WO2019088396A1 - Polymer, organic film composition, and method for forming pattern - Google Patents

Polymer, organic film composition, and method for forming pattern Download PDF

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Publication number
WO2019088396A1
WO2019088396A1 PCT/KR2018/007366 KR2018007366W WO2019088396A1 WO 2019088396 A1 WO2019088396 A1 WO 2019088396A1 KR 2018007366 W KR2018007366 W KR 2018007366W WO 2019088396 A1 WO2019088396 A1 WO 2019088396A1
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group
polymer
formula
layer
independently
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PCT/KR2018/007366
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French (fr)
Korean (ko)
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임재범
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삼성에스디아이 주식회사
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Priority to CN201880071469.0A priority Critical patent/CN111295409B/en
Publication of WO2019088396A1 publication Critical patent/WO2019088396A1/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
    • 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
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • 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
    • 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
    • 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
    • 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
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • 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
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment

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 material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do.
  • 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 gap-fill and planarization properties.
  • the embedding characteristic of embedding the pattern in the film without voids is required.
  • One embodiment provides a novel polymer having excellent heat resistance and corrosion resistance while ensuring solubility.
  • 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 moiety represented by the following formula (1).
  • X and y each independently represent a pentachloro ring containing at least one hetero atom.
  • the polymer may further include a substituted or unsubstituted fluorene moiety.
  • the polymer may include a structural unit represented by the following formula (2).
  • a and C are each independently a moiety represented by the formula (1):
  • B and D are each independently a divalent group including a substituted or unsubstituted fluorene moiety, n is 0 or 1,
  • a and C may each independently be any one of the moieties listed in the following group 1.
  • B and D are each independently any one of substituted or unsubstituted divalent groups listed in Group 2 below.
  • the weight average molecular weight of the above-mentioned compact may be 500 to 200,000.
  • an organic film composition comprising a polymer as described above and a solvent.
  • a method of manufacturing a semiconductor device comprising the steps of forming a material layer on a substrate, applying an organic film composition comprising the polymer and solvent described above onto the material layer, Forming a hard mask layer by heat treating the organic film composition; 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 a photo 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 using the photoresist pattern, and etching the exposed portion of the material layer And a pattern forming method.
  • the step of applying the organic film composition may be performed by a spin-on coating method.
  • BARC bottom anti-reflective layer
  • the polymer according to one embodiment is excellent in heat resistance and corrosion resistance.
  • the polymer is used as an organic film material, it is possible to provide an organic film which is excellent in film density and corrosion resistance and can satisfy flatness.
  • FIG. 1 is a flowchart for explaining a pattern forming method according to an embodiment
  • FIG. 2 is a reference diagram for explaining a method of evaluating a planarization characteristic.
  • 'substituted' means that the hydrogen atom in the compound is substituted by a halogen atom (F, Br, Cl, or 1), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, A C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C30 heteroaryl group, Substituted with a substituent selected from the group consisting of a C 2 -C 20 heteroarylalkyl group, a C3 to C30 heteroaryl group, Substi
  • '*' refers to the point of attachment of a compound or moiety.
  • Polymers according to one embodiment include moieties represented by the following formula (1). [Chemical Formula 1]
  • X and Y are each independently a pentachloro ring containing at least one hetero atom.
  • the moiety represented by the formula (1) is a heteroaromatic ring group having a bent structure. Since the moiety has a vent structure while securing the basic corrosion awareness due to the ring group characteristic, the degree of freedom degree of freedom. Accordingly, the polymer containing the moiety represented by Formula 1 may have softness as well as corrosion resistance.
  • X and Y may each independently contain 1 or 2 hetero atoms.
  • X and Y each independently represents a heteroaromatic ring group containing two nitrogen atoms, a heteroaromatic ring group containing one oxygen atom and one nitrogen atom, And may be a heteroaromatic ring group containing one nitrogen atom, but is not limited thereto.
  • the polymer may further include a substituted or unsubstituted fluorene moiety.
  • the substituted or unsubstituted fluorene moiety may be any one selected from the following group X, but is not limited thereto. [Group X] i
  • each hydrogen in each moiety is independently selected from the group consisting of a hydroxy group, a halogen group, 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 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, Substituted or unsubstituted.
  • the fluorene moiety can further enhance the corrosion-resisting property to the CFx fused gas by including the fourth carbon.
  • a quaternary carbon is defined as a carbon in which all four of four hydrogen atoms bonded to carbon are replaced with a group other than hydrogen.
  • the polymer may comprise a structural unit represented by the following formula
  • a and C are each independently a moiety represented by the above formula (1)
  • B and D are each independently a substituted or unsubstituted fluorene moiety-containing bivalent group, n is 0 or 1, and * is a connection point.
  • the polymer includes the same or different kinds of structural units represented by the general formula (2), and the number of structural units is not particularly limited.
  • the polymer may be formed, for example, by a 2-to 4-membered copolymerization process. From this viewpoint, in the above formula (1), A and C may be the same or different, and C and D may be the same or different.
  • the structural unit represented by the formula (1) is composed of A and B.
  • a and C may each independently be any one of the moieties listed in Group 1 below, but the present invention is not limited thereto.
  • the " " sign connected to the pentagonal ring on both sides of the benzene ring in group 1 means the point of connection in the structural unit of the moieties of group 1.
  • B and D in formula (2) may independently be any of substituted or unsubstituted divalent groups listed in the following group 2, but is not limited thereto.
  • Quot; in the group 1 means a connection point in the structural unit of the moieties of the group 2.
  • each hydrogen in each moiety is independently selected from the group consisting of a hydroxyl group, a halogen group, 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 C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, , Or is unsubstituted.
  • the compact may have a weight average molecular weight of about 500 to 200,000.
  • a weight average molecular weight in the above range, it is possible to optimize by controlling the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.
  • a uniform thin film can be formed without formation of pin-holes and voids or deterioration of thickness distribution in the baking process But can provide excellent gap-fill and planarization characteristics when a step is present in a lower substrate (or film) or when a pattern is formed.
  • an organic film composition comprising a polymer as described above and a solvent.
  • the solvent is not particularly limited as long as it has a layered solubility or dispersibility with respect to the polymer.
  • the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) N, N-dimethylacetamide, N, N-dimethylacetamide, methylpyridine, N-methylpyrrolidone, N, N-dimethylacetamide, propyleneglycol monomethyl ether acetate, cyclohexanone, ethyl lactate, At least one selected from ridon, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate.
  • the polymer may comprise from about 0.1 to 50 parts by weight 0/0, from about 0.1 to 30 parts by weight 0/0, preferably about 0.1 to 15 parts by weight 0/0 with respect to the total amount of the organic film composition.
  • the thickness, surface roughness, and leveling of the organic film can be controlled.
  • 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 an ammonium salt.
  • cross-linking agent examples include melamine-based, substitution-based, or polymer-based ones.
  • crosslinking agents having at least two crosslinking substituents are used, for example, as crosslinking agents, such as, for example, carboxymethylated glyceryl, glucosyl methylated glyceryl, meloxymethylated melamine, meloxymethylated melamine, meloxymethylated benzoguanamine, Methylated benzoguanamine, a meloxymethylated urea, a methylated urea, an isomerized methylated thioether, or a butoxymethylated thioether.
  • crosslinking agent a crosslinking agent having high heat resistance
  • a compound containing a crosslinking forming substituent group having an aromatic ring for example, a benzene ring or a naphthalene ring
  • an aromatic ring for example, a benzene ring or a naphthalene ring
  • the thermal acid generator may be an acidic compound such as rubenesulfonic acid, trifluoromethanesulfonic acid, pyridinium P-, rubenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but are not limited thereto.
  • an acidic compound such as rubenesulfonic acid, trifluoromethanesulfonic acid, pyridinium P-, rubenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,4,6
  • 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 it 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 curing the organic layer composition described above, for example, on a substrate followed by a heat treatment, and may include an organic thin layer used for electronic devices such as a hard mask layer, a planarization layer, a sacrificial layer, have.
  • 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, or the like.
  • the material layer may be formed, for example, by chemical vapor deposition
  • the organic film composition is as described above, and may be prepared in a solution form and applied by a spin-silver coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but can be applied, for example, to a thickness of about 50 to 200,000 A.
  • the heat treatment of the organic film composition may be performed at, for example, 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 further 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, a heat treatment process may be performed at about 100 to 700 ° C after exposure.
  • the step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BC 1 3 and a fused gas thereof.
  • 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.
  • Synthesis Example 2 A 1 L round bottom flask equipped with a condenser was charged with 21.3 g (0.10 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 40.6 g of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid 0.10 mol), and 300 g of polyphosphoric acid were charged, and a polymer (MW: 2300) represented by the formula (2-2) was obtained through the same synthetic procedure as in Synthesis Example 1.
