WO2019132153A1 - Polymer, organic film composition and pattern formation method - Google Patents

Polymer, organic film composition and pattern formation method Download PDF

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Publication number
WO2019132153A1
WO2019132153A1 PCT/KR2018/009108 KR2018009108W WO2019132153A1 WO 2019132153 A1 WO2019132153 A1 WO 2019132153A1 KR 2018009108 W KR2018009108 W KR 2018009108W WO 2019132153 A1 WO2019132153 A1 WO 2019132153A1
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substituted
unsubstituted
group
formula
polymer
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PCT/KR2018/009108
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French (fr)
Korean (ko)
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김진형
박유정
김유나
윤희찬
임상학
정슬기
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삼성에스디아이 주식회사
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Publication of WO2019132153A1 publication Critical patent/WO2019132153A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • a novel polymer, an organic film composition comprising the polymer, and a pattern forming method using the organic film composition is provided.
  • a typical lithographic technique involves forming a layer of material on a semiconductor substrate, coating a photoresist layer thereon, and exposing and developing the photoresist pattern . And etching the material layer using the photoresist pattern as a mask.
  • a fine pattern can be formed by forming an organic film called a hardmask layer between the material layer to be etched and the photoresist layer.
  • the hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs to have heat resistance and resistance to erosion resistance so as to withstand the multiple etching process.
  • the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method.
  • the spin-on coating method is not only easy to process but also can improve planarization characteristics.
  • One embodiment provides a novel polymer that is not only excellent in corrosion resistance, but also has cap-fill and planarization properties.
  • Another embodiment provides an organic film composition comprising the polymer.
  • Another embodiment provides a method of forming a pattern using the organic film composition.
  • a polymer comprising a structural unit represented by the following formula (1).
  • the show is a moiety represented by the following formula (2)
  • the seedling is a moiety represented by the following formula (3)
  • I are each independently 0, 8, 80 , or carbonyl
  • II 2 to II 5 each independently represent a hydroxyl group, a halogen group, a substituted or unsubstituted
  • II 6 to II 11 are each independently hydrogen, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 06 to 030 aryl group, or a combination thereof,
  • the polymer may have a weight average molecular weight of 1,000 to 200,000.
  • an organic film composition comprising a polymer as described above and a solvent.
  • the polymer may be contained in an amount of 0.1% by weight to 30% by weight based on the total amount of the organic film composition.
  • a method of manufacturing a semiconductor device comprising: forming a material layer on a substrate; applying an organic film composition comprising the polymer and the solvent on the material layer; heat treating the organic film composition to form a hard mask layer , Forming a silicon-containing thin film layer on the hard mask layer,
  • the step of applying the organic film composition may be performed by a spin-on coating method.
  • Polymers according to one embodiment include a heterocyclic group moiety and an aromatic ring moiety connected by a given linker. Accordingly, the polymer can provide both an anti-etching property and a gap-fill property and a planarization property, and when the polymer is used as an organic film material, an organic film having excellent etching resistance and flatness can be provided.
  • FIG. 1 is a flow chart for explaining a method of forming a pattern according to an embodiment of the present invention.
  • FIG. 2 is a reference diagram for explaining a calculation formula 2 related to a planarization characteristic
  • FIG. 3 is a reference diagram for explaining a calculation formula 3 related to a terminal characteristic .
  • 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (a hydrogen atom, (1 or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, A sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, (: 1 to 030 alkyl group, 02 to 030 alkenyl group, 02 to 030 alkenyl group, or a salt thereof), a hydrazino group, a hydrazino group, a carbonyl group, a carbamoyl group, 030 alkenyl group, 06 to 030 aryl group, 07 to 030 arylalkyl group, (1 to 030 alkoxy group, 01 to 020 heteroalkyl group, 03 to 020 heteroarylalkyl group, 030 < / RTI >
  • hetero means containing 1 to 3 heteroatoms selected from 0, 8, and.
  • the polymer according to one embodiment comprises a structural unit represented by the following formula (1). [Chemical Formula 1]
  • the show is a moiety represented by the following formula (2)
  • R is hydrogen, a substituted or unsubstituted 01 to O30 alkyl group, a substituted or unsubstituted 06 to O30 aryl group,
  • II 1 represents a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, a substituted or unsubstituted 02 to 030 alkynyl group , A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted 1 to 30 heteroalkyl group, a substituted or unsubstituted 02 to 030 heteroaryl group, or a combination thereof,
  • 6 and I are each independently 0, 8, 80 2, or carbonyl
  • To II 5 each independently represent a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, a substituted or unsubstituted 02 A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to O30 heteroaryl group,
  • Each of Mo 6 to II 11 is independently hydrogen, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 06 to 30 aryl group, or a combination thereof,
  • the polymer includes the structural unit represented by the formula (1), wherein the number and arrangement of these structural units are not limited.
  • the structural unit represented by the formula ( 1 ) includes a heterocyclic group moiety) and a predetermined linker, i.e., 0, 8, 80 , or a carbonyl-linked aromatic ring group moiety.
  • the heterocyclic group portion (shown) is represented by the formula (2) shown above, and the aromatic ring group moiety connected to the predetermined linker (represented by Formula 3).
  • the heterocyclic ring moiety in the heterocyclic group moiety may be connected to the aromatic ring group moiety connected to the predetermined linker.
  • the hetero atom contained in the pentagonal ring is 0 or 0.
  • the hexagonal ring includes, for example, a hydroxy group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, It may be in inverted form.
  • the polymer contains the structure represented by the formula (2) in its structural unit, it is basically excellent in corrosion resistance.
  • L 1 and L 2 may each be 0, that is, an ether linker, but the present invention is not limited thereto.
  • the polymer may increase the flexibility of the polymer by including a predetermined linking group represented by the general formula (3) in its structural unit.
  • This flexible structure not only improves the solubility of the polymer by increasing the free volume of the polymer but also lowers the glass transition temperature (Tg), thereby improving the gap-fill performance and planarization in the baking process.
  • 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. By having a weight average molecular weight in the above range, it is possible to optimize by adjusting the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.
  • the organic film composition for example, hard mask composition
  • a uniform thin film can be formed without forming pin-holes and voids in the baking process or deterioration in thickness scattering, and when a step is present in the lower substrate (or film) Can provide excellent cap-fill and planarization characteristics.
  • an organic film composition comprising a polymer as described above and a solvent.
  • the solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, and examples thereof include propylene glycol, propylene glycol
  • the polymer 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 organic film composition. remind ' ⁇ ° 2019/132153 8 1 mye containing the polymer as being 012018/009108 range may be adjusted to a thickness of organic layer, the surface roughness and the planarization.
  • the organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
  • additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
  • surfactant examples include, but are not limited to, a fluoroalkyl-based compound, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, and a quaternary ammonium salt.
  • the cross-linking agent examples include melamine-based, substitution-based, or polymer-based ones.
  • the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glycerol, a butoxymethylated glyceryl, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxy Methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea can be used.
  • crosslinking agent a crosslinking agent having high heat resistance
  • a compound containing a crosslinking forming substituent group having an aromatic ring (for example, benzene ring or naphthalene ring) in the molecule can be used.
  • the thermal acid generators may be, for example, I) -toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid,
  • Acidic compounds such as hydroxybenzoic acid and naphthalenecarboxylic acid and / or 2 , 4 , 4 , 6 -tetrabromocyclohexadienone, benzoinositolate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters But is not limited thereto.
  • the additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including the additives in the above range, the solubility can be improved without changing the optical properties of the organic film composition.
  • an organic film produced using the organic film composition described above may be formed by coating the above-described organic film composition on a substrate and then curing through a heat treatment process, for example, an organic thin film used for an electronic device such as a hard mask layer, a planarization layer, a sacrificial layer, and a filler.
  • FIG. 1 is a flowchart illustrating a pattern forming method according to an embodiment.
  • the pattern forming method includes the steps of forming a material layer on a substrate (S1), applying (S2) an organic film composition including the above-mentioned polymer and a solvent on the material layer, Forming a hard mask layer (S3) on the hard mask layer, forming a silicon-containing thin film layer on the hard mask layer (S4), forming a photoresist layer on the silicon-containing thin film layer (S5) (S6) selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a part of the material layer using the photoresist pattern, 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 and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon or an insulating layer such as silicon oxide, silicon nitride, etc.
  • the material layer may be formed by, for example, have.
  • the organic film composition may be prepared in the form of a solution and applied by a spin-on coating method.
  • the thickness of the organic film composition is not particularly limited, but may be about 50 to 200,000 A or about 50 To 10,000 A thick.
  • the step of heat treating the organic film composition may be carried out, for example, at about 100 to 700 ° C for about 10 seconds to 1 hour.
  • the silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and / or SiN.
  • a bottom anti-reflective coating may be formed on the silicon-containing thin film layer before the step of forming the photoresist layer.
  • the step of exposing the photoresist layer may be performed using ArF, KrF or EUV, for example. Further, the heat treatment can be performed at an exposure time of 100 to 700 ° C.
  • etching the exposed portion of the material layer comprises: 2019/132153 1 »(: 1 ⁇ ⁇ 2018/009108
  • the etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, or the like, and may be applied in various patterns, for example, in a semiconductor integrated circuit device.
  • Polymerization was carried out by stirring at 100 (: for 2 to 15 hours after the addition of silver 78.2 of monomethyl ether acetate.) A sample was taken from the polymerization reaction at intervals of 1 hour, and a weight average molecular weight of 2,000 ⁇ The reaction was completed at 3,500. After completion of the polymerization reaction, the reaction product was slowly cooled to room temperature, and the reaction product was distilled
  • the mixture was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), .
