WO2018088673A1 - 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
WO2018088673A1
WO2018088673A1 PCT/KR2017/007906 KR2017007906W WO2018088673A1 WO 2018088673 A1 WO2018088673 A1 WO 2018088673A1 KR 2017007906 W KR2017007906 W KR 2017007906W WO 2018088673 A1 WO2018088673 A1 WO 2018088673A1
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Prior art keywords
substituted
unsubstituted
group
formula
polymer
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PCT/KR2017/007906
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French (fr)
Korean (ko)
Inventor
정현일
김성환
김성현
박유신
임재범
Original Assignee
삼성에스디아이 주식회사
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Priority claimed from KR1020170055623A external-priority patent/KR102037818B1/en
Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Priority to US16/339,451 priority Critical patent/US11203662B2/en
Priority to EP17868972.5A priority patent/EP3521332A4/en
Priority to CN201780069472.4A priority patent/CN109983053A/en
Priority to JP2019524024A priority patent/JP7025422B2/en
Publication of WO2018088673A1 publication Critical patent/WO2018088673A1/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
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • 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
    • 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
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers

Definitions

  • a novel polymer, an organic film composition containing 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 a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask. do.
  • a fine pattern may be formed by forming an organic film called a hardmask layer between the material layer and the photoresist layer to be etched.
  • the hard mask layer serves as an interlayer that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Therefore, the hard mask layer needs the characteristics of heat resistance and etching resistance to withstand the multiple etching process.
  • the hard mask layer has recently been proposed to form by spin-on coating (spin-on coat ing) method instead of chemical vapor deposition method.
  • the spin-on coating method is easy to process and can improve gap-fill properties and planarization properties.
  • multiple pattern formation is essential.
  • a buried property of filling the film with a film without voids is required.
  • One embodiment provides a novel polymer that ensures solubility and yet has excellent heat and etching resistance.
  • Another embodiment provides an organic film composition comprising the polymer. Another embodiment provides a pattern forming method using the organic film composition.
  • a polymer comprising a structural unit represented by the following Chemical Formula 1, and a structural unit represented by the following Chemical Formula 2 is provided. '
  • a 1 is a moiety represented by the following formula (X),
  • a 2 is a substituted or unsubstituted C 6 to C 30 aromatic ring which is different from A 1.
  • B 1 and B 2 are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
  • Ar is a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof
  • R a is hydrogen, a hydroxy group, a halogen group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, 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 a combination thereof,
  • Z a is each independently 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 A C30 alkynyl group 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 a combination thereof,
  • n 0 or 1
  • B 1 and B 2 may each be any one of the substituted or unsubstituted moieties listed in Group 1 below.
  • a 1 may be any one of the moieties listed in Group 2 below.
  • R 1 and R 2 are each independently hydrogen, hydroxy group, halogen group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or Unsubstituted C2 To C30 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof:
  • hydrogen in each moiety is each independently 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 groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or these It is substituted by a combination of or unsubstituted.
  • a 2 may be any one of the substituted or unsubstituted moieties listed in Group 1.
  • ⁇ In Formula 2 may be substituted with at least one hydroxy group.
  • B 1 and B 2 may have the same structure as the substituted or unsubstituted C6 to C30 aromatic ring.
  • the weight average molecular weight of the polymer may be 1, 000 to 200, 000.
  • an organic film composition including the polymer described above and a solvent is provided.
  • the polymer may be included in an amount of 0.01 wt% to 50 wt% with respect to the total content of the organic layer composition.
  • forming a material layer on a substrate applying an organic film composition comprising the above-described polymer and solvent on the material layer, heat treating the organic film composition to form a hard mask layer
  • Forming a photoresist 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;
  • Selectively removing the silicon containing thin film layer and the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer It provides a formation method.
  • the applying of the organic film composition may be performed by a spin-on coating method.
  • the method may further include forming a bottom anti-reflection layer (BARC) before forming the photoresist layer.
  • BARC bottom anti-reflection layer
  • the polymer according to one embodiment is excellent in heat resistance and etching resistance.
  • the polymer is used as an organic film material, it is possible to provide an organic film that can satisfy flatness while having excellent film density and etching resistance.
  • FIG. 1 is a flowchart illustrating a pattern forming method according to an embodiment.
  • the 1-substituted ' is a hydrogen atom a halogen atom in the compound (F, Br, C1, or 1), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido, amino Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 C30 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycl
  • hetero means containing 1 to 3 heteroatoms selected from N, 0, S and P.
  • hetero indicates a point of connection of a compound or compound moiety.
  • the polymer according to one embodiment includes a structural unit represented by the following Chemical Formula 1, and a structural unit represented by the following Chemical Formula 2.
  • a 1 is a moiety represented by the following formula (X),
  • a 2 is a substituted or unsubstituted C 6 to C 30 aromatic ring having a structure with A 1 ,
  • B 1 and B 2 are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
  • Ar is a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring substituted or unsubstituted hexagonal ring, or a fused ring thereof
  • R a is hydrogen, 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 An 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 a combination thereof,
  • Z a is each independently 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 A C30 alkynyl group 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 a combination thereof,
  • n 0 or 1
  • the polymer includes both the structural units represented by Chemical Formula 1 and the structural units represented by Chemical Formula 2, wherein the number and arrangement of these structural units are not limited.