  • Synthesis Example 3 24.5 g (0.10 mol) of 2,4-diamino-1,3-benzenedithiol dihydrochloride and 40.6 g of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid were added to a 1 L isometric bottom flask equipped with a magnetic stirrer. (0.10 mol) of polyphosphoric acid and 300 g of polyphosphoric acid were charged, and the same synthetic procedure as in Synthesis Example 1 was carried out to obtain a polymer (MW: 2000) represented by Formula 2-3.
  • Synthesis Example 4 To a 1 L round bottom flask equipped with a condenser were added 28.4 g (0.10 mol) of 1,2,3,4-benzenetetramine tetrahydrochloride, 6,6 '- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic acid 50.7 g, and 300 g of polyphosphoric acid were charged into a reactor, and the same polymer was synthesized as in Synthesis Example 1 to obtain a polymer (MW: 2300) represented by Formula 2-4.
  • Synthesis Example 5 A 1 L round bottom flask equipped with a condenser was charged with 21.3 g (0.10 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 6,6 '- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic (0.10 mol), and polyphosphoric acid (300 g) were charged, and the same synthetic procedure as in Synthesis Example 1 was carried out to obtain a polymer (MW: 2400) represented by Formula 2-5.
  • Synthesis Example 10 In a 1 L isometric bottom flask equipped with a magnetic stirrer, 21.3 g (0.10 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 20.3 g of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid (0.05 mol) of 6,6'- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic acid and 300 g of polyphosphoric acid were charged and then subjected to the same synthetic procedure as in Synthesis Example 1 (MW: 3300) represented by the formula 2-10 was obtained.
  • 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 instead 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 compound 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 Synthesis Example 5 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 6 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 7 was used instead 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 9 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 10 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 instead 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.
  • Evaluation 1 Gap-fill property and planarization property
  • the hard mask composition according to Examples 1 to 10 and Comparative Examples 1 to 4 was spin-coated on a silicon wafer by adjusting the mass ratio of the solvent to the solute to 3 to 97, And the cut surface was observed using V-SEM. Under the above conditions, the mask thickness on the bare wafer was about 1100A.
  • the gap-fill and planarization characteristics were determined by observing the cross-section of the pattern using a scanning electron microscope (SEM) to determine whether or not a void was generated.
  • SEM scanning electron microscope
  • the planarization characteristic was measured by measuring the step represented by the value of (i -hs) Respectively.
  • 3 ⁇ 4 means a value obtained by averaging thicknesses of thin films measured at arbitrary three points where no pattern is formed in the substrate
  • h 2 denotes a value measured at any three points where a pattern is formed on the substrate Means the thickness of the thin film.
  • the planarization characteristics are improved as the difference between 1 and h 2 will be.
  • Evaluation 2 adjusting the hard mask composition of the Comparative Examples 1 to 3 and the etch-resistant Examples 1 to 10 the weight ratio of the solute compared to the solvent 15 to 85 was spin-on silicon wafer was coated to the next, 400 ° C on a hot plate Treated for 2 minutes to form a thin film having a thickness of 4,000 A, and the thickness of the formed thin film was measured. Subsequently, the thin film was dry-etched for 100 seconds and 60 seconds using CHF 3 / CF 4 fog gas and N 2 / O 2 fog gas, respectively, The thickness was again measured. The bulk etch rate (BER) was calculated from the thickness and etch time of the thin film before and after dry etching according to the following equation.
  • BER bulk etch rate
  • the thin films formed from the hard mask compositions according to Examples 1 to 10 had a superb corrosion resistance to etching gas compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 3, It can be confirmed that it is improved.

Abstract

The present invention relates to: a polymer comprising a moiety 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. [Chemical Formula 1] In chemical formula 1, X and Y are respectively and independently a five-membered ring group containing at least one hetero atom.

Description

【명세서】  【Specification】
【발명의 명칭】 ·  Title of the Invention
중합체, 유기막 조성물 및 패턴 형성 방법  Polymer, organic film composition and pattern forming method
【기술분야】  TECHNICAL FIELD
신규한 중합체, 상기 중합체를 포함하는 유기막 조성물, 그리고 상기 유기막 조성물을 사용하는 패턴 형성 방법에 관한 것이다.  A novel polymer, an organic film composition comprising the polymer, and a pattern forming method using the organic film composition.
【배경기술】  BACKGROUND ART [0002]
최근 반도체 산업은 수백 나노미터 크기의 패턴에서 수 내지 수십 나노미터 크기의 패턴을 가지는 초미세 기술로 발전하고 있다. 이러한 초미세 기술을 실현하기 위해서는 효과적인 리쏘그래픽 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.
전형적인 리쏘그래픽 기법은 반도체 기판 위에 재료 층을 형성하고 그 위에 포토레지스트 층을 코팅하고 노광 및 현상을 하여 포토레지스트 패턴을 형성한 후， 상기 포토레지스트 패턴을 마스크로 하여 재료 층을 식각하는 과정을 포함한다. 근래， 형성하고자 하는 패턴의 크기가 감소함에 따라 상술한 전형적인 리쏘그래픽 기법만으로는 양호한 프로파일을 가진 미세 패턴을 형성하기 어렵다. 이에 따라 식각하고자 하는 재료 층과 포토레지스트 층 사이에 일명 하드마스크 층 (hardmask layer)이라고 불리는 유기막을 형성하여 미세 패턴을 형성할 수 있다. 하드마스크 층은 선택적 식각 과정을 통하여 포토레지스트의 미세 패턴을 재료 층으로 전사해주는 중간막으로서 역할을 한다. 따라서 하드마스크 층은 다중 식각 과정 동안 견딜 수 있도록 내열성 및 내식각성의 특성이 필요하다.  A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do. 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, 근래 하드마스크 층은 화학기상증착 방법 대신 스핀-온 코팅 (spin-on coating) 방법으로 형성하는 것이 제안되었다. 스핀-온 코팅 방법은 공정이 용이할 뿐만 아니라 갭-필 (gap-fill) 특성 및 평탄화 특성을 개선할 수 있다. 미세 패턴을 실현하기 위해서는 다중 패턴 형성이 필수적인데 이때 패턴 안을 공극 없이 막으로 매립하는 매립 특성이 필요하게 된다. 또한, 피가공 기판에 단차가 있는 경우나 패턴 밀집 부분 및 패턴이 없는 영역이 웨이퍼 상에 함께 존재하는 경우， 하층막에 의해서 막 표면을 평탄화시킬 필요가 있다.  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 gap-fill and planarization properties. In order to realize a fine pattern, it is necessary to form multiple patterns. In this case, the embedding characteristic of embedding the pattern in the film without voids is required. Further, in the case where there is a step on the substrate to be processed, or in the case where a pattern dense portion and an area having no pattern exist together on the wafer, it is necessary to planarize the film surface by the underlayer film.
상술한 하드마스크 층에 요구되는 특성들을 만족할 수 있는 유기막 재료가 요구된다.  There is a demand for an organic film material which can satisfy the properties required for the hard mask layer described above.
【발명의 상세한 설명】 【기술적 과제】 DETAILED DESCRIPTION OF THE INVENTION [Technical Problem]
일 구현예는 용해도를 확보하면서도 내열성 및 내식각성이 우수한 신규한 중합체를 제공한다.  One embodiment provides a novel polymer having excellent heat resistance and corrosion resistance while ensuring solubility.
다른 구현예는 상기 중합체를 포함하는 유기막 조성물을 제공한다.  Another embodiment provides an organic film composition comprising the polymer.
또 다른 구현예는 상기 유기막 조성물을 사용한 패턴 형성 방법을 제공한다. Another embodiment provides a method of forming a pattern using the organic film composition.
【기술적 해결방법】 [Technical Solution]
일 구현예에 따르면, 하기 화학식 1로 표현되는 모이어티를 포함하는 중합체를 제공한다.  According to one embodiment, there is provided a polymer comprising a moiety represented by the following formula (1).
[화학식 1]  [Chemical Formula 1]
Figure imgf000003_0001
Figure imgf000003_0001
상기 화학식 1에서,  In Formula 1,
X 및 γ는 각각 독립적으로 적어도 하나의 헤테로 원자를 함유하는 오각 고리기이다.  X and y each independently represent a pentachloro ring containing at least one hetero atom.
상기 중합체는 치환또는 비치환된 플루오렌 모이어티를 더 포함할 수 있다. 상기 중합체는 하기 화학식 2로 표현되는 구조 단위를 포함할 수 있다.  The polymer may further include a substituted or unsubstituted fluorene moiety. The polymer may include a structural unit represented by the following formula (2).