  • PGMEA propylene glycol monomethyl ether acetate
  • cyclohexanone 7: 3 (v / v)
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 3 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 4 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 1 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 3 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 4 was used in place of the polymer obtained in Synthesis Example 1.
  • a hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 5 was used in place of the polymer obtained in Synthesis Example 1.
  • the thin films formed from the hard mask compositions according to Examples 1 to 4 had sufficient erosion-resistance to the etching gas as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 5, Can be confirmed.
  • Evaluation 2 gap-fill (Gap-fill), and applying a hardmask composition according to an embodiment 1-4 Wabi Comparative Example 1-5 in the wafer is formed planarization characteristic pattern] After forming a thin film through a baking process using a hot plate , The contact characteristics and planarization characteristics were observed. The cap-fill characteristic was determined by observing the cross section of the pattern with FE-SEM equipment (Hitachi, S-4800) and determining the occurrence of voids. The planarity was determined by K- And the thickness of the film was measured by the equation 2 shown in Fig. The results are shown in Table 2.
  • planarization characteristics are as follows. As the difference in the thickness of the thin film formed on the space pattern in the line / space (0/8 ? 6) pattern, that is, the difference between 1 11 and 1x 2 in FIG. 2, 2019/132153 1 »(: 1 ⁇ ⁇ 2018/009108
  • FIG. 3 is a reference diagram for explaining the calculation formula 3 for calculating the end sum. Referring to FIG. 3, since the film thickness in the cell portion varies according to the distance from the ferry, four cells are selected in the order close to the ferry , And the step characteristics are superior as the sum of the steps of the cell and the ferry area is smaller at four points.
  • the thin films formed from the hard mask compositions according to Examples 1 to 4 are superior to the thin films formed from the hard mask composition according to Comparative Examples 1 to 5 because the step sum according to Equation 3 is a relatively small value It can be seen that the film has flatness.
  • the thin films formed from the hard mask compositions according to Examples 1 to 4 are excellent in corrosion resistance, gap-fill and 1 -p 1), planarization characteristics, and step characteristics.
  • the thin films formed from the hard mask compositions according to Comparative Examples 1 to 5 exhibited poor flatness when the overall thin film characteristics were unsatisfactory, or when the corrosion resistance was satisfied, or when the step characteristics were satisfied, , It is difficult to uniformly satisfy the required physical properties of the hard mask thin film.

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Abstract

The present invention relates to: a polymer comprising a structural unit represented by the following chemical formula 1; an organic film composition comprising the polymer; and a method for forming a pattern by using the organic film composition. (I) In chemical formula 1, A is a moiety represented by the following chemical formula 2, B is a moiety represented by the following chemical formula 3, and * is a linking point. (II) (III) The definitions of chemical formulas 2 and 3 are the same as those described in the specification.

Description

【명세서】  【Specification】
【발명의 명칭】  Title of the Invention
중합체,유기막조성물및 패턴형성 방법  Polymer, organic film composition and pattern forming method
【기술분야】  TECHNICAL FIELD
신규한중합체，상기 중합체를포함하는유기막조성물,그리고상기 유기막 조성물을사용하는패턴형성 방법에 관한것이다.  A novel polymer, an organic film composition comprising the polymer, and a pattern forming method using the organic film composition.
【배경기술】  BACKGROUND ART [0002]
최근반도체산업은수백나노미터 크기의 패턴에서수내지 수십 나노미터 크기의 패턴을가지는초미세 기술로발전하고있다. 이러한초미세 기술을 실현하기 위해서는효과적인리쏘그래픽 기법이 필수적이다.  BACKGROUND ART [0002] In recent years, the semiconductor industry has developed into an ultrafine technology having a pattern of a few to a few nanometers in a pattern of a size of several hundred nanometers. Effective lithographic techniques are essential to realize this ultrafine technology.
전형적인리쏘그래픽 기법은반도체 기판위에 재료층을형성하고그위에 포토레지스트층을코팅하고노광및 현상을하여 포토레지스트패턴을.형성한후, 상기 포토레지스트패턴을마스크로하여 재료층을식각하는과정을포함한다. 근래,형성하고자하는패턴의 크기가감소함에 따라상술한전형적인 리쏘그래픽 기법만으로는양호한프로파일을가진미세 패턴을형성하기 어렵다. 이에 따라식각하고자하는재료층과포토레지스트층사이에 일명 하드마스크 층 (hardmask layer)이라고불리는유기막을형성하여 미세 패턴을형성할수있다. 하드마스크층은선택적 식각과정을통하여 포토레지스트의 미세 패턴을 재료층으로전사해주는중간막으로서 역할을한다. 따라서 하드마스크층은다중 식각과정 동안견딜수있도록내열성 및내식각성의 특성이 필요하다. A typical lithographic technique involves forming a layer of material on a semiconductor substrate, coating a photoresist layer thereon, and exposing and developing the photoresist pattern . And etching the material layer using the photoresist pattern as a mask. In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a fine pattern can be formed by forming an organic film called a hardmask layer between the material layer to be etched and the photoresist layer. The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs to have heat resistance and resistance to erosion resistance so as to withstand the multiple etching process.
한편,근래하드마스크층은화학기상증착방법 대신스핀-온코팅 (spin-on coating)방법으로형성하는것이 제안되었다. 스핀-온코팅 방법은공정이 용이할 뿐만아니라평탄화특성을개선할수있다. 미세 패턴을실현하기 위해서는다중 패턴형성이 필수적인데 이때 패턴내부를공극없이 막으로매립하는매립 특성 (gap-fill특성)이 필요하게 된다.  Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. The spin-on coating method is not only easy to process but also can improve planarization characteristics. In order to realize a fine pattern, it is necessary to form multiple patterns. In this case, a gap-fill characteristic in which the inside of a pattern is filled with a film without a gap is required.
또한,피가공기판에 단차가있는경우나,패턴밀집부분및 패턴이 없는 영역이 웨이퍼 상에 함께존재하는경우，하드마스크층을이용하여 막표면을 평탄화시킬필요가있다.그러나하드마스크층에 요구되는상술한특성들은서로 상충관계에 있어서 이들을모두만족할수있는하드마스크조성물이 필요하다. 【발명의 상세한설명】 2019/132153 1»（：1^1{2018/009108 It is also necessary to planarize the surface of the film using the hard mask layer when there is a step on the substrate to be processed or when there is a pattern dense portion and an area having no pattern on the wafer. The above-mentioned characteristics are in conflict with each other, and a hard mask composition capable of satisfying all of them is required. DETAILED DESCRIPTION OF THE INVENTION 2019/132153 1 »(: 1 ^ {2018/009108
2  2
【기술적 과제】 [Technical Problem]
일구현예는내식각성이 우수할뿐만아니라캡-필특성 및평탄화특성 또한확보할수있는신규한중합체를제공한다.  One embodiment provides a novel polymer that is not only excellent in corrosion resistance, but also has cap-fill and planarization properties.
다른구현예는상기 중합체를포함하는유기막조성물을제공한다.  Another embodiment provides an organic film composition comprising the polymer.
또다른구현예는상기 유기막조성물을사용한패턴형성 방법을제공한다. Another embodiment provides a method of forming a pattern using the organic film composition.
【기술적 해결방법】 [Technical Solution]
일구현예에 따르면,하기 화학식 1로표현되는구조단위를포함하는 중합체를제공한다.  According to one embodiment, there is provided a polymer comprising a structural unit represented by the following formula (1).
[화학식 1]
Figure imgf000004_0001
상기 화학식 1에서, [Chemical Formula 1]
Figure imgf000004_0001
In Formula 1,
쇼는하기 화학식 2로표현되는모이어티이고,  The show is a moiety represented by the following formula (2)
묘는하기 화학식 3으로표현되는모이어티이고,  The seedling is a moiety represented by the following formula (3)
*은연결지점이다:  * Is the connection point:
[화학식 2]  (2)
Figure imgf000004_0002
Figure imgf000004_0002
상기 화학식 2에서,  In Formula 2,
å는 ,。또는요이고,여기서 11°는수소,치환또는비치환된 01내지 30 알킬기，치환또는비치환된 6내지 030아릴기,또는이들의 조합이고,  or is hydrogen, substituted or unsubstituted 01 to 30 alkyl group, substituted or unsubstituted 6 to 30 aryl group, or a combination thereof,
은히드록시기，할로겐기，치환또는비치환된 01내지 030알콕시기，치환 또는비치환된＜그1내지 030알킬기，치환또는비치환된 02내지 030알케닐기, 치환또는비치환된 02내지 030알키닐기,치환또는비치환된 06내지 030 아릴기,치환또는비치환된 Cl내지 030헤테로알킬기,치환또는비치환된 02 내지 030헤테로아릴기,또는이들의 조합이고,  A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, , A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted Cl to O30 heteroalkyl group, a substituted or unsubstituted C2 to O30 heteroaryl group,
는 0내지 3인정수이고，  Is an integer of 0 to 3,
*은연결지점이다: 2019/132153 1»(：1^1{2018/009108 * Is the connection point: 2019/132153 1 »(: 1 ^ {2018/009108
[화학식 3]
Figure imgf000005_0001
(3)
Figure imgf000005_0001
상기 화학식 3에서,  In Formula 3,
및 I?는각각독립적으로 0, 8, 802,또는카르보닐이고， And I are each independently 0, 8, 80 , or carbonyl,
II2내지 II5는각각독립적으로히드록시기,할로겐기,치환또는비치환된II 2 to II 5 each independently represent a hydroxyl group, a halogen group, a substituted or unsubstituted
01내지 030알콕시기,치환또는비치환된 01내지 030알킬기,치환또는 비치환된 02내지〔30알케닐기,치환또는비치환된 02내지 030알키닐기,치환 또는비치환된 06내지 030아릴기，치환또는비치환된 01내지 030헤테로알킬기， 치환또는비치환된 01내지 030헤테로아릴기，또는이들의 조합이고, A substituted or unsubstituted C2 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkoxy group, A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group,
1?내지 6는각각독립적으로 0내지 4인정수아고, 1 ? To 6 each independently represent an integer of 0 to 4,
II6내지 II11은각각독립적으로수소，치환또는비치환된 01내지 030 알킬기,치환또는비치환된 06내지 030아릴기，또는이들의조합이고, II 6 to II 11 are each independently hydrogen, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 06 to 030 aryl group, or a combination thereof,
II은 0내지 5인정수이고,  II is an integer from 0 to 5,
*은연결지점이다.  * Is the connection point.