  • the structural units represented by Formulas 1 and 2 consist of one part represented by A 1 and A 2 , and a second part represented by hydrogen atom (H), carbon, B 1 and B 2 .
  • a 1 and A 2 have different structures.
  • a 1 is represented by Formula X as an indol compound, or a derivative thereof.
  • Ar represents a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof, wherein the fused ring is, for example, benzene
  • the ring may be in two, three or four fused form, but is not limited thereto.
  • a 1 may be, for example, any one of the moieties listed in Group 2, but is not limited thereto.
  • R 1 and R 2 are each independently hydrogen, hydroxy group, halogen group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, 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 a combination thereof:
  • hydrogen in each moiety is each independently 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 groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or these It is substituted by a combination of or unsubstituted.
  • the position at which each moiety is linked to Formula 1 in Group 2 is not particularly limited.
  • the polymer can be easily controlled by selecting the type and number of Z 1 to Z 7 representing a functional group substituted with a cyclic group.
  • a 2 has a structure different from A 1 representing indole, or a derivative thereof, as a substituted or unsubstituted aromatic ring of C6 to C30.
  • a 2 may be any one of the substituted or unsubstituted moieties listed in Group 1 below, but is not limited thereto.
  • the position at which each moiety is linked to Formula 2 in Group 1 is not particularly limited.
  • at least one hydrogen in the moiety is a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alke. It may be a form substituted by a silyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof.
  • the A 2 May be substituted by at least one hydroxy group.
  • the polymers can be secured etch-resistant, having a cyclic group portion is represented by A 1, and A 2 in the general formula (2) in formula (I).
  • the polymer includes an indole moiety (A 1 ) in the structural unit represented by Chemical Formula 1, whereby one side of the pentagonal ring moiety containing a nitrogen atom (N) has a structure (fused) blocked by a ring. The branches but the other side By having an open structure without fusion (ie, one side of the pentagonal ring in Formula X is fused with Ar, the other side is not), the pentagonal ring portion containing the nitrogen atom is baked compared to the blocked carbazole series.
  • the inside of the polymer or the bond between the polymers may be promoted to have an effect of increasing the carbon content, and thus the etching resistance may be further improved.
  • the structural units represented by Chemical Formulas 1 and 2 include a hydrogen atom (H), carbon, a second portion represented by B 1 and B 2 .
  • B 1 and B 2 may be any one of the substituted or unsubstituted moieties listed in the following Group 1, but is not limited thereto.
  • B 1 and B 2 may have the same structure. Since the polymer basically includes a carbon ring group represented by A 1 , A 2 , B 1, and B 2 , etching resistance can be ensured.
  • the carbon contained in the crab 2 corresponds to 'tertiary carbon'.
  • the tertiary carbon refers to carbon in a form in which three sites of four hydrogens bonded to carbon are substituted with a group other than hydrogen.
  • the ring parameter of the polymer may be maximized to further enhance the etching resistance.
  • the solubility of the hard mask layer may be improved, which is advantageous to apply to the spin-on coating method.
  • the polymer can be polymerized, for example, by terpolymerization.
  • the tertiary carbon structure in the polymer can be formed, for example, by introducing an aldehyde compound, or derivative thereof, as an electrophile in the synthesis of the polymer.
  • the polymer has a structure that reduces the number of hydrogen present in the bonding position while increasing the carbon content of the polymer by using the aldehyde compound or a derivative thereof, and a monomer having a high carbon content in the ternary copolymerization. This can be enhanced.
  • 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.
  • a weight average molecular weight in the above range it can be optimized by adjusting the carbon content and the solubility in the solvent of the organic film composition (eg hard mask composition) comprising the polymer.
  • the polymer is used as an organic film material, it is possible to form a uniform thin film without formation of pin-holes and voids or deterioration of thickness distribution during the baking process, as well as when a step is present in the lower substrate (or film) or pattern It can provide excellent gap-fill and planarization properties when forming a.
  • an organic film composition including the polymer described above and a solvent is provided.
  • the solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, for example, propylene glycol, Propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclonucleanone, ethyl lactate At least one selected from gamma-butyrolactone, ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide, methylpyridone, methylpyridinone, acetylacetone and ethyl 3-ethoxypropionate It may include.
  • the polymer is about 0.1% to 50% by weight, based on the total content of the organic film composition, about 0. 1 to 30 weight percent, or about 0. It may be included in 1 to 15% by weight. By including the polymer in the above range it is possible to control the thickness, surface roughness and degree of planarization of the organic film.
  • 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.
  • the surfactant may be, for example, fluoroalkyl-based compounds, alkylbenzenesulfonic acid salts, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts and the like, but is not limited thereto.
  • the crosslinking agent may be, for example, melamine type, substituted element type, or these polymer type.
  • a crosslinking agent having at least two crosslinking substituents for example, methoxymethylated glycoryl, subspecific methylated glycoryl, methoxymethylated melamine, appendoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or subspecific methylated thiourea can be used.
  • a crosslinking agent having high heat resistance may be used as the crosslinking agent.
  • numerator can be used.