[화학식 2
Figure imgf000003_0002
상기 화학식 2에서, [Chemical Formula 2
Figure imgf000003_0002
In Formula 2,
A 및 C는 각각 독립적으로 상기 화학식 1로 표현되는 모이어티이고: A and C are each independently a moiety represented by the formula (1):
B 및 D는 각각 독립적으로 치환 또는 비치환된 플루오렌 모이어티를 포함하는 2가의 기이고 n은 0 또는 1이고 B and D are each independently a divalent group including a substituted or unsubstituted fluorene moiety, n is 0 or 1,
*는 연결지점이다. 상기 화학식 2에서 A 및 C는 각각 독립적으로 하기 그룹 1에 나열된 모이어티들 증 어느 하나일 수 있다. * Is the connection point. In the formula (2), A and C may each independently be any one of the moieties listed in the following group 1.
[그룹 1]
Figure imgf000004_0001
[Group 1]
Figure imgf000004_0001
상기 화학식 2에서 B 및 D는 각각 독립적으로 하기 그룹 2에 나열된 치환 또는 비치환된 2가의 기들 중 어느 하나일 수 있다. In Formula 2, B and D are each independently any one of substituted or unsubstituted divalent groups listed in Group 2 below.
그룹 2]  Group 2]
Figure imgf000004_0002
Figure imgf000004_0002
상기 증합체의 중량평균분자량이 500 내지 200,000일 수 있다.  The weight average molecular weight of the above-mentioned compact may be 500 to 200,000.
다른 구현예에 따르면， 상술한 중합체, 그리고 용매를 포함하는 유기막 조성물을 제공한다.  According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.
또 다른 구현예에 따르면, 기판 위에 재료 층을 형성하는 단계, 상기 재료 층 위에 상술한 중합체 및 용매를 포함하는 유기막 조성물을 적용하는 단계， 상기 정정용지 (규칙제 91조) ISA/KR 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계, 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계, 상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계， 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하는 단계, 상기 포토레지스트 패턴을 이용하여 상기 실리콘 함유 박막층 및 상기 하드마스크 층을 선택적으로 제거하고 상기 재료 층의 일부를 노출하는 단계, 그리고 상기 재료 층의 노출된 부분을 식각하는 단계를 포함하는 패턴 형성 방법을 제공한다. According to yet another embodiment, there is provided a method of manufacturing a semiconductor device, comprising the steps of forming a material layer on a substrate, applying an organic film composition comprising the polymer and solvent described above onto the material layer, Forming a hard mask layer by heat treating the organic film composition; 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 a photo 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 using the photoresist pattern, and etching the exposed portion of the material layer And a pattern forming method.
상기 유기막 조성물을 적용하는 단계는 스핀-온 코팅 방법으로 수행할 수 있다.  The step of applying the organic film composition may be performed by a spin-on coating method.
상기 포토레지스트 층을 형성하는 단계 전에 바닥 반사 방지 층 (BARC)을 형성하는 단계를 더 포함할 수 있다.  And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
【발명의 효과】  【Effects of the Invention】
일 구현예에 따른 중합체는 내열성과 내식각성이 우수하다. 상기 중합체를 유기막 재료로 사용할 경우 막 밀도 및 내식각성이 우수하면서도 평탄성을 만족할 수 있는 유기막을 제공할 수 있다.  The polymer according to one embodiment is excellent in heat resistance and corrosion resistance. When the polymer is used as an organic film material, it is possible to provide an organic film which is excellent in film density and corrosion resistance and can satisfy flatness.
【도면의 간단한 설명】  BRIEF DESCRIPTION OF THE DRAWINGS
도 1은 일 구현예에 따른 패턴 형성 방법을 설명하기 위한흐름도이고, 도 2는 평탄화 특성의 평가 방법을 설명하기 위한 참고도아다.  FIG. 1 is a flowchart for explaining a pattern forming method according to an embodiment, and FIG. 2 is a reference diagram for explaining a method of evaluating a planarization characteristic.
【발명의 실시를 위한 최선의 형태】 BEST MODE FOR CARRYING OUT THE INVENTION
이하, 본 발명의 구현예에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 구현예에 한정되지 않는다.  Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
본 명세서에서 별도의 정의가 없는 한, '치환된'이란, 화합물 중의 수소 원자가 할로겐 원자 (F, Br, C1, 또는 1)， 히드록시기, 니트로기, 시아노기, 아미노기, 아지도기, 아미디노기, 히드라지노기, 히드라조노기， 카르보닐기, 카르바밀기, 티올기， 에스테르기, 카르복실기나 그의 염, 술폰산기나 그의 염， 인산이나 그의 염, C1 내지 C30 알킬기， C2 내지 C30 알케닐기, C2 내지 C30 알키닐기， C6 내지 C30 아릴기, C7 내지 C30 아릴알킬기, C1 내지 C30 알콕시기， C1 내지 C20 헤테로알킬기, C3 내지 C20 헤테로아릴알킬기, C3 내지 C30 사이클로알킬기， C3 내지 C15의 사이클로알케닐기, C6 내지 C15 사이클로알키닐기, C3 내지 C30 헤테로사이클로알킬기 및 이들의 조합에서 선택된 치환기로 치환된 것을 의미한다. 또한, 본 명세서에서 별도의 정의가 없는 한， '헤테로'란， N, O, S 및 P에서 선택된 헤테로 원자를 1 내지 3개 함유한 것을 의미한다. Unless otherwise defined herein, 'substituted' means that the hydrogen atom in the compound is substituted by a halogen atom (F, Br, Cl, or 1), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, A C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C30 heteroaryl group, Substituted with a substituent selected from the group consisting of a C 2 -C 20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof. In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.
또한, 본 명세서에서 별도의 정의가 없는 한, '*'는 화합물 또는 화합물 부분 (moiety)의 연결 지점을 가리킨다.  Also, unless otherwise defined herein, '*' refers to the point of attachment of a compound or moiety.
이하 일 구현예에 따른 중합체를 설명한다.  Polymers according to one embodiment are described below.
일 구현예에 따른 중합체는 하기 화학식 1로 표현되는 모이어티를 포함한다. [화학식 1]  Polymers according to one embodiment include moieties represented by the following formula (1). [Chemical Formula 1]
Figure imgf000006_0001
Figure imgf000006_0001
X 및 Y는 각각 독립적으로 적어도 하나의 헤테로 원자를 함유하는 오각 고리기이다.  X and Y are each independently a pentachloro ring containing at least one hetero atom.
상기 화학식 1로 표현되는 모이어티는 벤트 (bent) 구조를 가지는 헤테로 방향족 고리기로서, 고리기 특성에서 기인하는 기본적인 내식각성을 확보하면서도 벤트 구조를 가짐에 따라 통상의 메틸렌기과 같은 수준의 자유도 (degree of freedom)를 확보할 수 있다. 이에 따라， 상기 화학식 1로 표현되는 모이어티를 포함하는 중합체는 내식각성 뿐만 아니라 유연한 특성을 가질 수 있다.  The moiety represented by the formula (1) is a heteroaromatic ring group having a bent structure. Since the moiety has a vent structure while securing the basic corrosion awareness due to the ring group characteristic, the degree of freedom degree of freedom. Accordingly, the polymer containing the moiety represented by Formula 1 may have softness as well as corrosion resistance.
상기 화학식 1에서 X 및 Y는 각각 독립적으로 1개 또는 2개의 헤테로 원자를 함유할 수 있다. 예를 들어， 상기 화학식 1에서 X 및 Y는 각각 독립적으로 두 개의 질소 원자를 함유하는 헤테로 오각 고리기， 하나의 산소원자 및 하나의 질소 원자를 함유하는 헤테로 오각 고리기, 또는 하나의 황 원자 및 하나의 질소 원자를 함유하는 헤테로 오각 고리기일 수 있으나, 이에 한정되는 것은 아니다. 상기 중합체는 치환 또는 비치환된 플루오렌 모이어티를 더 포함할 수 있다. 예를 들어, 상기 치환 또는 비치환된 플루오렌 모이어티는 하기 그룹 X에서 선택되는 어느 하나일 수 있으나 이에 한정되는 것은 아니다. [그룹 X] i In Formula 1, X and Y may each independently contain 1 or 2 hetero atoms. For example, in the above formula (1), X and Y each independently represents a heteroaromatic ring group containing two nitrogen atoms, a heteroaromatic ring group containing one oxygen atom and one nitrogen atom, And may be a heteroaromatic ring group containing one nitrogen atom, but is not limited thereto. The polymer may further include a substituted or unsubstituted fluorene moiety. For example, the substituted or unsubstituted fluorene moiety may be any one selected from the following group X, but is not limited thereto. [Group X] i
Figure imgf000007_0001
상기 그룹 X에서, 각 모이어티 내의 수소는 각각 독립적으로 히드록시기， 할로겐기, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C2 내지 C30 알케닐기, 치환 또는 비치환된 C2 내지 C30 알키 ^기， 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 또는 이들의 조합으로 치환된 것이거나， 또는 비치환된 것이다.
Figure imgf000007_0001
In the group X, each hydrogen in each moiety is independently selected from the group consisting of a hydroxy group, a halogen group, 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 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, Substituted or unsubstituted.