상기 중합체의 중량평균분자량이 1,000내지 200,000일수있다.  The polymer may have a weight average molecular weight of 1,000 to 200,000.
다른구현예에 따르면,상술한중합체,그리고용매를포함하는유기막 조성물을제공한다.  According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.
상기 중합체는상기 유기막조성물의 총함량에 대하여 0.1중량%내지 30 중량%로포함될수있다.  The polymer may be contained in an amount of 0.1% by weight to 30% by weight based on the total amount of the organic film composition.
또다른구현예에 따르면,기판위에 재료층을형성하는단계,상기 재료층 위에상술한중합체 및용매를포함하는유기막조성물을적용하는단계,상기 유기막조성물을열처리하여 하드마스크층을형성하는단계,상기 하드마스크층 위에실리콘함유박막층을형성하는단계,상기 실리콘함유박막층위에  According to another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: forming a material layer on a substrate; applying an organic film composition comprising the polymer and the solvent on the material layer; heat treating the organic film composition to form a hard mask layer , Forming a silicon-containing thin film layer on the hard mask layer,
포토레지스트층을형성하는단계,상기 포토레지스트층을노광및 현상하여 포토레지스트패턴을형성하는단계,상기 포토레지스트패턴을이용하여 상기 실리콘함유박막층및상기 하드마스크층을선택적으로제거하고상기 재료층의 일부를노출하는단계，그리고상기 재료층의 노출된부분을식각하는단계를 포함하는패턴 형성 방법을제공한다. 2019/132153 4 1»（：1^1{2018/009108 상기 유기막조성물을적용하는단계는스핀-온코팅 방법으로수행할수 있다. Forming a photoresist layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern, Exposing a portion of the material layer, and etching the exposed portion of the material layer. The step of applying the organic film composition may be performed by a spin-on coating method.
상기 포토레지스트층을형성하는단계 전에 바닥반사방지 층 쇼11（：）을 형성하는단계를더 포함할수있다.  And forming a bottom antireflective layer show 11 (:) before the step of forming the photoresist layer.
【발명의 효과】  【Effects of the Invention】
일구현예에 따른중합체는헤테로고리기 부분및소정의 링커로연결된 방향족고리기 부분을포함한다. 이에 따라상기 중합체는내식각성과함께 갭-필 특성 및 평탄화특성을동시에 확보할수있으며 ,상기 중합체를유기막재료로 사용할경우내식각성과평탄성이 우수한유기막을제공할수있다.  Polymers according to one embodiment include a heterocyclic group moiety and an aromatic ring moiety connected by a given linker. Accordingly, the polymer can provide both an anti-etching property and a gap-fill property and a planarization property, and when the polymer is used as an organic film material, an organic film having excellent etching resistance and flatness can be provided.
【도면의 간단한설명】  BRIEF DESCRIPTION OF THE DRAWINGS
도 1은일구현예에 따른패탄형성 방법을설명하기 위한흐름도이고, 도 2는평탄화특성과관련한계산식 2를설명하기 위한참고도이고, 도 3은단차특성과관련한계산식 3을설명하기 위한참고도이다.  FIG. 1 is a flow chart for explaining a method of forming a pattern according to an embodiment of the present invention. FIG. 2 is a reference diagram for explaining a calculation formula 2 related to a planarization characteristic, and FIG. 3 is a reference diagram for explaining a calculation formula 3 related to a terminal characteristic .
【발명의 실시를위한최선의 형태】  BEST MODE FOR CARRYING OUT THE INVENTION
이하,본발명의 구현예에 대하여 본발명이 속하는기술분야에서 통상의 지식을가진자가용이하게실시할수있도록상세히 설명한다.그러나본발명은 여러 가지 상이한형태로구현될수있으며 여기에서 설명하는구현예에 한정되지 않는다.  Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art will be able to carry out the present invention in detail. However, the present invention can be embodied in various different forms, It is not limited.
본명세서에서 별도의 정의가없는한,’치환된’이란,화합물중의 수소원자가 할로겐원자（民 ，（그 1,또는 I）,히드록시기 ,니트로기,시아노기 ,아미노기，아지도기, 아미디노기，히드라지노기 ,히드라조노기 ,카르보닐기 ,카르바밀기 ,티올기 , 에스테르기,카르복실기나그의 염,술폰산기나그의 염,인산이나그의 염,（：1내지 030알킬기， 02내지 030알케닐기, 02내지 030알키닐기, 06내지 030아릴기， 07 내지 030아릴알킬기，（그1내지 030알콕시기， 01내지 020헤테로알킬기, 03내지 020헤테로아릴알킬기,
Figure imgf000006_0001
030사이클로알킬기, 03내지 015의 Unless defined otherwise herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (a hydrogen atom, (1 or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, A sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, (: 1 to 030 alkyl group, 02 to 030 alkenyl group, 02 to 030 alkenyl group, or a salt thereof), a hydrazino group, a hydrazino group, a carbonyl group, a carbamoyl group, 030 alkenyl group, 06 to 030 aryl group, 07 to 030 arylalkyl group, (1 to 030 alkoxy group, 01 to 020 heteroalkyl group, 03 to 020 heteroarylalkyl group,
Figure imgf000006_0001
030 < / RTI > cycloalkyl groups,
사이클로알케닐기, 06내지 015사이클로알키닐기, 03내지 030 A cycloalkenyl group, a cyanoalkynyl group, a cyanoalkynyl group,
헤테로사이클로알킬기 및 이들의 조합에서 선택된치환기로치환된 것을의미한다. 또한，본명세서에서 별도의 정의가없는한,’헤테로’란，代 0, 8및뼤서 선택된헤테로원자를 1내지 3개함유한것을의미한다. ≪ / RTI > a heterocycloalkyl group, and combinations thereof. In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from 0, 8, and.
또한,본명세서에서 별도의 정의가없는한，내’는화합물또는화합물 2019/132153 1»（：1^1{2018/009108 Also, unless otherwise defined herein, the term " compound " 2019/132153 1 »(: 1 ^ {2018/009108
5 부분如0 功의 연결지점을가리킨다. 5 Point to point 0 connection point.
이하일구현예에 따른중합체를설명한다.  Polymers according to embodiments below will be described.
일구현예에 따른중합체는하기 화학식 1로표현되는구조단위를포함한다. [화학식 1]  The polymer according to one embodiment comprises a structural unit represented by the following formula (1). [Chemical Formula 1]
6 ★ 상기 화학식 1에서， ★ 6 in formula (I),
쇼는하기 화학식 2로표현되는모이어티이고,  The show is a moiety represented by the following formula (2)
6는하기 화학식 3으로표현되는모이어티이고,  6 is a moiety represented by the following formula (3)
*은연결지점이다:  * Is the connection point:
[화학식 2]  (2)
Figure imgf000007_0001
Figure imgf000007_0001
상기 화학식 2에서,  In Formula 2,
는 NR0, O또는 이고，여기서 는수소,치환또는비치환된 01내지 030 알킬기，치환또는비치환된 06내지 030아릴기，또는이들의 조합이고， Is NR < 0 > O, or wherein R is hydrogen, a substituted or unsubstituted 01 to O30 alkyl group, a substituted or unsubstituted 06 to O30 aryl group,
II1은히드록시기，할로겐기,치환또는비치환된 01내지 030알콕시기,치환 또는비치환된 01내지 030알킬기,치환또는비치환된 02내지 030알케닐기, 치환또는비치환된 02내지 030알키닐기,치환또는비치환된 06내지 030 아릴기,치환또는비치환된＜그1내지 30헤테로알킬기,치환또는비치환된 02 내지 030헤테로아릴기,또는이들의 조합이고， II 1 represents a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, a substituted or unsubstituted 02 to 030 alkynyl group , A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted 1 to 30 heteroalkyl group, a substituted or unsubstituted 02 to 030 heteroaryl group, or a combination thereof,
는 0내지 3인정수이고,  Is an integer of 0 to 3,
*은연결지점이다:  * Is the connection point:
[화학식 3]
Figure imgf000007_0002
(3)
Figure imgf000007_0002
상기 화학식 3에서, 2019/132153 1»（：1^1{2018/009108 In Formula 3, 2019/132153 1 »(: 1 ^ {2018/009108
6 및 I?는각각독립적으로 0, 8, 802,또는카르보닐이고, 6 and I are each independently 0, 8, 80 2, or carbonyl,
내지 II5는각각독립적으로히드록시기,할로겐기,치환또는비치환된 01내지 030알콕시기,치환또는비치환된 01내지 030알킬기，치환또는 비치환된 02내지 030알케닐기,치환또는비치환된 02내지 030알키닐기,치환 또는비치환된 06내지 030아릴기，치환또는비치환된 01내지 030헤테로알킬기, 치환또는비치환된 02내지 030헤테로아릴기,또는이들의조합이고, To II 5 each independently represent a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, a substituted or unsubstituted 02 A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to O30 heteroaryl group,
내지 6는각각독립적으로 0내지 4인정수이고, To 6 are independently 0 to 4 numbers,
모6내지 II11은각각독립적으로수소,치환또는비치환된 01내지 030 알킬기，치환또는비치환된 06내지 030아릴기,또는이들의조합이고, Each of Mo 6 to II 11 is independently hydrogen, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 06 to 30 aryl group, or a combination thereof,
II은 0내지 5인정수이고,  II is an integer from 0 to 5,
*은연결지점이다.  * Is the connection point.