  • the thermal acid generator is, for example, an acidic compound such as ⁇ -luluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium ⁇ —lurusulsulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and / or 2 , 4,4,6- Tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other alkyl sulfonic acid alkyl esters may be used, but is not limited thereto.
  • an acidic compound such as ⁇ -luluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium ⁇ —lurusulsulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzo
  • 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 in the said range, solubility can be improved without changing the optical characteristic of an organic film composition.
  • an organic film prepared using the organic film composition described above is provided.
  • the organic layer may be in the form of the organic layer composition, for example, coated on a substrate and then cured through a heat treatment process, and may include, for example, an organic thin film used in an electronic device such as a hard mask layer, a planarization layer, a regenerative layer, a layer release agent, and the like. can do.
  • a pattern forming method includes forming a material layer on a substrate (S1), applying an organic film composition including the polymer and a solvent on the material layer (S2), and heat treating the organic film composition. Forming a hard mask layer (S3), 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), and exposing the photoresist layer.
  • 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, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like.
  • the material layer can be formed, for example, by chemical vapor deposition.
  • the organic film composition is as described above, it may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the organic film composition is not particularly limited, and for example, may be applied to a thickness of about 50 to ⁇ , ⁇ .
  • the heat treatment of the organic film composition is, for example, about 100 to about 100
  • 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 layer may be further formed on the silicon-containing thin film layer before the forming of the photoresist layer.
  • Exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV.
  • the heat treatment may be performed at about 100 to 700 ° C. after the exposure.
  • Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may use, for example, CHF 3 ) CF 4) Cl 2) BC1 3 and combinations 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 insulation pattern, or the like, and may be applied to, for example, various patterns in a semiconductor integrated circuit device.
  • the internal silver is lowered to 60-70 ° C, and then 300 g of tetrahydrofuran is added to make the compound not hardened.
  • the pH of the compound is increased to 5-6 with 7% aqueous sodium bicarbonate solution.
  • 1000 ml of ethyl acetate was poured and stirring continued, and then the organic layer was extracted using a separatory funnel.
  • 500 ml of water is added to a separatory funnel, shaken to remove the remaining acid and sodium salt three or more times, and the organic layer is finally extracted.
  • the organic solution was concentrated by an evaporator, and 1 L of tetrahydrofuran was added to the obtained compound to obtain a solution.
  • the solution was slowly added dropwise to a beaker containing 5 L of the nucleic acid being stirred to form a precipitate to obtain a polymer including the structural units represented by the formula la.
  • the weight average molecular weight (Mw) and the polydispersity (PD) of the polymer obtained by gel permeation chromatography (GPC) were measured, and the weight average molecular weight (Mw) was 1,890. (Polydispersity, PD) was 1.35.
  • the weight average molecular weight (Mw) of the obtained polymer was 3,100, and polydispersity (PD) was 1.43. 2a]
  • the weight average molecular weight (Mw) of the obtained polymer was 2,140, and polydispersity (PD) was 1.32.
  • the weight average molecular weight (Mw) of the obtained polymer was 2,470, and polydispersity (PD) was 1.29.
  • a polymer comprising the structural units shown in Chemical Formula 5a was obtained using the same method as in Synthesis Example 1, except that 1-nap was used instead of phenanthren-9-ol (Phenanthren® 9-ol).
  • the weight average molecular weight (Mw) of the obtained polymer was 1,760, and polydispersity (Polydi spersi ty, PD) was 1.43.
  • the weight average molecular weight (Mw) of the obtained polymer was 2,410, and polydispersity (Polydi spersi ty, PD) was 1.55.
  • the weight average molecular weight (Mw) of the obtained polymer was 1,570, and polydispersity (Polydi spersi ty, PD) was 1.26.
  • the weight average molecular weight (Mw) of the obtained polymer was 1,940, and polydispersity (Polydi spersi ty, PD) was 1.35.
  • Polydispersity (PD) was 1.31.
  • the increase average molecular weight (Mw) of the obtained polymer was 1,920, and polydispersity (Polydi spersi ty, PD) was 1.34.
  • the weight average molecular weight (Mw) of the obtained polymer was 3,200, and polydispersity (Polydi spers i ty, PD) was 1.85.
  • the weight average molecular weight (Mw) of the obtained polymer was 2,680, and polydispersity (PD) was 1.56.
  • Synthesis Example 4 was synthesized using the same method as in Synthesis Example 4, except that [2,3-b] carbazole (1,3-dihydroindolo [2,3-b] carbazole was used as 1,3-dihydroindo instead of indole. A polymer was obtained comprising the structural units indicated.
  • the weight average molecular weight (Mw) of the obtained polymer was 4,620, and polydispersity (PD) was 1.73.
  • the polymer obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), followed by 0.1 Teflon. Filtration with a filter produced a hardmask composition. According to the desired thickness, the weight of the polymer was adjusted to 5.0 to 30.0 wt% based on the total weight of the hard mask composition.
  • PGMEA propylene glycol monomethyl ether acetate
  • cyclohexanone 7: 3 (v / v)
  • a hardmask supernatant was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 3 was used instead of the compound obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 6 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 7 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 8 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 9 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 10 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 1 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1. Comparative Example 3
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1. 3 ⁇ 4>
  • the hard mask compositions according to Examples 1 to 10 and Comparative Examples 1 to 4 were spin-on coated on the silicon wafer to a thickness of 4,000 A, and then heat-treated at 240 ° C. on a hot plate for 1 minute to form a thin film.