상기 플루오렌 모이어티는 4차 탄소를 포함함으로써 CFx 흔합 가스에 대한 내식각성을 더욱 향상시킬 수 있다. 본 명세서에서, 4차 탄소란 탄소에 결합된 4개의 수소 중 4개 자리 모두가 수소 이외의 다른 기로 치환된 형태의 탄소인 것으로 정의한다.  The fluorene moiety can further enhance the corrosion-resisting property to the CFx fused gas by including the fourth carbon. In the present specification, a quaternary carbon is defined as a carbon in which all four of four hydrogen atoms bonded to carbon are replaced with a group other than hydrogen.
예를 들어, 상기 중합체는 하기 화학식 2로 표현되는 구조단위를 포함할 수  For example, the polymer may comprise a structural unit represented by the following formula
[화학식 2] (2)
*+A一 B"fC—D "ᅡ 상기 화학식 2에서, * + A < 1 > B " fC-D "
A 및 C는 각각 독립적으로 상기 화학식 1로 표현되는 모이어티이고, A and C are each independently a moiety represented by the above formula (1)
B 및 D는 각각 독립적으로 치환 또는 비치환된 플루오렌 모이어티- 포함하는 2가의 기이고, n은 0 또는 1이고, *는 연결지점이다. 상기 중합체는 상기 화학식 2로 표현되는 동종 또는 이종의 구조 단위를 포함하며， 구조 단위의 개수는 특별히 한정되지 않는다. 상기 중합체는 예컨대 2원 내지 4원 공중합 과정에 의해 형성될 수 있다. 이러한 관점에서， 상기 화학식 1에서 A 및 C는 서로 같아도 되고 달라도 되며, C 및 D도 마찬가지로 같아도 되고 달라도 된다. 또한， 상기 화학식 2에서 n이 0인 경우, 상기 화학식 1로 표현되는 구조 단위는 A 및 B로 이루어진다. 예를 들어， 상기 화학식 2에서 A 및 C는 각각 독립적으로 하기 그룹 1에 나열된 모이어티들 중 어느 하나일 수 있으나， 이에 한정되는 것은 아니다. B and D are each independently a substituted or unsubstituted fluorene moiety-containing bivalent group, n is 0 or 1, and * is a connection point. The polymer includes the same or different kinds of structural units represented by the general formula (2), and the number of structural units is not particularly limited. The polymer may be formed, for example, by a 2-to 4-membered copolymerization process. From this viewpoint, in the above formula (1), A and C may be the same or different, and C and D may be the same or different. When n is 0 in the formula (2), the structural unit represented by the formula (1) is composed of A and B. For example, in Formula 2, A and C may each independently be any one of the moieties listed in Group 1 below, but the present invention is not limited thereto.
[그룹 1] [Group 1]
Figure imgf000008_0001
Figure imgf000008_0001
상기 그룹 1에서 벤젠 고리 양측의 오각 고리기에 연결된 " " 표시는 상기 그룹 1의 모이어티들의 상기 구조 단위 내 연결 지점올 의미한다.  The " " sign connected to the pentagonal ring on both sides of the benzene ring in group 1 means the point of connection in the structural unit of the moieties of group 1.
예를 들어, 상기 화학식 2에서 B 및 D는 각각 독립적으로 하기 그룹 2에 나열된 치환 또는 비치환된 2가의 기들 중 어느 하나일 수 있으나， 이에 한정되는 것은 아니다.  For example, B and D in formula (2) may independently be any of substituted or unsubstituted divalent groups listed in the following group 2, but is not limited thereto.
7 7
정정용지 (규칙제 91조) ISA/KR 그룹 2] Correction paper (Rule 91) ISA / KR Group 2]
Figure imgf000009_0001
Figure imgf000009_0001
상기 그룹 1에서 " 표시는 상기 그룹 2의 모이어티들의 상기 구조 단위 내 연결 지점을 의미한다.  Quot; in the group 1 means a connection point in the structural unit of the moieties of the group 2.
상기 그룹 2에서, 각 모이어티 내의 수소는 각각 독립적으로 히드록시기， 할로겐기， 치환 또는 비치환된 C1 내지 C30 알콕시기， 치환 또는 비치환된 C1 내지 C30 알킬기， 치환 또는 비치환된 C2 내지 C30 알케닐기， 치환 또는 비치환된 C2 내지 C30 알키닐기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C1 내지 C30 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기， 또는 이들의 조합으로 치환된 것이거나, 또는 비치환된 것이다.  In the group 2, each hydrogen in each moiety is independently selected from the group consisting of a hydroxyl group, a halogen group, 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 C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, , Or is unsubstituted.
상기 증합체는 약 500 내지 200,000의 중량평균분자량을 가질 수 있다. 상기 범위의 중량평균분자량을 가짐으로써 상기 중합체를 포함하는 유기막 조성물 (예컨대， 하드마스크 조성물)의 탄소 함량 및 용매에 대한 용해도를 조절하여 최적화할 수 있다.  The compact may have a weight average molecular weight of about 500 to 200,000. By having a weight average molecular weight in the above range, it is possible to optimize by controlling the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.
상기 중합체를 유기막 재료로서 사용할 경우， 베이크 공정 중 핀-홀 및 보이드의 형성이나 두께 산포의 열화 없이 균일한 박막을 형성할 수 있을 뿐만 아니라 하부 기판 (혹은 막)에 단차가 존재하는 경우 혹은 패턴을 형성하는 경우 우수한 갭-필 및 평탄화 특성을 제공할 수 있다. When the polymer is used as an organic film material, a uniform thin film can be formed without formation of pin-holes and voids or deterioration of thickness distribution in the baking process But can provide excellent gap-fill and planarization characteristics when a step is present in a lower substrate (or film) or when a pattern is formed.
다른 구현예에 따르면, 상술한 중합체, 그리고 용매를 포함하는 유기막 조성물을 제공한다.  According to another embodiment, there is provided an organic film composition comprising a polymer as described above and a solvent.
상기 용매는 상기 중합체에 대한 층분한 용해성 또는 분산성을 가지는 것이면 특별히 한정되지 않으나, 예컨대 프로필렌글리콜， 프로필렌글리콜 디아세테이트, 메톡시 프로판디올, 디에틸렌글리콜, 디에틸렌글리콜 부틸에테르, 트리 (에틸렌글리콜)모노메틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노메틸에테르 아세테이트, 사이클로핵사논, 에틸락테이트, 감마-부티로락톤， Ν,Ν- 디메틸포름아미드, Ν,Ν-디메틸아세트아미드， 메틸피를리돈, 메틸피롤리디논, 아세틸아세톤및 에틸 3-에록시프로피오네이트에서 선택되는 적어도 하나를 포함할 수 있다.  The solvent is not particularly limited as long as it has a layered solubility or dispersibility with respect to the polymer. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) N, N-dimethylacetamide, N, N-dimethylacetamide, methylpyridine, N-methylpyrrolidone, N, N-dimethylacetamide, propyleneglycol monomethyl ether acetate, cyclohexanone, ethyl lactate, At least one selected from ridon, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate.
상기 중합체는 상기 유기막 조성물의 총 함량에 대하여 약 0.1 내지 50 중량0 /0, 약 0.1 내지 30 중량0 /0, 또는 약 0.1 내지 15 중량0 /0로 포함될 수 있다. 상기 범위로 중합체가 포함됨으로써 유기막의 두께， 표면 거칠기 및 평탄화 정도를 조절할 수 있다. The polymer may comprise from about 0.1 to 50 parts by weight 0/0, from about 0.1 to 30 parts by weight 0/0, preferably about 0.1 to 15 parts by weight 0/0 with respect to the total amount of the organic film composition. By including the polymer in the above range, the thickness, surface roughness, and leveling of the organic film can be controlled.
상기 유기막 조성물은 추가적으로 계면활성게, 가교제, 열산 발생제, 가소제 등의 첨가제를 더 포함할 수 있다.  The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
상기 계면활성제는 예컨대 플루오로알킬계 화합물， 알킬벤젠설폰산염， 알킬피리디늄염, 폴리에틸렌글리콜, 게 4암모늄염 등을 사용할 수 있으나 이에 한정되는 것은 아니다.  Examples of the surfactant include, but are not limited to, a fluoroalkyl-based compound, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, and an ammonium salt.
상기 가교제는 예컨대 멜라민계， 치환요소계, 또는 이들 폴리머계 등을 들 수 있다. 바람직하게는, 적어도 2개의 가교 형성 치환기를 갖는 가교제로, 예를 들면， 메록시메틸화 글리코루릴, 부록시메틸화 글리코루릴, 메록시메틸화 멜라민, 부록시메틸화 멜라민, 메록시메틸화 벤조구아나민, 부록시메틸화 벤조구아나민, 메록시메틸화요소, 부록시메틸화요소, 메특시메틸화 티오요소， 또는 부톡시메틸화 티오요소 등의 화합물을사용할 수 있다.  Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, crosslinking agents having at least two crosslinking substituents are used, for example, as crosslinking agents, such as, for example, carboxymethylated glyceryl, glucosyl methylated glyceryl, meloxymethylated melamine, meloxymethylated melamine, meloxymethylated benzoguanamine, Methylated benzoguanamine, a meloxymethylated urea, a methylated urea, an isomerized methylated thioether, or a butoxymethylated thioether.