상기 중합체는상기 화학식 1로표현되는구조단위를포함하며,여기서 이들구조단위의 개수및 배열은한정되지 않는다.  The polymer includes the structural unit represented by the formula (1), wherein the number and arrangement of these structural units are not limited.
상기 화학식 1로표현되는구조단위는헤테로고리기 부분 ）및소정의 링커,즉 0, 8, 802,또는카르보닐로연결된방향족고리기 부분（미을포함한다. The structural unit represented by the formula ( 1 ) includes a heterocyclic group moiety) and a predetermined linker, i.e., 0, 8, 80 , or a carbonyl-linked aromatic ring group moiety.
상기 헤테로고리기 부분（쇼）은상기 화학식 2로표현되고,상기 소정의 링커로연결된방향족고리기 부분（미은상기 화학식 3으로표현된다. 예를들어， 상기 헤테로고리기 부분（시에서 오각고리 부분이 상기 소정의 링커로연결된 방향족고리기 부분（미과연결될수있다.  The heterocyclic group portion (shown) is represented by the formula (2) shown above, and the aromatic ring group moiety connected to the predetermined linker (represented by Formula 3). For example, the heterocyclic ring moiety in the heterocyclic group moiety may be connected to the aromatic ring group moiety connected to the predetermined linker.
상기 화학식 2에서오각고리 내에 포함된헤테로원자는代0또는요이다. 상기 화학식 2에서 육각고리는예컨대히드록시기,할로겐기，치환또는비치환된 01내지 030알콕시기，치환또는비치환된 01내지 030알킬기,치환또는 비치환된 02내지 030알케닐기 ,치환또는비치환된 02내지 030알키닐기 ,치환 또는비치환된 06내지 30아릴기 ,치환또는비치환된 01내지 030헤테로알킬기 , 또는치환또는비치환된 02내지 030헤테로아릴기와같은작용기에 의해 치환될 수도있고,비치환된형태일수도있다.  In the formula (2), the hetero atom contained in the pentagonal ring is 0 or 0. In formula (2), the hexagonal ring includes, for example, a hydroxy group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, It may be in inverted form.
이와같이,상기 중합체는그구조단위 내에 상기 화학식 2로표현되는 구조를포함하므로기본적으로내식각성이 우수하다.  Thus, since the polymer contains the structure represented by the formula (2) in its structural unit, it is basically excellent in corrosion resistance.
상기 화학식 3으로표현되는부분（미은 2개의 벤젠고리가 0, 8, 802,또는 카르보닐인링커에 의해 연결되어 있는구조를가지며,이러한구조는 1개일수도 있고（즉,상기 화학식 3에서 n=0인경우）， 2개내지 6개일수도있다（즉,상기 화학식 3에서 n이 1내지 5인경우）. The moiety represented by the above formula (3) has a structure in which two benzene rings are linked by 0, 8, and 80 2, or a linker such as a carbonyl linker, (That is, when n = 0 in the formula (3)), it may be 2 to 6 (that is, n is 1 to 5 in the formula (3)).
예를들어，상기 화학식 3에서 L1및 L2는각각 0,즉에테르링커일수 있으나이에 한정되는것은아니다. For example, in Formula 3, L 1 and L 2 may each be 0, that is, an ether linker, but the present invention is not limited thereto.
상기 중합체는그구조단위 내에 상기 화학식 3으로표현되는소정의 연결기를포함함으로써 중합체의 유연성（flexibility）을증가시킬수있다. 이러한 유연한구조는중합체의 자유부피（free volume）을증가시켜 용해도를향상시킬뿐만 아니라,유리전이온도（Tg）를낮춤으로써 베이크공정 시 갭-필성능및평탄화 향상을가져올수있다.  The polymer may increase the flexibility of the polymer by including a predetermined linking group represented by the general formula (3) in its structural unit. This flexible structure not only improves the solubility of the polymer by increasing the free volume of the polymer but also lowers the glass transition temperature (Tg), thereby improving the gap-fill performance and planarization in the baking process.
상기 중합체는약 500내지 200, 000의 중량평균분자량을가질수있다. 보다 구체적으로상기 중합체는약 1,000내지 20, 000의 중량평균분자량을가질수있다. 상기 범위의 중량평균분자량을가짐으로써 상기 중합체를포함하는유기막 조성물（예컨대,하드마스크조성물）의 탄소함량및용매에 대한용해도를조절하여 최적화할수있다.  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. By having a weight average molecular weight in the above range, it is possible to optimize by adjusting the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.
상기 중합체를유기막재료로서사용할경우，베이크공정 중핀-홀및 보이드의 형성이나두께산포의 열화없이 균일한박막을형성할수있을뿐만 아니라하부기판（혹은막）에 단차가존재하는경우혹은패턴을형성하는경우 우수한캡-필및평탄화특성을제공할수있다.  When the polymer is used as an organic film material, a uniform thin film can be formed without forming pin-holes and voids in the baking process or deterioration in thickness scattering, and when a step is present in the lower substrate (or film) Can provide excellent cap-fill and planarization characteristics.
다른구현예에 따르면，상술한중합체，그리고용매를포함하는유기막 조성물을제공한다.  According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.
상기 용매는상기 중합체에 대한충분한용해성 또는분산성을가지는 것이면특별히 한정되지 않으나,예컨대프로필렌글리콜,프로필렌글리콜  The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, and examples thereof include propylene glycol, propylene glycol
디아세테이트，메톡시 프로판디올，디에틸렌글리콜,디에틸렌글리콜부틸에테르, 트리（에틸렌글리콜）모노메틸에테르,프로필렌글리콜모노메틸에테르,프로필렌글리콜 모노메틸에테르아세테이트,사이클로핵사논,에틸락테이트,감마-부티로락톤， N,N- 디메틸포름아미드, N,N-디메틸아세트아미드,메틸피롤리돈，메틸피롤리디논, 아세틸아세톤및 에틸 3 -에톡시프로피오네이트에서 선택되는적어도하나를포함할 수있다. (Ethyleneglycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, diethylene glycol, diethylene glycol diethyl ether, May include at least one selected from among butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate have.
상기 중합체는상기 유기막조성물의총함량에 대하여 약 0.1내지 50 중량%，약 0.1내지 30중량%,또는약 0.1내지 15중량%로포함될수있다. 상기 '¥° 2019/132153 8 1몌012018/009108 범위로중합체가포함됨으로써 유기막의 두께,표면거칠기 및평탄화정도를 조절할수있다. The polymer 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 organic film composition. remind '¥ ° 2019/132153 8 1 mye containing the polymer as being 012018/009108 range may be adjusted to a thickness of organic layer, the surface roughness and the planarization.
상기 유기막조성물은추가적으로계면활성제,가교제,열산발생제,가소제 등의 첨가제를더 포함할수있다.  The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
상기 계면활성제는예컨대플루오로알킬계화합물，알킬벤젠설폰산염， 알킬피리디늄염,폴리에틸렌글리콜,제 4암모늄염 등을사용할수있으나이에 한정되는것은아니다.  Examples of the surfactant include, but are not limited to, a fluoroalkyl-based compound, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, and a quaternary ammonium salt.
상기 가교제는예컨대 멜라민계，치환요소계，또는이들폴리머계등을들수 있다. 바람직하게는,적어도 2개의 가교형성 치환기를갖는가교제로,예를들면, 메톡시메틸화글리코루릴,부톡시메틸화글리코루릴,메톡시메틸화멜라민, 부톡시메틸화멜라민,메톡시메틸화벤조구아나민,부톡시메틸화벤조구아나민, 메톡시메틸화요소，부톡시메틸화요소,메톡시메틸화티오요소，또는부톡시메틸화 티오요소등의 화합물을사용할수있다.  Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glycerol, a butoxymethylated glyceryl, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxy Methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea can be used.
또한,상기 가교제로는내열성이 높은가교제를사용할수있다.내열성이 높은가교제로는분자내에 방향족고리（예를들면벤젠고리，나프탈렌고리）를 가지는가교형성 치환기를함유하는화합물을사용할수있다.  As the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having high heat resistance, a compound containing a crosslinking forming substituent group having an aromatic ring (for example, benzene ring or naphthalene ring) in the molecule can be used.
상기 열산발생제는예컨대 I）-톨루엔술폰산，트리플루오로메탄술폰산, 피리디늄 톨루엔술폰산,살리실산，술포살리실산,구연산,안식향산,  The thermal acid generators may be, for example, I) -toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid,
하이드록시안식향산,나프탈렌카르본산등의산성 화합물또는/및 2, 4,4,6- 테트라브로모시클로핵사디에논,벤조인토실레이트, 2 -니트로벤질토실레이트,그밖에 유기술폰산알킬에스테르등을사용할수있으나이에 한정되는것은아니다. Acidic compounds such as hydroxybenzoic acid and naphthalenecarboxylic acid and / or 2 , 4 , 4 , 6 -tetrabromocyclohexadienone, benzoinositolate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters But is not limited thereto.