  • the thickness of the thin film was measured. Then on the thin film
  • Example 4 24.6 24.9 Example 5 26.2 24.8 Example 6 25.4 23. 1 Example 7 22.9 22.7 Example 8 22.5 22.4 Example 9 22.3 21.9 Example 10 26.9 25.0 Comparative Example 1 29.4 28.4 Comparative Example 2 28.7 29.5 Comparative Example 3 30.2 27.7 Comparative Example 4 29.4 27.5
  • the etch rate was recalculated by changing the heat treatment temperature and time to 400 ° C. and 2 minutes, respectively. The results are shown in Table 2.
  • Example 9 23.3 21.5
  • Example 10 28. 1 23.9 Comparative Example 1 31. 1 27.0 Comparative Example 2 30.2 26.6 Comparative Example 3 31.4 26.4 Comparative Example 4 30.7 25.5
  • the hardware according to Examples 1 to 10 Compared with the thin film formed from the hard mask compositions according to Comparative Examples 1 to 4, the thin film formed from the mask composition may have sufficient etching resistance against the etching gas, thereby improving bulk etch characteristics.
  • Evaluation 2 film density
  • a hard mask composition according to Examples 1 to 10 and Comparative Examples 1 to 4 was spin-on coated on a silicon wafer and heat-treated at 240 ° C. for 1 minute on a hot plate to form a thin film having a thickness of 1,000 A.
  • FIG. 1 A hard mask composition according to Examples 1 to 10 and Comparative Examples 1 to 4 was spin-on coated on a silicon wafer and heat-treated at 240 ° C. for 1 minute on a hot plate to form a thin film having a thickness of 1,000 A.
  • the film density of the thin film was measured using an X-ray diffraction analysis (X-ray diffraction ion) equipment of PANalyt i cal.
  • Comparative Example 4 1.24 Referring to Table 3, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 10 has a high level of film density compared with the thin films according to Comparative Examples 1 to 4.

Abstract

The present invention relates to: a polymer comprising a structural unit represented by chemical formula 1 and a structural unit represented by chemical formula 2; an organic film composition containing the polymer; and a method for forming a pattern by using the organic film composition. The definition of chemical formulas 1 and 2 is the same as that described in the specification.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
중합체， 유기막 조성물 및 패턴형성방법  Polymer, Organic Film Composition and Pattern Forming Method
【기술분야】  Technical Field
신규한 중합체， 상기 중합체를 포함하는 유기막 조성물， 그리고 상기 유기막 조성물을 사용하는 패턴형성방법에 관한 것이다.  A novel polymer, an organic film composition containing the polymer, and a pattern forming method using the organic film composition.
【배경기술】  Background Art
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. 전형적인 리쏘그래픽 기법은 반도체 기판 위에 재료층을 형성하고 그 위에 포토레지스트 층을 코팅하고 노광 및 현상을 하여 포토레지스트 패턴을 형성한 후, 상기 포토레지스트 패턴을 마스크로 하여 재료층을 식각하는 과정을 포함한다.  Recently, the semiconductor industry has been developed from ultra-fine technology having a pattern of several hundred nanometers to several tens of nanometers. Effective lithographic techniques are essential to realizing this ultrafine technology. A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask. do.
근래， 형성하고자 하는 패턴의 크기가 감소함에 따라 상술한 전형적인 리쏘그래픽 기법만으로는 양호한 프로파일을 가진 미세 패턴을 형성하기 어렵다. 이에 따라 식각하고자 하는 재료층과 포토레지스트 층 사이에 일명 하드마스크 층 (hardmask layer )이라고 불리는 유기막을 형성하여 미세 패턴을 형성할 수 있다.  In recent years, as the size of a pattern to be formed is reduced, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a fine pattern may be formed by forming an organic film called a hardmask layer between the material layer and the photoresist layer to be etched.
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.  The hard mask layer serves as an interlayer that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Therefore, the hard mask layer needs the characteristics of heat resistance and etching resistance to withstand the multiple etching process.
한편， 근래 하드마스크 층은 화학기상증착 방법 대신 스핀-온 코팅 (spin-on coat ing) 방법으로 형성하는 것이 제안되었다. 스핀-온 코팅 방법은 공정이 용이할 뿐만 아니라 갭-필 (gap-f i l l ) 특성 및 평탄화 특성을 개선할 수 있다. 미세 패턴을 실현하기 위해서는 다중 패턴 형성이 필수적인데 이 때 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. On the other hand, the hard mask layer has recently been proposed to form by spin-on coating (spin-on coat ing) method instead of chemical vapor deposition method. The spin-on coating method is easy to process and can improve gap-fill properties and planarization properties. In order to realize a fine pattern, multiple pattern formation is essential. In this case, a buried property of filling the film with a film without voids is required. In addition, when there is a step in the substrate to be processed or when the pattern dense portion and the region without a pattern exist together on the wafer, It is necessary to flatten the film surface.
상술한 하드마스크 층에 요구되는 특성들을 만족할 수 있는 유기막 재료가요구된다.  There is a need for an organic film material that can satisfy the properties required for the above-mentioned hard mask layer.