또한, 상기 가교제로는 내열성이 높은 가교제를 사용할 수 있다. 내열성이 높은 가교제로는 분자 내에 방향족 고리 (예를 들면 벤젠 고리, 나프탈렌 고리)를 가지는 가교 형성 치환기를 함유하는 화합물을 사용할 수 있다. 상기 열산발생제는 예컨대 P-를루엔술폰산, 트리플루오로메탄술폰산, 피리디늄 P-를루엔술폰산, 살리실산, 술포살리실산, 구연산, 안식향산， 하이드록시안식향산, 나프탈렌카르본산 등의 산성 화합물 또는 /및 2,4,4,6- 테트라브로모시클로핵사디에논, 벤조인토실레이트, 2-니트로벤질토실레이트, 그 밖에 유기술폰산알킬에스테르 등을사용할 수 있으나 이에 한정되는 것은 아니다. 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, a benzene ring or a naphthalene ring) in the molecule can be used. The thermal acid generator may be an acidic compound such as rubenesulfonic acid, trifluoromethanesulfonic acid, pyridinium P-, rubenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but are not limited thereto.
상기 첨가제는 상기 유기막 조성물 100 중량부에 대하여 약 0.001 내지 40 중량부로 포함될 수 있다. 상기 범위로 포함함으로써 유기막 조성물의 광학적 특성을 변경시키지 않으면서 용해도를 향상시킬 수 있다.  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 it in the above range, the solubility can be improved without changing the optical properties of the organic film composition.
또 다른 구현예에 따르면, 상술한 유기막 조성물을 사용하여 제조된 유기막을 제공한다. 상기 유기막은 상술한 유기막 조성물을 예컨대 기판 위에 코팅한 후 열처리 과정을 통해 경화된 형태일 수 있으며， 예컨대 하드마스크 층， 평탄화막, 희생막, 충진제 등 전자 디바이스에 사용되는 유기 박막을 포함할 수 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 curing the organic layer composition described above, for example, on a substrate followed by a heat treatment, and may include an organic thin layer used for electronic devices such as a hard mask layer, a planarization layer, a sacrificial layer, have.
이하 상술한 유기막 조성물을 사용하여 패턴을 형성하는 방법에 대하여 도 1을 참고하여 설명한다.  Hereinafter, a method of forming a pattern using the above-described organic film composition will be described with reference to FIG.
도 1은 일 구현예에 따른 패턴 형성 방법을 설명하는 흐름도이다.  1 is a flowchart illustrating a pattern forming method according to an embodiment.
일 구현예에 따른 패턴 형성 방법은 기판 위에 재료 층을 형성하는 단계 (S1), 상기 재료 층 위에 상술한 중합체 및 용매를 포함하는 유기막 조성물을 적용하는 단계 (S2), 상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계 (S3), 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계 (S4), 상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계 (S5), 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하는 단계 (S6), 상기 포토레지스트 패턴을 이용하여 상기 실리콘 함유 박막층 및 상기 하드마스크 층을 선택적으로 제거하고 상기 재료 층의 일부를 노출하는 단계 (S7), 그리고 상기 재료 층의 노출된 부분을 식각하는 단계 (S8)를 포함한다.  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 기판은 예컨대 실리콘 웨이퍼, 유리 기판또는 고분자 기판일 수 있다. 상기 재료 층은 최종적으로 패턴하고자 하는 재료이며, 예컨대 알루미늄， 구리 등과 같은 금속층, 실리콘과 같은 반도체 층 또는 산화규소, 질화규소 등과 같은 절연층일 수 있다. 상기 재료 층은 예컨대 화학기상증착 방법으로 형성될 수 있다ᅳ 상기 유기막 조성물은 전술한 바와 같으며， 용액 형태로 제조되어 스핀-은 코팅 방법으로 도포될 수 있다. 이 때 상기 유기막 조성물의 도포 두께는 특별히 한정되지 않으나， 예컨대 약 50 내지 200,000 A 두께로 도포될 수 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, or the like. The material layer may be formed, for example, by chemical vapor deposition The organic film composition is as described above, and may be prepared in a solution form and applied by a spin-silver coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but can be applied, for example, to a thickness of about 50 to 200,000 A.
상기 유기막 조성물을 열처리하는 단계는 예컨대 약 100 내지 700 °C에서 약 10초 내지 1시간 동안 수행할 수 있다. The heat treatment of the organic film composition may be performed at, for example, about 100 to 700 ° C for about 10 seconds to 1 hour.
상기 실리콘 함유 박막층은 예컨대 SiCN, SiOC, SiON, SiOCN, SiC, SiO 및 /또는 SiN등의 물질로 형성할수 있다.  The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and / or SiN.
또한 상기 포토레지스트 층을 형성하는 단계 전에 상기 실리콘 함유 박막층 상부에 바닥 반사방지 충 (bottom anti-reflective coating, BARC)을 더 형성할 수도 있다. 상기 포토레지스트 충을 노광하는 단계는 예컨대 ArF, KrF 또는 EUV 등을 사용하여 수행할 수 있다. 또한 노광 후 약 100 내지 700°C에서 열처리 공정을 수행할 수 있다. Further, a bottom anti-reflective coating (BARC) may be further 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, a heat treatment process may be performed at about 100 to 700 ° C after exposure.
상기 재료 층의 노출된 부분을 식각하는 단계는 식각 가스를 사용한 건식 식각으로 수행할 수 있으며, 식각 가스는 예컨대 CHF3, CF4, Cl2, BC13 및 이들의 흔합 가스를 사용할 수 있다. The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BC 1 3 and a fused gas thereof.
상기 식각된 재료 충은 복수의 패턴으로 형성될 수 있으며, 상기 복수의 패턴은 금속 패턴， 반도체 패턴, 절연 패턴 등 다양할 수 있으며， 예컨대 반도체 집적 회로 디바이스 내의 다양한 패턴으로 적용될 수 있다. 【발명의 실시를 위한 형태】  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. DETAILED DESCRIPTION OF THE INVENTION
이하 실시예를 통하여 상술한 본 발명의 구현예를 보다 상세하게 설명한다. 다만 하기의 실시예는 단지 설명의 목적을 위한 것이며 본 발명의 범위를 제한하는 것은 아니다. 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 웅축기 (Condenser)를 장착한 1L 등근 바닥 폴라스크 (2-neck round-bottomed flask)에 1 ,2,3,4-benzenetetramine tetrahydrochloride 28.4g(0.10mol), 4,4'-(9H-fluorene-9- ylidene)bisbenzoic acid 40.6g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후, 15( C에서 24 시간 내지 48 시간 동안 교반하여 증합 반웅을 수행하였다. 중량평균분자량이 1,000 내지 5,000일 때 반응올 완료하였다. 중합 반웅 완료 후, 반웅물을 상온으로 서서하 냉각시킨 후, 상기 반웅물을 1M NaOH 용액으로 중화하고 생성되는 고체를 여과하였다. 증류수， 에탄올, 디에틸에테르 순서로 씻어 주었으며 건조 후 화학식 2-1로 표현되는 화합물 (MW: 2100)을 얻었다. Synthesis Example 1 A 1-L round bottom-bottomed flask equipped with a condenser was charged with 28.4 g (0.10 mol) of 1,2,3,4-benzenetetramine tetrahydrochloride, 4,4 '- (9H -fluorene-9-ylidene) bisbenzoic acid (40.6 g, 0.10 mol) and polyphosphoric acid (300 g) The reaction was completed when the weight average molecular weight was 1,000 to 5,000. After completion of the polymerization reaction, the reaction mixture was allowed to stand at room temperature and then cooled, The water was neutralized with 1M NaOH solution and the resulting solid was filtered. The filtrate was washed with distilled water, ethanol and diethyl ether, and dried to obtain the compound (MW: 2100) represented by the formula (2-1).
[화학식 2-1] [Formula 2-1]
Figure imgf000013_0001
합성예 2 응축기를 장착한 1L 둥근 바닥 플라스크에 2,4-diamino-l,3-benzenediol dihydrochloride 21.3g(0.10mol), 4,4'-(9H-fluorene-9-ylidene)bisbenzoic acid 40.6g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 화학식 2-2로 표현되는 중합체 (MW: 2300)를 얻었다.