상기 첨가제는상기 유기막조성물 100중량부에 대하여 약 0.001내지 40 중량부로포함될수있다.상기 범위로포함함으로써 유기막조성물의 광학적 특성을변경시키지 않으면서 용해도를향상시킬수있다.  The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including the additives in the above range, the solubility can be improved without changing the optical properties of the organic film composition.
또다른구현예에 따르면,상술한유기막조성물을사용하여 제조된 유기막을제공한다. 상기 유기막은상술한유기막조성물을예컨대 기판위에 코팅한후열처리 과정을통해 경화된형태일수있으며，예컨대하드마스크층， 평탄화막,희생막,충진제등전자디바이스에사용되는유기 박막을포함할수 있다.  According to another embodiment, there is provided an organic film produced using the organic film composition described above. The organic layer may be formed by coating the above-described organic film composition on a substrate and then curing through a heat treatment process, for example, an organic thin film used for an electronic device such as a hard mask layer, a planarization layer, a sacrificial layer, and a filler.
이하상술한유기막조성물을사용하여 패턴을형성하는방법에 대하여 도 1을참고하여 설명한다. Hereinafter, a method of forming a pattern using the organic film composition described above 1.
도 1은일구현예에 따른패턴형성 방법을설명하는흐름도이다.  1 is a flowchart illustrating a pattern forming method according to an embodiment.
일구현예에 따른패턴 형성 방법은기판위에 재료층을형성하는단계 (S1), 상기 재료층위에상술한중합체 및용매를포함하는유기막조성물을적용하는 단계 (S2),상기 유기막조성물을열처리하여 하드마스크층을형성하는단계 (S3), 상기 하드마스크층위에 실리콘함유박막층을형성하는단계 (S4),상기 실리콘 함유박막층 위에 포토레지스트층을형성하는단계 (S5),상기 포토레지스트층을 노광및 현상하여포토레지스트패턴을형성하는단계 (S6),상기 포토레지스트 패턴을이용하여 상기 실리콘함유박막층및상기 하드마스크층을선택적으로 제거하고상기 재료층의 일부를노출하는단계 (S7),그리고상기 재료층의 노출된 부분을식각하는단계 (S8)를포함한다.  The pattern forming method according to one embodiment includes the steps of forming a material layer on a substrate (S1), applying (S2) an organic film composition including the above-mentioned polymer and a solvent on the material layer, Forming a hard mask layer (S3) on the hard mask layer, forming a silicon-containing thin film layer on the hard mask layer (S4), forming a photoresist layer on the silicon-containing thin film layer (S5) (S6) selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a part of the material layer using the photoresist pattern, And etching the exposed portion of the material layer (S8).
상기 기판은예컨대실리콘웨이퍼,유리 기판또는고분자기판일수있다. 상기 재료층은최종적으로패턴하고자하는재료이며,예컨대 알루미늄， 구리 등과같은금속층,실리콘과같은반도체층또는산화규소，질화규소등과 같은절연층일수있다.상기 재료층은예컨대화학기상증착방법으로형성될수 있다.  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 and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon or an insulating layer such as silicon oxide, silicon nitride, etc. The material layer may be formed by, for example, have.
상기 유기막조성물은전술한바와같으며，용액 형태로제조되어 스핀-온 코팅 방법으로도포될수있다.이 때상기 유기막조성물의 도포두께는특별히 한정되지 않으나,예컨대 약 50내지 200,000A또는약 50내지 10,000 A두께로 도포될수있다.  The organic film composition may be prepared in the form of a solution and applied by a spin-on coating method. The thickness of the organic film composition is not particularly limited, but may be about 50 to 200,000 A or about 50 To 10,000 A thick.
상기 유기막조성물욜열처리하는단계는예컨대 약 100내지 700°C에서 약 10초 내지 1시간 동안수행할수있다.  The step of heat treating the organic film composition may be carried out, for example, at about 100 to 700 ° C for about 10 seconds to 1 hour.
상기 실리콘함유박막층은예컨대 SiCN, SiOC， SiON, SiOCN, SiC， SiO및/또는 SiN등의 물질로형성할수있다.  The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and / or SiN.
또한상기 포토레지스트층을형성하는단계 전에 상기 실리콘함유박막층 상부에 바닥반사방지 증 (bottom anti-reflective coating, BARC)을더 형성할수도있다. 상기 포토레지스트층을노광하는단계는예컨대 ArF, KrF또는 EUV등을 사용하여 수행할수있다. 또한노광후약 100내지 700°C에서 열처리 공정을 수행할수있다.  Further, a bottom anti-reflective coating (BARC) may be formed on the silicon-containing thin film layer before the step of forming the photoresist layer. The step of exposing the photoresist layer may be performed using ArF, KrF or EUV, for example. Further, the heat treatment can be performed at an exposure time of 100 to 700 ° C.
상기 재료층의 노출된부분을식각하는단계는식각가스를사용한건식 2019/132153 1»（：1^1{2018/009108 Wherein etching the exposed portion of the material layer comprises: 2019/132153 1 »(: 1 ^ {2018/009108
10
Figure imgf000012_0001
10
Figure imgf000012_0001
혼합가스를사용할수있다. Mixed gas may be used.
상기 식각된재료층은복수의 패턴으로형성될수있으며，상기 복수의 패턴은금속패턴，반도체 패턴,절연패턴등다양할수있으며,예컨대 반도체 집적 회로디바이스내의 다양한패턴으로적용될수있다.  The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, or the like, and may be applied in various patterns, for example, in a semiconductor integrated circuit device.
【발명의 실시를위한형태】 DETAILED DESCRIPTION OF THE INVENTION
이하실시예를통하여 상술한본발명의 구현예를보다상세하게설명한다. 다만하기의 실시예는단지 설명의 목적을위한것이며 본발명의 범위를제한하는 것은아니다. 합성예  Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention. Synthetic example
합성예 1 플라스크에 6 -하이드록시인돌 (26.6& 0.211101), 4,4’-비스메톡시메틸 Synthesis Example 1 In a flask, 6-hydroxyindole (26.6 & 0.211101), 4,4'-bismethoxymethyl
Figure imgf000012_0002
Figure imgf000012_0002
모노메틸에테르아세테이트 0\1표시78.2은을투입한후, 100 (：에서 2내지 15시간 동안교반하여 중합반응을수행하였다 . 1시간간격으로상기 중합반응물로부터 시료를취하여,중량평균분자량이 2,000내지 3,500일 때 반응을완료하였다. 중합 반응이 완료된후,반응물을상온으로서서히 냉각시킨후상기 반응물을증류수 Polymerization was carried out by stirring at 100 (: for 2 to 15 hours after the addition of silver 78.2 of monomethyl ether acetate.) A sample was taken from the polymerization reaction at intervals of 1 hour, and a weight average molecular weight of 2,000 ~ The reaction was completed at 3,500. After completion of the polymerization reaction, the reaction product was slowly cooled to room temperature, and the reaction product was distilled
40§및 메탄올 400§에 투입하여 강하게교반한후,정치시켜 침전을형성시켰다. 형성된침전물을프로필렌글리콜모노메틸에테르아세테이트 (PGMEA) 80g에 녹인후, 메탄올 320 &물 32(¾를이용하여 강하게교반하고침전을형성시켰다.이때 40 및 and methanol 400 § , stirred vigorously, and then allowed to stand to form a precipitate. The resulting precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and then stirred vigorously to form a precipitate using methanol 320 and water 32 (¾)
얻어지는침전물을프로필렌글리콜모노메틸에테르아세테이트 (PGMEA) 8 에 녹였다. 침전물을 2회 형성시키는상기 정제공정을총 3회 실시하였다.정제가끝난 중합체를프로필렌글리콜모노메틸에테르아세테이트 (PGMEA) 80g에 녹인후,감압 하에서 용액에 남아있는메탄올및증류수를제거하여 하기 화학식 1-1로표현되는 구조단위를포함하는중합체를얻었다 (1 : 2,900). 2019/132153 1»（：1^1{2018/009108 The resulting precipitate was dissolved in propylene glycol monomethyl ether acetate (PGMEA) 8. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and the methanol and distilled water remaining in the solution were removed under reduced pressure to obtain the following formula -1 was obtained (1: 2,900). 2019/132153 1 »(: 1 ^ {2018/009108
11  11
［화학식 1-1］
Figure imgf000013_0001
합성예 2 시아나프텐 (26.8 0.211101), 4,4’-비스메톡시메틸다이페닐에테르 (51.6& 0.211101), 프로필렌글리콜모노메틸에테르아세테이트 ^SAg및 디에틸설페이트 (0.9& 6_01)을 사용하여 합성예 1과동일한합성 과정을거쳐 화학식 1-2로표현되는구조단위를 포함하는중합체를얻었다 ( \¥: 2,700). [Formula 1-1]
Figure imgf000013_0001
Synthesis Example 2 cyano naphthenes (26.8 0.211101), 4, 4'-bis methoxymethyl diphenyl ether (51.6 & 0.2 0 11 101), propylene glycol monomethyl ether acetate ^ SAg, and diethyl sulfate (0.9 and 6 _ 01 ) , A polymer containing the structural unit represented by the general formula (1-2) was obtained through the same synthesis procedure as in Synthesis Example 1 (\: 2,700).