【발명의 상세한 설명]  [Detailed Description of the Invention]
【기술적 과제】  [Technical problem]
일 구현예는 용해도를 확보하면서도 내열성 및 내식각성이 우수한 신규한 중합체를 제공한다.  One embodiment provides a novel polymer that ensures solubility and yet has excellent heat and etching resistance.
다른 구현예는 상기 중합체를 포함하는 유기막 조성물을 제공한다. 또 다른 구현예는 상기 유기막 조성물을 사용한 패턴 형성 방법을 제공한다.  Another embodiment provides an organic film composition comprising the polymer. Another embodiment provides a pattern forming method using the organic film composition.
【기술적 해결방법】  Technical Solution
일 구현예에 따르면， 하기 화학식 1로 표현되는 구조단위， 그리고 하기 화학식 2로 표현되는 구조단위를 포함하는 중합체를 제공한다. '  According to one embodiment, a polymer comprising a structural unit represented by the following Chemical Formula 1, and a structural unit represented by the following Chemical Formula 2 is provided. '
Figure imgf000004_0001
Figure imgf000004_0001
[화학식 2]
Figure imgf000004_0002
상기 화학식 1 및 2에서， [Formula 2]
Figure imgf000004_0002
In Chemical Formulas 1 and 2,
A1은 하기 화학식 X로 표현되는 모이어티이고， A 1 is a moiety represented by the following formula (X),
A2는 치환 또는 비치환된 C6 내지 C30의 방향족 고리로서 상기 A1과 다른 A 2 is a substituted or unsubstituted C 6 to C 30 aromatic ring which is different from A 1.
구조를 가지고，  With structure,
B1 및 B2는 각각 독립적으로 치환 또는 비치환된 C6 내지 C30의 방향족 고리이고， B 1 and B 2 are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
*은 연결지점이다:  * Is the connection point:
[화학식 X] [Formula X]
Figure imgf000005_0001
상기 화학식 X에서，
Figure imgf000005_0001
In Chemical Formula X,
Ar은 치환 또는 비치환된 사각 고리， 치환 또는 비치환된 오각 고리 , 치환또는 비치환된 육각 고리， 또는 이들의 융합 고리 ( fused r ing)이고, Ra는 수소， 히드록시기， 할로겐 기， 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 조합이고, Ar is a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof, and R a is hydrogen, a hydroxy group, a halogen group, a substituted or Unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, 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 a combination thereof,
Za는 각각 독립적으로 히드록시기， 할로겐 기， 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 조합이고, Z a is each independently 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 A C30 alkynyl group 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 a combination thereof,
m은 0 또는 1이다. m is 0 or 1;
상기 화학식 1 및 2에서 B1 및 B2는 각각 하기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나일 수 있다. In Formulas 1 and 2, B 1 and B 2 may each be any one of the substituted or unsubstituted moieties listed in Group 1 below.
[그룹 1] [Group 1]
Figure imgf000006_0001
Figure imgf000006_0001
상기 화학식 1에서 A1은 하기 그룹 2에 나열된 모이어티들 중 어느 하나일 수 있다. In Formula 1, A 1 may be any one of the moieties listed in Group 2 below.
[그룹 2] [Group 2]
Figure imgf000007_0001
상기 그룹 2에서，
Figure imgf000007_0001
In group 2 above,
R1 및 R2는 각각 독립적으로 수소， 히드록시기， 할로겐 기, 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 조합이다: R 1 and R 2 are each independently hydrogen, hydroxy group, halogen group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or Unsubstituted C2 To C30 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof:
단， 상기 그룹 2에서， 각 모이어티 내의 수소는 각각 독립적으로 히드록시기， 할로겐 기， 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. However, in Group 2, hydrogen in each moiety is each independently 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 groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or these It is substituted by a combination of or unsubstituted.
상기 화학식 2에서 A2는 상기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나일 수 있다. In Formula 2, A 2 may be any one of the substituted or unsubstituted moieties listed in Group 1.
상기 화학식 2에서 ^는 적어도 하나의 히드록시기에 의해 치환된 것일 수 있다.  ^ In Formula 2 may be substituted with at least one hydroxy group.
상기 화학식 1 및 2에서 B1 및 B2는 치환 또는 비치환된 C6 내지 C30 방향족 고리로서 서로 동일한구조를 가질 수 있다. In Formulas 1 and 2, B 1 and B 2 may have the same structure as the substituted or unsubstituted C6 to C30 aromatic ring.
상기 중합체의 중량평균분자량이 1 , 000 내지 200， 000일 수 있다. 다른 구현예에 따르면， 상술한 중합체， 그리고 용매를 포함하는 유기막 조성물을 제공한다.  The weight average molecular weight of the polymer may be 1, 000 to 200, 000. According to another embodiment, an organic film composition including the polymer described above and a solvent is provided.
상기 중합체는 상기 유기막 조성물의 총 함량에 대하여 0. 1 중량 % 내지 50 중량 %로 포함될 수 있다.  The polymer may be included in an amount of 0.01 wt% to 50 wt% with respect to the total content of the organic layer composition.