Figure imgf000013_0001
Synthesis Example 2 A 1 L round bottom flask equipped with a condenser was charged with 21.3 g (0.10 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 40.6 g of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid 0.10 mol), and 300 g of polyphosphoric acid were charged, and a polymer (MW: 2300) represented by the formula (2-2) was obtained through the same synthetic procedure as in Synthesis Example 1.
[화학식 2-2] [Formula 2-2]
Figure imgf000013_0002
합성예 3 웅축기를 장착한 1L 등근 바닥 플라스크에 2,4-diamino-l,3-benzenedithiol dihydrochloride 24.5g(0.10mol), 4,4'-(9H-fluorene-9-ylidene)bisbenzoic acid 40.6g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후， 합성예 1과 동일한 합성 과정을 거쳐 화학식 2-3으로 표현되는 증합체 (MW: 2000)를 얻었다.
Figure imgf000013_0002
Synthesis Example 3 24.5 g (0.10 mol) of 2,4-diamino-1,3-benzenedithiol dihydrochloride and 40.6 g of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid were added to a 1 L isometric bottom flask equipped with a magnetic stirrer. (0.10 mol) of polyphosphoric acid and 300 g of polyphosphoric acid were charged, and the same synthetic procedure as in Synthesis Example 1 was carried out to obtain a polymer (MW: 2000) represented by Formula 2-3.
12 12
정정용지 (규칙제 91조) ISA/KR [화학식 2-3] Correction paper (Rule 91) ISA / KR [Formula 2-3]
Figure imgf000014_0001
합성예 4 응축기를 장착한 1L 둥근 바닥 플라스크에 1,2,3,4-benzenetetramine tetrahydrochloride 28.4g(0.10mol), 6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid 50.7g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 2-4로 표현되는 중합체 (MW: 2300)를 얻었다.
Figure imgf000014_0001
Synthesis Example 4 To a 1 L round bottom flask equipped with a condenser were added 28.4 g (0.10 mol) of 1,2,3,4-benzenetetramine tetrahydrochloride, 6,6 '- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic acid 50.7 g, and 300 g of polyphosphoric acid were charged into a reactor, and the same polymer was synthesized as in Synthesis Example 1 to obtain a polymer (MW: 2300) represented by Formula 2-4.
[화학식 2-4] [Chemical Formula 2-4]
Figure imgf000014_0002
합성예 5 응축기를 장착한 1L 등근 바닥 플라스크에 2,4-diamino-l,3-benzenediol dihydrochloride 21.3g(0.10mol), 6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid 50.7g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 2-5로 표현되는 증합체 (MW: 2400)를 얻었다.
Figure imgf000014_0002
Synthesis Example 5 A 1 L round bottom flask equipped with a condenser was charged with 21.3 g (0.10 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 6,6 '- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic (0.10 mol), and polyphosphoric acid (300 g) were charged, and the same synthetic procedure as in Synthesis Example 1 was carried out to obtain a polymer (MW: 2400) represented by Formula 2-5.
[화학식 2-5] [Chemical Formula 2-5]
Figure imgf000014_0003
합성예 6 웅축기를 장착한 1L 등근 바닥 플라스크에 2,4-diamino-l,3-benzenedithiol dihydrochloride 24.5g(0.10mol), 6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid
Figure imgf000014_0003
Synthesis Example 6 In a 1 L isometric bottom flask equipped with a magnetic stirrer, 24.5 g (0.10 mol) of 2,4-diamino-1,3-benzenedithiol dihydrochloride, 6,6 '- (9H-fluorene- 나프thalenecarboxylic acid
13  13
정정용지 (규칙제 91조) ISA/KR 50.7g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 2-6으로 표현되는 중합체 (MW: 2500)를 얻었다. Correction paper (Rule 91) ISA / KR (MW: 2500) represented by Formula 2-6 was obtained through the same synthetic procedure as in Synthesis Example 1, after adding 50.7 g (0.10 mol) of polyphosphoric acid and 300 g of polyphosphoric acid.
[화학식 2—6] [Chemical Formula 2-6]
Figure imgf000015_0001
합성예 7 응축기를 장착한 1L 등근 바닥 플라스크에 2,4-diamino-l,3-benzenediol dihydrochloride 10.7g(0.05mol), 2,4-diamino-l,3-benzenedithiol dihydrochloride 12.3g(0.05mol), 4,4'-(9H-fluorene-9-ylidene)bisbenzoic acid 40.6g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후， 합성예 1과 동일한 합성 과정을 거쳐 화학식 2- 7로 표현되는 증합체 (MW: 3000)를 얻었다.
Figure imgf000015_0001
Synthesis Example 7 To a 1 L round bottom flask equipped with a condenser were added 10.7 g (0.05 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 12.3 g (0.05 mol) of 2,4-diamino-1,3-benzenedithiol dihydrochloride, 40.6 g (0.10 mol) of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid and 300 g of polyphosphoric acid were charged, (MW: 3000).
[화학식 2-7] [Chemical Formula 2-7]
Figure imgf000015_0002
합성예 8 웅축기를 장착한 1L 등근 바닥 플라스크에 2,4-diamino-l,3-benzenediol dihydrochloride 10.7g(0.05mol), 2,4-diamino- 1 ,3-benzenedithiol dihydrochloride 12.3g(0.05mol), 6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid 50.7g(0.10mol), 그리고 polyphosphoric acid 300g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 2-8로 표현되는 중합체 (MW: 2400)를 얻었다.
Figure imgf000015_0002
Synthesis Example 8 To a 1 L round bottom flask equipped with a magnetic stirrer were added 10.7 g (0.05 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride and 12.3 g (0.05 mol) of 2,4-diamino-1,3-benzenedithiol dihydrochloride, (0.10 mol) of 6,6 '- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic acid and 300 g of polyphosphoric acid. ≪ / RTI > (MW: 2400).
14 14
정정용지 (규칙제 91조) ISA/KR [화학식 2-8] Correction paper (Rule 91) ISA / KR [Chemical Formula 2-8]
Figure imgf000016_0001
합성예 9 응축기를 장착한 1L 등근 바닥 플라스크에 l,2,3,4-benzenetetramine tetrahydrochloride 28.4g(0.10mol), 4,4'-(9H-fluorene-9-ylidene)bisbenzoic acid 20.3g(0.05mol), 6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid 25.4g(0.05mol), 그리고 polyphosphoric acid 300g을 투입한 후， 합성예 1과 동일한 합성 과정을 거쳐 화학식 2- 9로 표현되는 증합체 (MW: 3100)를 얻었다.
Figure imgf000016_0001
Synthesis Example 9 In a 1 L isometric bottom flask equipped with a condenser, 28.4 g (0.10 mol) of 1,2,3,4-benzenetetramine tetrahydrochloride and 20.3 g (0.05 mol) of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid ), 25.4 g (0.05 mol) of 6,6'- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic acid and 300 g of polyphosphoric acid. 9 (MW: 3100) was obtained.
[화학식 2-9] [Chemical Formula 2-9]
Figure imgf000016_0002
합성예 10 웅축기를 장착한 1L 등근 바닥 플라스크에 2,4-diamino-l,3-benzenediol dihydrochloride 21.3g(0.10mol), 4,4'-(9H-fluorene-9-ylidene)bisbenzoic acid 20.3g(0.05mol), 6,6'-(9H-fluorene-9-ylidene)bis-2-naphthalenecarboxylic acid 25.4g(0.05mol), 그리고 polyphosphoric acid 300g을 투입한 후， 합성예 1과 동일한 합성 과정을 거쳐 화학식 2- 10으로 표현되는 증합체 (MW: 3300)를 얻었다ᅳ
Figure imgf000016_0002
Synthesis Example 10 In a 1 L isometric bottom flask equipped with a magnetic stirrer, 21.3 g (0.10 mol) of 2,4-diamino-1,3-benzenediol dihydrochloride, 20.3 g of 4,4 '- (9H-fluorene-9-ylidene) bisbenzoic acid (0.05 mol) of 6,6'- (9H-fluorene-9-ylidene) bis-2-naphthalenecarboxylic acid and 300 g of polyphosphoric acid were charged and then subjected to the same synthetic procedure as in Synthesis Example 1 (MW: 3300) represented by the formula 2-10 was obtained.
[화학식 2-10] [Chemical Formula 2-10]
Figure imgf000016_0003
비교합성예
Figure imgf000016_0003
Comparative Synthetic Example
15  15
정정용지 (규칙제 91조) ISA/KR 웅축기를 장착한 500mL 2-neck 등근 바닥 플라스크에 4,4'-(9H-fluorene-9- ylidene)bisphenol 35.0g(0.10mol), l,4-bis(methoxymethyl)benzene 16.6g(0.10mol), diethyl sulfate 15.4g(0.10mol), 그리고 PGMEA 134g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 A로 표현되는 중합체 (MW: 1700)를 얻었다. Correction paper (Rule 91) ISA / KR (0.10 mol) of 4,4 '- (9H-fluorene-9-ylidene) bisphenol and 16.6 g (0.10 mol) of 1,4-bis (methoxymethyl) benzene were placed in a 500 mL 2-neck, , 15.4 g (0.10 mol) of diethyl sulfate, and 134 g of PGMEA were charged, followed by the same synthesis procedure as in Synthesis Example 1 to obtain a polymer (MW: 1700) represented by Formula A.