［화학식 1-2］
Figure imgf000013_0002
합성예 3 인돌 (23.4生 0.211101), 4,4’-비스메톡시메틸다이페닐에테르 (51.6生 0.211101), 프로필렌글리콜모노메틸에테르아세테이트
Figure imgf000013_0003
[Formula 1-2]
Figure imgf000013_0002
SYNTHESIS EXAMPLE 3 A mixture of indole (23.4 raw 0.2 11101) , 4,4'- bismethoxymethyl diphenyl ether (51.6 raw 0.2 11101), propylene glycol monomethyl ether acetate
Figure imgf000013_0003
사용하여 합성예 1과동일한합성 과정을거쳐 화학식 1-3으로표현되는구조 단위를포함하는중합체를얻었다 ( 1 2,700). ［화학식 1-3］ , A polymer containing the structural unit represented by Formula 1-3 was obtained (1,2,700) by the same synthetic procedure as Synthesis Example 1. [Formula 1-3]
Figure imgf000013_0004
인돌 (23.始, 0.2뻬), 2, 2’-비스［4-(4 -메톡시메틸페녹시)페닐］프로판 (94.4生 ( 뻬), 프로필렌글리콜모노메틸에테르아세테이트 117.8§및 디에틸설페이트 (0.9&
Figure imgf000013_0004
Indole (3. 2始, Peroni 0.2), 2,2'-bis [4- (4-methoxymethyl) phenyl] propane (94.4生(Peroni), propylene glycol monomethyl ether acetate and diethyl § 117.8 Sulfate (0.9 &
611111101)을사용하여 합성예 1과동일한합성 과정을거쳐 화학식 1-4로표현되는 구조단위를포함하는중합체를얻었다 ( 1 : 3,800). 2019/132153 1»（：1/10公018/009108 611111101), a polymer containing the structural unit represented by the general formula (1-4) was obtained (1: 3,800) through the same synthesis procedure as in Synthesis Example 1. 2019/132153 1 »(: 1/10/10/01/009108
12  12
［화학식 1-4］
Figure imgf000014_0001
비교합성예 1 플라스크에 4,4’-911-플루오렌-9,9-다이일다이페놀 (70¾ 0.211101), 1,4- 비스메톡시메틸벤젠 (34& 0.211101),프로필렌글리콜모노메틸에테르아세테이트 104§및 디에틸설페이트 (0.9 & 6_01)을사용하여 합성예 1과동일한합성 과정을거쳐 화학식쇼로표현되는구조단위를포함하는중합체를얻었다 ( 1 3,700). [Formula 1-4]
Figure imgf000014_0001
Comparative Synthesis Example 1 Into a flask were introduced 4,4'-911-fluorene-9,9-diyl diphenol (70 ¾ 0.211101) , 1,4- bismethoxymethylbenzene (34 & 0.211101), propylene glycol monomethyl ether Acetate 104 및 and diethylsulfate (0.9 & 6 01) were used to obtain a polymer containing structural units represented by the formula show (13,700) through the same synthetic procedure as in Synthesis Example 1.
［화학식시 [Chemical formula
Figure imgf000014_0002
Figure imgf000014_0002
비교합성예 2  Comparative Synthesis Example 2
4,4’-9표-플루오렌-9,9-다이일다이페놀 (70 & 0.211101), 4,4’-비스메톡시메틸 다이페닐에테르 (51.6& 0,211101),프로필렌글리콜모노메틸에테르아세테이트 121.6§및 디에틸설페이트 (0.9& 611111101)을사용하여 합성예 1과동일한합성 과정을거쳐 화학식 8로표현되는구조단위를포함하는중합체를얻었다 ( 1 3,800). 4,4'-9 Toluene-9,9-diallyl diphenol (70 & 0 .2 11101), 4,4' -bismethoxymethyl diphenyl ether (51.6 & 0,211101), propylene glycol using monomethyl ether acetate 121.6 § and diethyl sulfate (0.9 and 611 111 101) through the same synthetic procedure as in Preparation example 1 to obtain a polymer comprising a structural unit represented by the formula (8) (1 3800).
［화학식미 [Chemical formula
Figure imgf000014_0003
비교합성예 3 플라스크에 6 -하이드록시인돌 (26.6¾ 0.21X101)， 1,4 -비스메톡시메틸벤젠 (34용， 0.211101),프로필렌글리콜모노메틸에테르아세테이트 60.6용및 디에틸설페이트 (0.9 2019/132153 13 1»（：1^1{2018/009108
Figure imgf000014_0003
Comparative Synthesis Example 3 In a flask, 6-hydroxyindole (26.6 0 0 .2 1 X 101) , 1,4-bismethoxymethylbenzene (34, 0.211101), propylene glycol monomethyl ether acetate 60.6 and diethyl sulfate (0.9 2019/132153 13 1 »(: 1 ^ {2018/009108
611111101)을사용하여 합성예 1과동일한합성 과정을거쳐 화학식 (：로표현되는구조 단위를포함하는중합체를얻었다 ( 1 : 2,500). 611111101), a polymer containing a structural unit represented by the following formula (: (1: 2,500) was obtained through the same synthesis procedure as in Synthesis Example 1.
［화학식 (：］
Figure imgf000015_0001
[Chemical formula (:
Figure imgf000015_0001
비교합성예 4 플라스크에 1 -나프톨 (28.8邑 0.21X101), 3,5 -비스 (메톡시메틸)비페닐 (48.4¾ 0.21^1), 프로필렌글리콜모노메틸에테르아세테이트 112色및 디에틸설페이트 (0.9& 6_01)을 사용하여 합성예 1과동일한합성 과정을거쳐 화학식 I)로표현되는구조단위를 포함하는중합체를얻었다 ( 1 : 2,800). Comparative Synthesis Example 4 In a flask, 1-naphthol (28.8 eups 0.2 1X101) , 3,5-bis (methoxymethyl) biphenyl (48.4 ¾ 0.21 ^ 1), propylene glycol monomethyl ether acetate 112 colors and diethylsulfate & Lt; 6 & gt; 01) , a polymer containing the structural unit represented by the formula (I) was obtained (1: 2,800) through the same synthetic procedure as in Synthesis Example 1.
［화학식 D］
Figure imgf000015_0002
[Chemical Formula D]
Figure imgf000015_0002
비교합성예 5 플라스크에 1 -하이드록시파이렌 (43.6生 0.211101), 1,4 -비스메톡시메틸벤젠 (34 & 0.21!101)，프로필렌글리콜모노메틸에테르아세테이트ᄁ.6엉및 디에틸설페이트 (0.9& 6_01)을사용하여 합성예 1과동일한합성 과정을거쳐 화학식 £로표현되는구조 단위를포함하는중합체를얻었다 (Mw: 3,000). Comparative Synthesis Example 5 To a flask was added 1-hydroxy pyrene (43.6 raw 0.2 11101) , 1,4- bismethoxymethyl benzene (34 & 0.2 0.11 ) , propylene glycol monomethyl ether acetate? Sulfate (0.9 & 6_01 ) was synthesized in the same manner as in Synthesis Example 1 to obtain a polymer containing a structural unit represented by the formula (Mw : 3,000) .
［화학식 E］
Figure imgf000015_0003
하드마스크조성물의 제조 실시예 1 (E)
Figure imgf000015_0003
Preparation of hard mask composition Example 1
합성예 1에서 얻은중합체 lg을  1 g of the polymer obtained in Synthesis Example 1
프로필렌글리콜모노메틸에테르아세테이트 (propylene glycol monomethyl ether acetate, PGMEA)와사이클로핵사논 (cyclohexanone)(7:3(v/v))의 혼합용매 10g에 녹인후 0.1_의 테플론필터로여과하여 하드마스크조성물을제조하였다. The mixture was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), .
실시예 2  Example 2
합성예 1에서 얻은중합체 대신합성예 2에서 얻은중합체를사용한것을 제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.
실시예 3  Example 3
합성예 1에서 얻은중합체 대신합성예 3에서 얻은중합체를사용한것을 제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 3 was used in place of the polymer obtained in Synthesis Example 1.
실시예 4  Example 4
합성예 1에서 얻은중합체 대신합성예 4에서 얻은중합체를사용한것을 제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 4 was used in place of the polymer obtained in Synthesis Example 1.
비교예 1  Comparative Example 1
합성예 1에서 얻은중합체 대신비교합성예 1에서 얻은중합체를사용한 것을제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 1 was used in place of the polymer obtained in Synthesis Example 1.
비교예 2  Comparative Example 2
합성예 1에서 얻은중합체 대신비교합성예 2에서 얻은중합체를사용한 것을제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.
비교예 3  Comparative Example 3
합성예 1에서 얻은중합체 대신비교합성예 3에서 얻은중합체를사용한 것을제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 3 was used in place of the polymer obtained in Synthesis Example 1.
비교예 4  Comparative Example 4
합성예 1에서 얻은중합체 대신비교합성예 4에서 얻은중합체를사용한 것을제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 4 was used in place of the polymer obtained in Synthesis Example 1.
비교예 5  Comparative Example 5
합성예 1에서 얻은중합체 대신비교합성예 5에서 얻은중합체를사용한 것을제외하고는실시예 1과동일한방법으로하드마스크조성물을제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 5 was used in place of the polymer obtained in Synthesis Example 1.
l· 평가 1:내식각성 실리콘웨이퍼위에 실시예 1내지 4와비교예 1내지 5에 따른하드마스크 조성물을실리콘웨이퍼 위에 스핀-온코팅한후핫플레이트위에서 4001：로 120초간열처리하여 박막을형성한
Figure imgf000017_0001
815000박막두께측정기로 형성된박막의 두께를측정하였다. 이어서 상기 박막에 2/02 l · Evaluation 1: Austenitic-awakening A hard mask composition according to Examples 1 to 4 and Comparative Examples 1 to 5 was spin-on coated on a silicon wafer on a silicon wafer, followed by heat treatment at 4001: for 120 seconds on a hot plate to form a thin film
Figure imgf000017_0001
815000 Thickness of thin film formed by thin film thickness meter was measured. Then the thin film 2/0 2
혼합가스（5011117300\¥/02 10 011/此 50 011）를사용하여 각각 60초동안드라이 에칭을진행한후,박막의 두께를측정하여 그차이로부터 하기 계산식 1에 의해 식각율（加止 此 8표11）을계산하였다.