또 다른 구현예에 따르면， 기판 위에 재료 층을 형성하는 단계， 상기 재료 층 위에 상술한 중합체 및 용매를 포함하는 유기막 조성물을 적용하는 단계， 상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계， 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계， 상기 실리콘 함유 박막충 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， 그리고상기 재료 층의 노출된 부분을 식각하는 단계를 포함하는 패턴 형성 방법을 제공한다. According to another embodiment, forming a material layer on a substrate, applying an organic film composition comprising the above-described polymer and solvent on the material layer, heat treating the organic film composition to form a hard mask layer Forming a photoresist 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; Selectively removing the silicon containing thin film layer and the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer. It provides a formation method.
- 상기 유기막 조성물을 적용하는 단계는 스핀-온 코팅 방법으로 수행할 수 있다.  The applying of 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.  The method may further include forming a bottom anti-reflection layer (BARC) before 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 etching resistance. When the polymer is used as an organic film material, it is possible to provide an organic film that can satisfy flatness while having excellent film density and etching resistance.
【도면의 간단한 설명】  [Brief Description of Drawings]
도 1은 일 구현예에 따른 패턴 형성 방법을 설명하기 위한 흐름도이다.  1 is a flowchart illustrating a pattern forming method according to an embodiment.
【발명을 실시를 위한 최선의 형태】  [The best form for carrying out invention]
이하， 본 발명의 구현예에 대하여 본 발명이 속하는 기술분야에서 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, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
본 명세서에서 별도의 정의가 없는 한, 1치환된 '이란， 화합물 중의 수소 원자가 할로겐 원자 (F , Br , C1 , 또는 1 )， 히드록시기， 알콕시기, 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 사이클로알케닐기ᅳ C6 내지 C15 사이클로알키닐기， C3 내지 C30 헤테로사이클로알킬기 및 이들의 조합에서 선택된 치환기로 치환된 것을 의미한다ᅳ Unless otherwise defined herein, the 1-substituted 'is a hydrogen atom a halogen atom in the compound (F, Br, C1, or 1), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido, amino Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 C30 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group A C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, or a combination thereof.
또한， 본 명세서에서 별도의 정의가 없는 한， '헤테로'란, N, 0， S 및 P에서 선택된 헤테로 원자를 1 내지 3개 함유한 것을 의미한다. 또한， 본 명세서에서 별도의 정의가 없는 한， 는 화합물 또 화합물 부분 (moiety)의 연결 지점을 가리킨다. In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, 0, S and P. In addition, unless otherwise defined in this specification, indicates a point of connection of a compound or compound moiety.
이하 일 구현예에 따른 중합체를 설명한다.  Hereinafter, a polymer according to one embodiment is described.
일 구현예에 따른 중합체는 하기 화학식 1로 표현되는 구조단위， 그리고 하기 화학식 2로 표현되는 구조단위를 포함한다.  The polymer according to one embodiment includes a structural unit represented by the following Chemical Formula 1, and a structural unit represented by the following Chemical Formula 2.
[화학식 1]
Figure imgf000010_0001
[Formula 1]
Figure imgf000010_0001
[화학식 2]
Figure imgf000010_0002
상기 화학식 1 및 2에서， [Formula 2]
Figure imgf000010_0002
In Chemical Formulas 1 and 2,
A1은 하기 화학식 X로 표현되는 모이어티이고， A 1 is a moiety represented by the following formula (X),
A2는 치환 또는 비치환된 C6 내지 C30의 방향족 고리로서 상기 A1과 구조를 가지고， A 2 is a substituted or unsubstituted C 6 to C 30 aromatic ring having a structure with A 1 ,
B1 및 B2는 각각 독립적으로 치환 또는 비치환된 C6 내지 C30의 방향족 고리이고， B 1 and B 2 are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
*은 연결지점이다:  * Is the connection point:
[화학식 X]  [Formula X]
Figure imgf000010_0003
상기 화학식 X에서，
Figure imgf000010_0003
In Chemical Formula X,
Ar은 치환 또는 비치환된 사각 고리， 치환 또는비치환된 오각 고리 치환또는 비치환된 육각 고리， 또는 이들의 융합 고리 ( fused r ing)이고， Ra는 수소， 히드록시기， 할로겐 기， 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 조합이고， Ar is a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring substituted or unsubstituted hexagonal ring, or a fused ring thereof, R a is hydrogen, 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 An 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 a combination thereof,
Za는 각각 독립적 로 히드록시기， 할로겐 기， 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 조합이고， Z a is each independently 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 A C30 alkynyl group 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 a combination thereof,
m은 0 또는 1이다. m is 0 or 1;
상기 중합체는 상기 화학식 1로 표현되는 구조단위， 및 상기 화학식 2로 표현되는 구조단위를 모두 포함하며, 여기서 이들 구조단위의 개수 및 배열은 한정되지 않는다.  The polymer includes both the structural units represented by Chemical Formula 1 and the structural units represented by Chemical Formula 2, wherein the number and arrangement of these structural units are not limited.
' 상기 화학식 1 및 2로 표현되는 구조단위는 A1 및 A2로 표현되는 게 1 부분， 그리고 수소원자 (H) , 탄소， B1 및 B2로 표현되는 제 2 부분으로 이루어진다. The structural units represented by Formulas 1 and 2 consist of one part represented by A 1 and A 2 , and a second part represented by hydrogen atom (H), carbon, B 1 and B 2 .
