copper iodide and 3 mole% (2.1327 g) bis (triphenylphosphine) dichloride were added dropwise to the reaction mixture. Palladium (II) (bis (triphenylphosphine) palladium (II)), 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 reactant was slowly cooled to room temperature to obtain a compound represented by 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 ether / methanol mixed at a ratio of 1: 1 was put into 50 ml of a sphere The flask was then stirred. Subsequently, K ₂ CO ₃ (7.18 g, 51.93 mmol) was slowly added to this mixture while stirring, and the obtained 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 was extracted three times with dichloromethane (125 ml each time). The organic layer obtained therefrom was dehydrated with MgSO ₄ , and the solvent therein was removed under vacuum and reduced pressure to obtain a compound represented by Chemical Formula B.

[Chemical Formula B]

Comparative Synthesis Example 3

21.8 grams (0.1 mole) of 1-hydroxyamidine, 14.5 grams (0.1 mole) of 1-naphthol, 6 grams (0.2 mole) of p-formaldehyde, 15.4 grams (0.1 mole) of diethyl sulfate and 115 grams of propylene glycol Monomethyl ether acetate (PGMEA) was put into a 500 ml two-necked round bottom flask equipped with a condenser to obtain a polymer represented by Chemical Formula C (MW: 1,500) by a synthetic process. .

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 4,4'- (1,4-phenylene) bis (2,3,5-triphenylcyclopentane-2,4-dienone) (4,4 '-(1,4-phenylene) bis (2,3, 5-triphenylcylopenta-2,4-dienone)) The solution was diluted with a molar ratio of 1: 1 and then filtered using a 0.1 micron Teflon (tetrafluoroethylene) filter to prepare a hard Mask composition. Based on the total weight of the hard cover composition, the weight of the polymer is adjusted to be within a range of 5 to 20% by weight 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 in 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 in 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 in the same manner as in 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 in the same manner as in 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 dissolving a polymer (Chemical Formula C) according to Comparative Synthesis Example 3 in propylene glycol monomethyl ether acetate (PGMEA) and In a mixed solvent of cyclohexanone (7: 3 (v / v)), this solution was filtered using a 0.1 micron Teflon (tetrafluoroethylene) filter.

Evaluation

Evaluation 1: Etching resistance

Each hard mask composition 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 ° C for 30 minutes to Each thin film was formed separately.

Subsequently, the thickness of each film was measured. Next, the film was dry-etched using a gas mixed with CHF ₃ / CF ₄ and a gas mixed with N ₂ / O ₂ for 100 seconds and 60 seconds, respectively, and the thickness was measured again. The thickness of the thin film before and after the dry etching and its etching time 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 / second)

The results are shown in Table 1.

Referring to Table 1, compared with the respective films formed from the hard mask compositions according to Comparative Examples 1 to 3, the respective films formed from the hard mask compositions according to Examples 1 to 4 showed sufficient Etching resistance against etching gas, and shows improved bulk etching characteristics.

Although the present invention has been described in connection with exemplary embodiments that are presently considered practical, it should be understood that the invention is not limited to the disclosed embodiments, but instead is intended to cover the spirit and scope included within the scope of the accompanying patent application. Various retouching and equivalent configurations.

Claims (9)

A hard mask composition comprising: a polymer including a structural unit represented by Chemical Formula 1; and a solvent, Wherein, in Chemical Formula 1, X is a polycyclic cyclic group including at least three fused substituted or unsubstituted benzene rings, and * is a point of attachment. The hard mask composition according to item 1 of the scope of patent application, wherein in Chemical Formula 1, X is a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted phenanthrene moiety, a substituted or unsubstituted Fused tetraphenyl moiety, substituted or unsubstituted Part, substituted or unsubstituted terphenylene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted benzofluorene moiety, or substituted or Unsubstituted Cardamom. The hard mask composition according to item 1 of the patent application scope, wherein the polymer is obtained by using a substituted or unsubstituted butadiyne derivative and a substituted or unsubstituted dicyclopentadienone To get. The hard mask composition according to item 3 of the scope of patent application, wherein the substituted or unsubstituted butadiyne derivative is represented by Chemical Formula 2: Wherein, in Chemical Formula 2, X is a polycyclic cyclic group including at least three fused substituted or unsubstituted benzene rings, and is a substituted or unsubstituted anthracene moiety, a substituted or unsubstituted Phenanthrene moiety, substituted or unsubstituted fused tetraphenyl moiety, substituted or unsubstituted Part, substituted or unsubstituted terphenylene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted pyrene moiety, substituted or unsubstituted benzofluorene moiety, or substituted or Unsubstituted Cardamom. The hard mask composition according to item 1 of the patent application range, wherein the weight average molecular weight of the polymer is in the range of 500 to 200,000. The hard mask composition according to item 1 of the patent application scope, wherein the polymer is included in an amount of 0.1% to 30% by weight based on the total amount of the hard mask composition. A method for forming a pattern, comprising: providing a material layer on a substrate; and coating the material layer with the polymer and the solvent according to any one of claims 1 to 6 of a patent application scope on the material layer. A hard mask composition; heat-treating the hard mask composition to form a hard mask layer; forming a silicon-containing thin layer on the hard mask layer; forming light on the silicon-containing thin layer A resist layer; exposing and developing the photoresist layer to form a photoresist pattern; using the photoresist pattern to selectively remove the silicon-containing thin layer and the hard cover curtain layer to expose all A portion of the material layer; and etching an exposed portion of the material layer. The pattern forming method according to item 7 of the scope of patent application, wherein the hard mask composition is applied by a spin coating method. The method for forming a pattern according to item 7 of the patent application scope, wherein the method further comprises: before forming the photoresist layer, forming a bottom anti-reflection coating (BARC).