Figure imgf000017_0002
Proceed to dry etching for 60 seconds each using a mixed gas (50 1111 7300 \ ¥ / 0 2 10 0 11 /此50 0 11), by measuring the thickness of a thin film etch rate by the following formula 1 from the difference (Table 11) were calculated.
Figure imgf000017_0002
428（X111/^ 600^011/02 1580011）를사용하여 120초동안드라이 에칭을진행한후 박막의 두께를측정하여 그차이로부터 하기 계산식 1에
Figure imgf000017_0003
To 42 8 (X 111 / ^ 600 ^ 0 11/02 1580011) and then proceed with the dry etching for 120 seconds by using the measurement of the film thickness to the difference from the first calculation,
Figure imgf000017_0003
요표幻을계산하였다.  I calculated the illusion.
[계산식 1] [Equation 1]
（초기 박막두께 -식각후박막두께）/식각시간（ᅀ/300 그결과는표 1과같다. [표 1] (Initial thin film thickness - thin film thickness after etching) / etching time (ᅀ / 30 0) The results are shown in Table 1. [Table 1]
Figure imgf000017_0004
표 1을참고하면,실시예 1내지 4에 따른하드마스크조성물로부터 형성된 박막은비교예 1내지 5에 따른하드마스크조성물로부터 형성된박막과비교하여 식각가스에 대한충분한내식각성이 있어서 벌크에치 특성이 향상됨을확인할수 있다. 평가 2:갭-필 (Gap-fill)및평탄화특성 패턴이 형성된웨이퍼에실시예 1내지 4와비교예 1내지 5에 따른 하드마스크조성물을도포하고핫플레이트를이용한베이크공정을거쳐 박막을 형성시킨 이후에,접-필특성과평탄화특성을관찰하였다. 캡-필특성은패턴의 단면을 FE-SEM설비 (Hitachi, S-4800)로관찰하여 보이드 (Void)발생유무로판별하였고,평탄화특성 (Planarity)은 K-MAC社의 박막두께측정기로패턴주변의 박막두께를측정하여 도 2에 나타낸계산식 2로 수치화하였다. 그결과를표 2에 나타낸다.
Figure imgf000017_0004
Referring to Table 1, the thin films formed from the hard mask compositions according to Examples 1 to 4 had sufficient erosion-resistance to the etching gas as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 5, Can be confirmed. Evaluation 2: gap-fill (Gap-fill), and applying a hardmask composition according to an embodiment 1-4 Wabi Comparative Example 1-5 in the wafer is formed planarization characteristic pattern] After forming a thin film through a baking process using a hot plate , The contact characteristics and planarization characteristics were observed. The cap-fill characteristic was determined by observing the cross section of the pattern with FE-SEM equipment (Hitachi, S-4800) and determining the occurrence of voids. The planarity was determined by K- And the thickness of the film was measured by the equation 2 shown in Fig. The results are shown in Table 2.
[표 2] [Table 2]
Figure imgf000018_0001
평탄화특성은라인/스페이스 (0 /8?^6)패턴에서 스페이스패턴위에 형성된박막의 두께차이，즉,도 2에서 111과 1x2의 차이가크지 않을수록우수한- 2019/132153 1»（：1^1{2018/009108
Figure imgf000018_0001
The planarization characteristics are as follows. As the difference in the thickness of the thin film formed on the space pattern in the line / space (0/8 ? 6) pattern, that is, the difference between 1 11 and 1x 2 in FIG. 2, 2019/132153 1 »(: 1 ^ {2018/009108
17 것이다. 표 2를참고하면,실시예 1내지 4에 따른하드마스크조성물로부터 형성된 박막은비교예 1내지 5에 따른하드마스크조성물로부터 형성된박막과비교하여 평탄화특성 및 갭-필특성을동시에 확보가능함을확인할수있다. 평가 3:단차특성 패턴화된웨이퍼에 실시예 1내지 4와비교예 1내지 5에 따른하드마스크 조성물을도포하고베이크공정을거친후， FE-SEM장비를이용하여 단차특성을 관찰하였다. 단차특성은하기 계산식 3으로수치화하였다. 도 3은단차합계를 산출하는계산식 3을설명하기 위한참고도이다.도 3을참고하면,페리와의 거리에 따라셀부분에서의 막두께가달라지므로페리에서 가까운순서로 4개의 셀을 선정하여 , 4개지점에서 셀과페리 영역의 단차의 합이 작을수록단차특성이 우수한것으로한다. 17. Referring to Table 2, it can be seen that the thin films formed from the hard mask compositions according to Examples 1 to 4 can simultaneously obtain planarization characteristics and gap-fill characteristics in comparison with the thin films formed from the hard mask compositions according to Comparative Examples 1 to 5 have. Evaluation 3: Step characteristics After the patterned wafers were coated with the hard mask composition according to Examples 1 to 4 and Comparative Examples 1 to 5, and subjected to the baking process, the step characteristics were observed using FE-SEM equipment. The step characteristic is numerically expressed by the following equation 3 . FIG. 3 is a reference diagram for explaining the calculation formula 3 for calculating the end sum. Referring to FIG. 3, since the film thickness in the cell portion varies according to the distance from the ferry, four cells are selected in the order close to the ferry , And the step characteristics are superior as the sum of the steps of the cell and the ferry area is smaller at four points.
[계산식 3][Equation 3]
Figure imgf000019_0001
그결과를표 3에 나타낸다. [표 3]
Figure imgf000019_0001
The results are shown in Table 3. [Table 3]
Figure imgf000019_0002
2019/132153 18 1»（：1^1{2018/009108
Figure imgf000020_0001
표 3을참고하면,실시예 1내지 4에 따른하드마스크조성물로부터 형성된 박막은비교예 1내지 5에 따른하드마스크조성물로부터 형성된박막과비교하여， 계산식 3에 따른단차합계가상대적으로작은값이므로우수한막평탄도를 가짐을알수있다. 표 1내지 3을참고하면,실시예 1내지 4에 따른하드마스크조성물로부터 형성된박막은내식각성,갭-필 &1 -피1)및평탄화특성,그리고단차특성이 종합적으로우수함을확인할수있다. 이에 반해，비교예 1내지 5에 따른따른 하드마스크조성물로부터 형성된박막은전반적인박막특성이 좋지 않거나,또는 내식각성을만족하는경우평탄성이 매우떨어지거나，또는단차특성을만족하는 경우내식각성이 매우떨어지는등,하드마스크박막에서 요구되는제물성을 고르게충족시키지 못함을알수있다.
Figure imgf000019_0002
2019/132153 18 1 »(: 1 ^ 1 {2018/009108
Figure imgf000020_0001
Referring to Table 3, the thin films formed from the hard mask compositions according to Examples 1 to 4 are superior to the thin films formed from the hard mask composition according to Comparative Examples 1 to 5 because the step sum according to Equation 3 is a relatively small value It can be seen that the film has flatness. Referring to Tables 1 to 3, it can be confirmed that the thin films formed from the hard mask compositions according to Examples 1 to 4 are excellent in corrosion resistance, gap-fill and 1 -p 1), planarization characteristics, and step characteristics. On the contrary, the thin films formed from the hard mask compositions according to Comparative Examples 1 to 5 exhibited poor flatness when the overall thin film characteristics were unsatisfactory, or when the corrosion resistance was satisfied, or when the step characteristics were satisfied, , It is difficult to uniformly satisfy the required physical properties of the hard mask thin film.
이상에서 본발명의 바람직한실시예들에 대하여 상세하게설명하였지만본 발명의 권리 범위는이에 한정되는것은아니고다음의 청구범위에서 정의하고 있는본발명의 기본개념을이용한당업자의 여러 변형 및 개량형태또한본 발명의 권리 범위에 속하는것이다. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. And falls within the scope of the present invention.