[화학식 A] (A)
Figure imgf000017_0001
비교합성예 2 웅축기를 장착한 500mL 2-neck 등근 바닥 플라스크에 1-hydroxypyrene 21.8g(0.10mol), 1-naphthol 14.5g(0.10mol), paraformaldehyde 6.0g(0.2mol), 그리고 diethyl sulfate 15.4g(0.10mol), 그리고 PGMEA 115g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 B로 표현되는 중합체 (MW: 1500)를 얻었다.
Figure imgf000017_0001
Comparative Synthesis Example 2 In a 500 mL 2-neck round bottom flask equipped with a magnetic stirrer, 21.8 g (0.10 mol) of 1-hydroxypyrene, 14.5 g (0.10 mol) of 1-naphthol, 6.0 g (0.2 mol) of paraformaldehyde, and 15.4 g (0.10 mol) of PGMEA, and 115 g of PGMEA were charged, and then the same synthesis procedure as in Synthesis Example 1 was carried out to obtain a polymer (MW: 1500) represented by the formula (B).
[화학식 B] [Chemical Formula B]
Figure imgf000017_0002
비교합성예 3 웅축기를 장착한 500mL 2-neck 등근 바닥 플라스크에 indole 11.72g(0.10mol), 9-fluorenone 18.02g(0.10mol), 그리고 p-toluenensulfonic acid 1.90g(0.01mol), 그리고 PGMEA 70g을 투입한 후, 합성예 1과 동일한 합성 과정을 거쳐 화학식 C로 표현되는 중합체 (MW: 1300)를 얻었다. [화학식 C]
Figure imgf000017_0002
Comparative Synthesis Example 3 In a 500 mL 2-neck round bottom flask equipped with a magnetic stirrer, 11.72 g (0.10 mol) of indole, 18.02 g (0.10 mol) of 9-fluorenone, 1.90 g (0.01 mol) of p-toluenensulfonic acid, and 70 g , The polymer (MW: 1300) represented by the formula (C) was obtained through the same synthesis procedure as in Synthesis Example 1. ≪ RTI ID = 0.0 &
Figure imgf000018_0001
Figure imgf000018_0001
하드마스크조성물의 제조 Preparation of hard mask composition
실시예 1  Example 1
합성예 1에서 얻은 중합체 3.0g을 사이클로핵사논 (cyclohexanone) 17g에 녹인 후 0.1 의 테플론 필터로 여과하여 하드마스크 조성물을 제조하였다.  3.0 g of the polymer obtained in Synthesis Example 1 was dissolved in 17 g of cyclohexanone, followed by filtration with a 0.1 Teflon filter to prepare a hard mask composition.
실시예 2  Example 2
합성예 1에서 얻은 중합체 대신 합성예 2에서 얻은 증합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  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 instead of the polymer obtained in Synthesis Example 1.
실시예 3  Example 3
합성예 1에서 얻은 화합물 대신 합성예 3에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  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 compound obtained in Synthesis Example 1.
실시예 4  Example 4
합성예 1에서 얻은 중합체 대신 합성예 4에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  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.
실시예 5  Example 5
합성예 1에서 얻은 중합체 대신 합성예 5에서 얻은 증합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 5 was used in place of the polymer obtained in Synthesis Example 1.
실시예 6  Example 6
합성예 1에서 얻은 중합체 대신 합성예 6에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 6 was used in place of the polymer obtained in Synthesis Example 1.
실시예 7  Example 7
합성예 1에서 얻은 중합체 대신 합성예 7에서 얻은 증합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물올 제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 7 was used instead of the polymer obtained in Synthesis Example 1.
실시예 8  Example 8
17  17
정정용지 (규칙제 91조) ISA/KR 합성예 1에서 얻은 중합체 대신 합성예 8에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과동일한 방법으로 하드마스크 조성물을 제조하였다. Correction paper (Rule 91) ISA / KR A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 8 was used in place of the polymer obtained in Synthesis Example 1.
실시예 9  Example 9
합성예 1에서 얻은 중합체 대신 합성예 9에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 9 was used in place of the polymer obtained in Synthesis Example 1.
실시예 10  Example 10
합성예 1에서 얻은 중합체 대신 합성예 10에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 10 was used in place of the polymer obtained in Synthesis Example 1.
비교예 1  Comparative Example 1
합성예 1에서 얻은 중합체 대신 비교합성예 1에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  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 instead of the polymer obtained in Synthesis Example 1.
비교예 2  Comparative Example 2
합성예 1에서 얻은 중합체 대신 비교합성예 2에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  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 얻은 중합체 대신 비교합성예 3에서 얻은 중합체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다. 평가 1: 갭-필 특성 및 평탄화특성 실시예 1 내지 10과 비교예 1 내지 4에 따른 하드마스크 조성물을 용질 대비 용매의 질량비를 3 대 97으로 조정하여 실리콘 웨이퍼에 스핀-코팅한 다음, 베이크 공정을 거쳐 절단면을 V-SEM을 이용하여 관찰하였다. 이상의 조건에서 베어 웨이퍼 상에서의 마스크 두께가 1100A정도가 되었다. 갭-필 및 평탄화 특성은 전자 주사 현미경 (SEM)을 사용하여 패턴 단면을 관찰하여 보이드 (void) 발생 유무로 판별하였고， 평탄화 특성은 도 2에서 (i -hs)의 값으로 나타내어지는 단차를 측정하였다. 도 2를 참고하면, ¾은 기판에서 패턴이 형성되지 않은 임의의 3개 지점에서 측정한 박막의 두께를 평균한 값을 의미하고， h2는 기판에서 패턴이 형성된 임의의 3개 지점에서 측정한 박막의 두께를 의미한다. 도 2를 참고하면, 평탄화 특성은 l 및 h2의 차이 (즉, 단차)가 크지 않을수록 우수한 것이다. 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. Evaluation 1: Gap-fill property and planarization property The hard mask composition according to Examples 1 to 10 and Comparative Examples 1 to 4 was spin-coated on a silicon wafer by adjusting the mass ratio of the solvent to the solute to 3 to 97, And the cut surface was observed using V-SEM. Under the above conditions, the mask thickness on the bare wafer was about 1100A. The gap-fill and planarization characteristics were determined by observing the cross-section of the pattern using a scanning electron microscope (SEM) to determine whether or not a void was generated. The planarization characteristic was measured by measuring the step represented by the value of (i -hs) Respectively. Referring to FIG. 2, ¾ means a value obtained by averaging thicknesses of thin films measured at arbitrary three points where no pattern is formed in the substrate, and h 2 denotes a value measured at any three points where a pattern is formed on the substrate Means the thickness of the thin film. Referring to FIG. 2, the planarization characteristics are improved as the difference between 1 and h 2 will be.
[표 1] [Table 1]
Figure imgf000020_0001
표 1을 참고하면， 갭-필 특성을 보여주는 보이드 유무， 그리고 평탄화 특성을 보여주는 단차 결과를 비교해보면, 실시예 1 내지 10에 따른 하드마스크 조성물과 비교예 1 내지 2에 따른 하드마스크 조성물이 거의 동등한 수준의 결과를 나타내고, 비교예 3 에 따른 하드마스크 조성물보다좋은 수준의 결과를 나타낸다.
Figure imgf000020_0001
Referring to Table 1, comparing the result of the step difference showing the presence of voids showing the gap-fill characteristic and the planarization characteristic, it can be seen that the hard mask composition according to Examples 1 to 10 and the hard mask composition according to Comparative Examples 1 and 2 are almost equal Level results and shows a better level of results than the hard mask composition according to Comparative Example 3. < tb >< TABLE >
. 평가 2: 내식각성 실시예 1 내지 10과 비교예 1 내지 3에 따른 하드마스크 조성물을 용질 대비 용매의 질량비를 15 대 85로 조정하여 실리콘 웨이퍼에 스핀-코팅한 다음, 핫플레이트 위에서 400°C로 2분간 열처리하여 4,000A 두께로 박막을 형성하고， 형성된 박막의 두께를 측정하였다. 이어서 상기 박막에 CHF3/CF4 흔합 가스 및 N2/02 흔합 가스를 사용하여 각각 100초 및 60초 동안 건식 식각한 후 박막의 두께를 다시 측정하였다. 건식 식각 전후의 박막의 두께와 식각 시간으로부터 하기 계산식 1에 의해 식각율 (bulk etch rate, BER)을 계산하였다. . Evaluation 2: adjusting the hard mask composition of the Comparative Examples 1 to 3 and the etch-resistant Examples 1 to 10 the weight ratio of the solute compared to the solvent 15 to 85 was spin-on silicon wafer was coated to the next, 400 ° C on a hot plate Treated for 2 minutes to form a thin film having a thickness of 4,000 A, and the thickness of the formed thin film was measured. Subsequently, the thin film was dry-etched for 100 seconds and 60 seconds using CHF 3 / CF 4 fog gas and N 2 / O 2 fog gas, respectively, The thickness was again measured. The bulk etch rate (BER) was calculated from the thickness and etch time of the thin film before and after dry etching according to the following equation.