상기 화학식 1 및 2에서， 상기 A1 및 A2는 서로 다른 구조를 가진다. 먼저， 상기 화학식 1에서 A1은 인돌 ( indol e) 화합물， 또는 이의 유도체로서 상기 화학식 X로 표현된다. In Formulas 1 and 2, A 1 and A 2 have different structures. First, in Formula 1, A 1 is represented by Formula X as an indol compound, or a derivative thereof.
상기 화학식 X에서, Ar은 치환 또는 비치환된 사각 고리， 치환 또는 비치환된 오각 고리， 치환 또는 비치환된 육각 고리， 또는 이들의 융합 고리 ( fused r ing)를 나타내며, 상기 융합 고리는 예컨대 벤젠 고리가 2개， 3개 또는 4개 융합된 형태일 수 있으나 이에 한정되는 것은 아니다.  In Formula X, Ar represents a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof, wherein the fused ring is, for example, benzene The ring may be in two, three or four fused form, but is not limited thereto.
상기 화학식 1에서 A1은 예컨대 하기 그룹 2에 나열된 모이어티들 중 어느 하나일 수 있으나 이에 한정되는 것은 아니다. In Formula 1, A 1 may be, for example, any one of the moieties listed in Group 2, but is not limited thereto.
[그룹 2] [Group 2]
Figure imgf000012_0001
상기 그룹 2에서，
Figure imgf000012_0001
In group 2 above,
R1 및 R2는 각각 독립적으로 수소， 히드록시기， 할로겐 기， 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 조합이다: R 1 and R 2 are each independently hydrogen, hydroxy group, halogen group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, 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 a combination thereof:
단， 상기 그룹 2에서, 각 모이어티 내의 수소는 각각 독립적으로 히드록시기， 할로겐 기， 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.  However, in Group 2, hydrogen in each moiety is each independently 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 groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or these It is substituted by a combination of or unsubstituted.
상기 그룹 2에서 각 모이어티가 화학식 1에 연결되는 위치는 특별히 한정되지 않는다. 상기 중합체는， 고리기에 치환된 작용기를 나타내는 Z1 내지 Z7의 종류 및 개수를 선택함으로써 물성 조절이 용이하다. The position at which each moiety is linked to Formula 1 in Group 2 is not particularly limited. The polymer can be easily controlled by selecting the type and number of Z 1 to Z 7 representing a functional group substituted with a cyclic group.
한편 , 상기 화학식 2에서 A2는 치환 또는 비치환된 C6 내지 C30의 방향족 고리로서 인돌, 또는 이의 유도체를 나타내는 A1과 다른 구조를 가진다. Meanwhile, in Formula 2, A 2 has a structure different from A 1 representing indole, or a derivative thereof, as a substituted or unsubstituted aromatic ring of C6 to C30.
상기 화학식 2에서 A2는 하기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나일 수 있으나， 이에 한정되는 것은 아니다. In Formula 2, A 2 may be any one of the substituted or unsubstituted moieties listed in Group 1 below, but is not limited thereto.
[그룹 1] [Group 1]
Figure imgf000014_0001
Figure imgf000014_0001
상기 그룹 1에서 각 모이어티가 화학식 2에 연결되는 위치는 특별히 한정되지 않는다. 예를 들어， 상기 그룹 1에 나타낸 모이어티들이 치환된 형태일 경우， 상기 모이어티 내의 하나의 적어도 하나의 수소가 히드록시기， 치환 또는 비치환된 C1 내지 C30 알킬기， 치환 또는 비치환된 C2 내지 C30 알케닐기， 치환 또는 비치환된 C2 내지 C30 알키닐기， 치환 또는 비치환된 C1 내지 C30 알콕시기, 또는 이들의 조합에 의해 치환된 형태일 수 있으나 이에 한정되는 것은 아니다.. 예를 들어, 상기 A2는 적어도 하나의 히드록시기에 의해 치환된 것일 수 있다. The position at which each moiety is linked to Formula 2 in Group 1 is not particularly limited. For example, when the moieties shown in Group 1 are substituted, at least one hydrogen in the moiety is a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alke. It may be a form substituted by a silyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof. For example, the A 2 May be substituted by at least one hydroxy group.