Claims

2019/132153 1»（：1^1{2018/009108 19 【청구의 범위】 【청구항 1] 하기 화학식 !로표현되는구조단위를포함하는중합체: Claims: 1. A polymer comprising a structural unit represented by the following formula: ???????? R 1 -
[화학식 1]  [Chemical Formula 1]
* - - 6 - * 상기 화학식 1에서, * - - 6 - * In Formula 1,
쇼는하기 화학식 2로표현되는모이어티이고，  The show is a moiety represented by the following formula (2)
8는하기 화학식 3으로표현되는모이어티이고,  8 is a moiety represented by the following formula (3)
*은연결지점이다:  * Is the connection point:
[화학식 2]  (2)
Figure imgf000021_0001
Figure imgf000021_0001
상기 화학식 2에서,  In Formula 2,
å는 NR0, O또는 이고,여기서 IIᄋ는수소,치환또는비치환된 01내지 030 알킬기,치환또는비치환된 C6내지 030아릴기,또는이들의 조합이고, å is NR 0, O or, wherein ᄋ II is hydrogen, substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted C6 to 030 an aryl group, or a combination of these,
II1은히드록시기，할로겐기,치환또는비치환된 01내지 030알콕시기，치환 또는비치환된 01내지 030알킬기,치환또는비치환된 02내지 030알케닐기, 치환또는비치환된 02내지 030알키닐기,치환또는비치환된 06내지 030 아릴기 ,치환또는비치환된 01내지 030헤테로알킬기，치환또는비치환된 02 내지 030헤테로아릴기,또는이들의 조합이고, II 1 represents a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, a substituted or unsubstituted 02 to 030 alkynyl group , A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted 01 to 030 heteroalkyl group, a substituted or unsubstituted 02 to 030 heteroaryl group,
는 0내지 3인정수이고，  Is an integer of 0 to 3,
*은연결지점이다:  * Is the connection point:
[화학식 3]
Figure imgf000021_0002
(3)
Figure imgf000021_0002
상기 화학식 3에서, 2019/132153 1»（：1^1{2018/009108 In Formula 3, 2019/132153 1 »(: 1 ^ {2018/009108
20 및 I?는각각독립적으로 0, 3, 302,또는카르보닐이고， 20, and I are each independently 0, 3, 30 2 , or carbonyl,
II2내지 II5는각각독립적으로히드록시기,할로겐기,치환또는비치환된 01 내지 030알콕시기,치환또는비치환된 01내지 030알킬기，치환또는비치환된 02내지 030알케닐기，치환또는비치환된 01내지 030알키닐기,치환또는 비치환된 C6내지 030아릴기,치환또는비치환된 01내지 030헤테로알킬기, 치환또는비치환된 02내지 030헤테로아릴기,또는이들의 조합이고, II 2 to II 5 each independently represent a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to O30 heteroaryl group, or a combination thereof,
내지 6는각각독립적으로 0내지 4인정수이고, To 6 are independently 0 to 4 numbers,
II6내지 II11은각각독립적으로수소,치환또는비치환된 01내지 030 알킬기，치환또는비치환된 06내지 030아릴기,또는이들의 조합이고, II 6 to II 11 are each independently hydrogen, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 06 to 030 aryl group, or a combination thereof,
II은 0내지 5인정수이고,  II is an integer from 0 to 5,
*은연결지점이다.  * Is the connection point.
【청구항 2】  [Claim 2]
제 1항에서，  The method of claim 1,
상기 화학식 3에서 II은 0또는 1인중합체.  In Formula 3, II is 0 or 1.
【청구항 3]  [3]
제 1항에서,  The method of claim 1,
상기 화학삭 3에서 및 I?는각각 0인중합체.  In the above chemical roux 3 and I?
【청구항 4】  Claim 4
제 1항에서,  The method of claim 1,
상기 화학식 2로표현되는모이어티의 오각고리 부분이상기 화학식 1의 8부분과연결되는것인중합체.  Wherein the pentachloro ring moiety of the moiety represented by Formula 2 is connected to the 8 moiety of Formula 1.
【청구항 5]  [Claim 5]
제 1항에서,  The method of claim 1,
중량평균분자량이 1,000내지 200,000인중합체.  A weight average molecular weight of 1,000 to 200,000.
【청구항 6】  [Claim 6]
하기 화학식 1로표현되는구조단위를포함하는중합체，그리고 A polymer comprising a structural unit represented by the following formula ( 1 ), and
용매  menstruum
를포함하는  Containing
유기막조성물: 2019/132153 1»（：1^1{2018/009108 Organic film composition: 2019/132153 1 »(: 1 ^ {2018/009108
21  21
[화학식 1] — 8 상기 화학식 1에서， [Formula 1] - 8 In Formula 1 ,
쇼는하기 화학식 2로표현되는모이어티이고,  The show is a moiety represented by the following formula (2)
8는하기 화학식 3으로표현되는모이어티이고，  8 is a moiety represented by the following formula (3)
*은연결지점이다:  * Is the connection point:
[화학식 2]  (2)
Figure imgf000023_0001
Figure imgf000023_0001
상기 화학식 2에서, In Formula 2,
는 0또는 이고,여기서 IIᄋ는수소,치환또는비치환된 01내지。30 알킬기，치환또는비치환된 6내지 30아릴기,또는이들의 조합이고，  Is 0 or, where II-C is hydrogen, a substituted or unsubstituted 01 to 30.30 alkyl group, a substituted or unsubstituted 6 to 30 aryl group, or a combination thereof,
II1은히드록시기,할로겐기,치환또는비치환된 01내지 030알콕시기, 치환또는비치환된（그1내지 030알킬기,치환또는비치환된 02내지 030 알케닐기,치환또는비치환된 02내지 030알키닐기,치환또는비치환된 06내지 030아릴기，치환또는비치환된（그1내지 030헤테로알킬기,치환또는비치환된 02내지 030헤테로아릴기,또는이들의 조합이고, II 1 represents a hydroxyl group, a halogen group, a substituted or unsubstituted 01 to 030 alkoxy group, a substituted or unsubstituted (1 to 030 alkyl group, a substituted or unsubstituted 02 to 030 alkenyl group, a substituted or unsubstituted 02 to 030 A substituted or unsubstituted C6 to O30 aryl group, a substituted or unsubstituted (1 to 030 heteroalkyl group, a substituted or unsubstituted 02 to 030 heteroaryl group, or a combination thereof,
는 0내지 3인정수이고,  Is an integer of 0 to 3,
*은연결지점이다:  * Is the connection point:
[화학식 3]
Figure imgf000023_0002
(3)
Figure imgf000023_0002
상기 화학식 3에서，  In Formula 3,
및 I?는각각독립적으로 0, 8, 802,또는카르보닐이고, And I? Are each independently 0, 8, 80 2, or a carbonyl,
내지 II5는각각독립적으로히드록시기,할로겐기,치환또는비치환된 1내지 030알콕시기,치환또는비치환된 0\내지 030알킬기,치환또는 2019/132153 1»（：1^1{2018/009108 To II 5 are each independently a hydroxy group, a halogen group, a substituted or unsubstituted 1 to 030 alkoxy groups, substituted or unsubstituted 0 \ to 030 alkyl group, a substituted or 2019/132153 1 »(: 1 ^ {2018/009108
22 비치환된 02내지 030알케닐기,치환또는비치환된 02내지 030알키닐기,치환 또는비치환된 06내지 030아릴기，치환또는비치환된 01내지 030헤테로알킬기, 치환또는비치환된 02내지 030헤테로아릴기,또는이들의 조합이고,  A substituted or unsubstituted C2 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, 030 heteroaryl group, or a combination thereof,
내지 6는각각독립적으로 0내지 4인정수이고，To 6 are independently 0 to 4 numbers,
Figure imgf000024_0001
독립적으로수소，치환또는비치환된 01내지 030 알킬기 ,치환또는비치환된 06내지 030아릴기，또는이들의 조합이고,
Figure imgf000024_0001
Independently, hydrogen, a substituted or unsubstituted 01 to 030 alkyl group, a substituted or unsubstituted 06 to 030 aryl group, or combinations thereof,
II은 0내지 5인정수이고,  II is an integer from 0 to 5,
*은연결지점이다.  * Is the connection point.
【청구항 7】  7.
제 6항에서，  The method of claim 6,
상기 화학식 3에서 II은 0또는 1인유기막조성물.  In Formula 3, II is 0 or 1.
【청구항 8】  8.
제 6항에서,  The method of claim 6,
상기 화학식 3에서 및 I?는각각 0인유기막조성물.  In the formula (3), I < - >
【청구항 9]  9]
제 6항에서,  The method of claim 6,
상기 화학식 2로표현되는모이어티의 오각고리 부분이상기 화학식 1의 8부분과연결되는것인유기막조성물. Wherein the pentagonal ring part of the moiety represented by the formula (2) is connected to the 8 part of the formula (1) .
【청구항 10】  Claim 10
제 6항에서,  The method of claim 6,
상기 중합체의 중량평균분자량이 1,000내지 200,000인유기막조성물.  Wherein the polymer has a weight average molecular weight of 1,000 to 200,000.
【청구항 11】  Claim 11
제 6항에서,  The method of claim 6,
상기 중합체는상기 유기막조성물의 총함량에 대하여 0.1중량%내지 30 중량%로포함되어 있는유기막조성물.  Wherein the polymer is contained in an amount of 0.1% by weight to 30% by weight based on the total amount of the organic film composition.
【청구항 12】  Claim 12
기판위에 재료층을제공하는단계，  Providing a layer of material over the substrate,
상기 재료층위에 제 6항내지 제 11항중어느한항에 따른유기막  The organic layer according to any one of claims 6 to 11,
조성물을적용하는단계， Applying the composition,
상기 유기막조성물을열처리하여 하드마스크층을형성하는단계, 2019/132153 1»（：1^1{2018/009108 Heat treating the organic film composition to form a hard mask layer, 2019/132153 1 »(: 1 ^ {2018/009108
23 상기 하드마스크층위에 실리콘함유박막층을형성하는단계， 상기 실리콘함유박막층 위에 포토레지스트층을형성하는단계, 상기 포토레지스트층을노광및 현상하여 포토레지스트패턴을형성하는 단계,  23. A method of manufacturing a semiconductor device comprising the steps of forming a silicon-containing thin film layer on the hard mask layer, forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern,
상기 포토레지스트패턴을이용하여 상기 실리콘함유박막층및상기 하드마스크층을선택적으로제거하고상기 재료층의 일부를노출하는단계, 그리고  Selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
상기 재료층의 노출된부분을식각하는단계  Etching the exposed portion of the material layer
를포함하는패턴형성 방법.  ≪ / RTI >
【청구항 13】  Claim 13
제 12항에서,  The method of claim 12,
상기 유기막조성물을적용하는단계는스핀-온코팅 방법으로수행하는 패턴 형성 방법.  Wherein the step of applying the organic film composition is performed by a spin-on coating method.
【청구항 14】  14.
제 12항에서，  The method of claim 12,
상기포토레지스트층을형성하는단계 전에
Figure imgf000025_0001
Before the step of forming the photoresist layer
Figure imgf000025_0001
형성하는단계를더 포함하는패턴형성 방법. To form a pattern.
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