[계산식 1]  [Equation 1]
(초기 박막 두께 -식각후 박막 두께) /식각 시간 (A/sec)  (Initial thin film thickness - thin film thickness after etching) / etching time (A / sec)
그 결과는 표 2과 같다.  The results are shown in Table 2.
[표 2]  [Table 2]
Figure imgf000021_0001
표 2를 참고하면, 실시예 1 내지 10에 따른 하드마스크 조성물로부터 형성된 박막은 비교예 1 내지 3에 따른 하드마스크 조성물로부터 형성된 박막과 비교하여 식각 가스에 대한 층분한 내식각성이 있어서 벌크 에치 특성이 향상됨을 확인할 수 있다.
Figure imgf000021_0001
Referring to Table 2, the thin films formed from the hard mask compositions according to Examples 1 to 10 had a superb corrosion resistance to etching gas compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 3, It can be confirmed that it is improved.
이상에서 본 발명의 바람직한 실시예들에 대하여 상세하게 설명하였지만 본 발명의 권리 범위는 이에 한정되는 것은 아니고 다음의 청구 범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리 범위에 속하는 것이다. 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, And falls within the scope of the invention.

Claims

【청구의 범위】 【청구항 11 하기 화학식 1로 표현되는 모이어티를 포함하는 중합체: 11. A polymer comprising a moiety represented by the following formula (1):
[화학식 1 ]  [Chemical Formula 1]
Figure imgf000023_0001
Figure imgf000023_0001
상기 화학식 1에서,  In Formula 1,
X 및 Y는 각각 독립적으로 적어도 하나의 헤테로 원자를 함유하는 오각 고리기이다.  X and Y are each independently a pentachloro ring containing at least one hetero atom.
【청구항 2 ]  [Claim 2]
제 1항에서,  The method of claim 1,
치환 또는 비치환된 플루오렌 모이어티를 더 포함하는 중합체.  Further comprising a substituted or unsubstituted fluorene moiety.
【청구항 3】  [Claim 3]
제 2항에서,  3. The method of claim 2,
하기 화학식 2로 표현되는 구조단위를 포함하는 중합체:  A polymer comprising a structural unit represented by the following formula (2): < EMI ID =
[화학식 2]
Figure imgf000023_0002
상기 화학식 2에서, (2)
Figure imgf000023_0002
In Formula 2,
A 및 C는 각각 독립적으로 상기 화학식 1로 표현되는 모이어티이고, A and C are each independently a moiety represented by the above formula (1)
B 및 D는 각각 독립적으로 치환 또는 비치환된 플루오렌 모이어티를 포함하는 2가의 기이고, n은 0 또는 1이고, B and D are each independently a divalent group including substituted or unsubstituted fluorene moieties, n is 0 or 1,
*는 연결지점이다. * Is the connection point.
【청구항 4】 제 3항에서, Claim 4 4. The method of claim 3,
상기 화학식 2에서 A 및 C는 각각 독립적으로  In Formula 2, A and C are each independently
모이어티들 중 어느 하나인 중합체: Polymers that are any of the moieties:
[그룹 1] [Group 1]
Figure imgf000024_0001
Figure imgf000024_0001
【청구항 5】  [Claim 5]
제 3항에서,  4. The method of claim 3,
상기 화학식 2에서 B 및 D는 각각 독립적으로 하기 그룹 2에 나열된 치환 또는 비치환된 2가의 기들 중 어느 하나인 중합체:  Wherein B and D are each independently any one of the substituted or unsubstituted divalent groups listed in the following group 2:
[그룹 2  [Group 2
Figure imgf000024_0002
Figure imgf000024_0002
【청구항 6]  [Claim 6]
제 1항에서,  The method of claim 1,
23  23
정정용지 (규칙제 91조) ISA/KR 중량평균분자량이 500 내지 200,000인 중합체. Correction paper (Rule 91) ISA / KR A polymer having a weight average molecular weight of 500 to 200,000.
【청구항 7】  7.
하기 화학식 1로 표현되는 모이어티를 포함하는 중합체, 그리고  A polymer comprising a moiety represented by the following formula (1), and
용매  menstruum
를 포함하는  Containing
유기막 조성물:  Organic film composition:
[화학식 1]  [Chemical Formula 1]
Figure imgf000025_0001
Figure imgf000025_0001
상기 화학식 1에서,  In Formula 1,
X 및 Y는 각각 독립적으로 적어도 하나의 헤테로 원자를 함유하는 오각 고리기이다.  X and Y are each independently a pentachloro ring containing at least one hetero atom.
【청구항 8】  8.
거 17항에서，  In Paragraph 17,
상기 중합체는 치환 또는 비치환된 플루오렌 모이어티를 더 포함하는 유기막 조성물.  Wherein the polymer further comprises a substituted or unsubstituted fluorene moiety.
【청구항 9]  9]
저 18항에서，  In that 18th paragraph,
상기 중합체는 하기 화학식 2로 표현되는 구조단위를 포함하는 유기막 조성물: Wherein the polymer comprises a structural unit represented by the following Formula 2:
화학식 2]
Figure imgf000025_0002
상기 화학식 2에서， . (2)
Figure imgf000025_0002
In the above formula (2).
A 및 C는 각각 독립적으로 상기 화학식 1로 표현되는 모이어티이고, A and C are each independently a moiety represented by the above formula (1)
B 및 D는 각각 독립적으로 치환 또는 비치환된 플루오렌 모이어티를 포함하는 2가의 기이고， n은 0 또는 1이고， *는 연결지점이다. B and D each independently represent a divalent group including substituted or unsubstituted fluorene moieties, n is 0 or 1, and * is a connection point.
【청구항 10】 Claim 10
제 9항에서,  The method of claim 9,
상기 화학식 2에서 A 및 C는 각각 독립적으로 하기 그룹 1에 나열된 모이어티들 중 어느 하나인 유기막 조성물:  Wherein A and C are independently any one of the moieties listed in Group 1 below:
[그룹 1] [Group 1]
Figure imgf000026_0001
Figure imgf000026_0001
【청구항 111  Claim 111
제 9항에서,  The method of claim 9,
상기 화학식 2에서 B 및 D는 각각 독립적으로 하기 그룹 2에 나열된 치환 또는 비치환된 2가의 기들 중 어느 하나인 유기막 조성물:  Wherein B and D are each independently any one selected from the group consisting of substituted or unsubstituted divalent groups listed in the following group 2:
25 25
정정용지 (규칙제 91조) ISA/KR 그룹 2] Correction paper (Rule 91) ISA / KR Group 2]
Figure imgf000027_0001
Figure imgf000027_0001
【청구항 12】  Claim 12
제 7항에서,  8. The method of claim 7,
상기 중합체의 중량평균분자량이 500 내지 200,000인 유기막 조성물.  Wherein the polymer has a weight average molecular weight of 500 to 200,000.
【청구항 13] [13]
기판 위에 재료 층을 제공하는 단계，  Providing a layer of material over the substrate,
상기 재료 층 위에 제 7항 내지 제 12항 중 어'느 한 항에 따른 조성물을 적용하는 단계， Applying a composition according to claim 7 to 12 wherein the control of 'a slow wherein on the material layer,
상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계, 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계, 상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계, 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하 단계,  Forming a hard mask layer by heat treating the organic film composition, 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 Forming a photoresist pattern,
상기 포토레지스트 패턴을 이용하여 상기 실리콘 함유 박막층 및 상기 하드마스크 층을 선택적으로 제거하고 상기 재료 층의 일부를 노출하는 단계, 그리고 Selectively removing said silicon-containing thin film layer and said hard mask layer using said photoresist pattern and exposing a portion of said material layer, And
상기 재료 층의 노출된 부분을 식각하는 단계  Etching the exposed portion of the material layer
를 포함하는  Containing
패턴 형성 방법.  Pattern formation method.
【청구항 14]  [14]
제 13항에서,  The method of claim 13,
상기 유기막 조성물을 적용하는 단계는 스핀-온 코팅 방법으로 수행하는 패턴 형성 방법.  Wherein the step of applying the organic film composition is performed by a spin-on coating method.
【청구항 15]  [15]
제 13항에서,  The method of claim 13,
상기 포토레지스트 층을 형성하는 단계 전에 바닥 반사 방지 층 (BARC)을 형성하는 단계를 더 포함하는 패턴 형성 방법.  Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
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