상기 중합체는, 상기 화학식 1에서 A1 , 그리고 상기 화학식 2에서 A2로 표현되는 고리기 부분을 가짐으로써 내식각성을 확보할 수 있다. 상기 중합체는 상기 화학식 1로 표현되는 구조 단위 내에 인돌 부분 (A1)을 포함함으로써， 질소 원자 (N)가 포함된 오각 고리 부분의 한쪽은 고리 (r ing)에 의해 막힌 (융합된) 구조를 가지나 다른 한쪽은 고리에 의해 융합되지 않고 열린 구조를 가짐으로써 (즉， 상기 화학식 X에서 오각 고리의 한쪽은 Ar과 융합되어 있으나， 다른 한쪽은 그렇지 않음)， 질소 원자가 포함된 오각 고리 부분이 모두 막힌 카바졸 계열과 비교하여 베이크 시 상대적으로 중합체 내부 혹은 중합체 간의 결합을 촉진하여 탄소 함량의 증가 효과를 가질 수 있고， 이에 따라 내식각성이 더욱 향상될 수 있다. 다음으로, 상술한 바와 같이， 상기 화학식 1 및 2로 표현되는 구조단위는 수소원자 (H) , 탄소， B1 및 B2로 표현되는 제 2 부분을 포함한다. 예를 들어， 상기 화학식 1 및 2에서 B1 및 B2는 각각 하기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나일 수 있으나， 이에 한정되는 것은 아니다.The polymers can be secured etch-resistant, having a cyclic group portion is represented by A 1, and A 2 in the general formula (2) in formula (I). The polymer includes an indole moiety (A 1 ) in the structural unit represented by Chemical Formula 1, whereby one side of the pentagonal ring moiety containing a nitrogen atom (N) has a structure (fused) blocked by a ring. The branches but the other side By having an open structure without fusion (ie, one side of the pentagonal ring in Formula X is fused with Ar, the other side is not), the pentagonal ring portion containing the nitrogen atom is baked compared to the blocked carbazole series. In the present invention, the inside of the polymer or the bond between the polymers may be promoted to have an effect of increasing the carbon content, and thus the etching resistance may be further improved. Next, as described above, the structural units represented by Chemical Formulas 1 and 2 include a hydrogen atom (H), carbon, a second portion represented by B 1 and B 2 . For example, in Formulas 1 and 2, B 1 and B 2 may be any one of the substituted or unsubstituted moieties listed in the following Group 1, but is not limited thereto.
그룹 1]  Group 1]
Figure imgf000015_0001
Figure imgf000015_0001
예를 들어 , 상기 화학식 1 및 2에서 B1 및 B2는 서로 동일한 구조 수 있다. 상기 중합체는 기본적으로 상기 A1 , A2 , B1 및 B2로 표현되는 탄소 고리기를 포함함으로써， 내식각성을 확보할 수 있다. For example, in Formulas 1 and 2, B 1 and B 2 may have the same structure. Since the polymer basically includes a carbon ring group represented by A 1 , A 2 , B 1, and B 2 , etching resistance can be ensured.
한편， 상기 게 2 부분에 포함되어 있는 탄소는 ' 3차 탄소'에 해당한다. 여기서， 3차 탄소란 탄소에 결합된 4개의 수소 중 3개 자리가 수소 이외의 다른 기로 치환된 형태의 탄소를 의미한다.  On the other hand, the carbon contained in the crab 2 corresponds to 'tertiary carbon'. Here, the tertiary carbon refers to carbon in a form in which three sites of four hydrogens bonded to carbon are substituted with a group other than hydrogen.
상기 중합체는 화학식 1 및 2로 표현되는 각각의 구조단위에 모두 3차 탄소를 포함함으로써, 중합체의 링 파리미터 (r ing parameter )가 극대화되어 내식각성을 더욱 강화시킬 수 있다. 또한， 이러한 형태의 탄소를 포함하는 중합체를 유기막 조성물에 사용할 경우 하드마스크 층의 용해성이 향상될 수 있어 스핀-온 코팅 방법에 적용하기 유리하다.  Since the polymer includes tertiary carbon in each structural unit represented by Chemical Formulas 1 and 2, the ring parameter of the polymer may be maximized to further enhance the etching resistance. In addition, when the polymer containing carbon of this type is used in the organic film composition, the solubility of the hard mask layer may be improved, which is advantageous to apply to the spin-on coating method.
상기 중합체는 예컨대 3원 공중합에 의해 중합될 수 있다. 상기 중합체에서 3차 탄소 구조는 예컨대 중합체 합성시 친전자체로서 알데히드 (aldehyde) 화합물, 또는 이의 유도체를 도입함으로써 형성될 수 있다. 상기 중합체는 상기 알데히드 화합물 또는 이의 유도체， 그리고 높은 탄소 함량을 가지는 단량체를 3원 공중합에 이용하여 중합체의 탄소 함량을 늘리면서도 단량체 간의 결합 위치에 존재하는 수소의 수를 저감시키는 구조를 가지게 되어 내식각성이 강화될 수 있다.  The polymer can be polymerized, for example, by terpolymerization. The tertiary carbon structure in the polymer can be formed, for example, by introducing an aldehyde compound, or derivative thereof, as an electrophile in the synthesis of the polymer. The polymer has a structure that reduces the number of hydrogen present in the bonding position while increasing the carbon content of the polymer by using the aldehyde compound or a derivative thereof, and a monomer having a high carbon content in the ternary copolymerization. This can be enhanced.
상기 중합체는 약 500 내지 200， 000의 중량평균분자량을 가질 수 있다. 보다 구체적으로 상기 중합체는 약 1 , 000 내지 20， 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. 상기 중합체를 유기막 재료로서 사용할 경우， 베이크 공정 중 핀-홀 및 보이드의 형성이나 두께 산포의 열화없이 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.  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 can be optimized by adjusting the carbon content and the solubility in the solvent of the organic film composition (eg hard mask composition) comprising the polymer. When the polymer is used as an organic film material, it is possible to form a uniform thin film without formation of pin-holes and voids or deterioration of thickness distribution during the baking process, as well as when a step is present in the lower substrate (or film) or pattern It can provide excellent gap-fill and planarization properties when forming a.
다른 구현예에 따르면， 상술한 중합체， 그리고 용매를 포함하는 유기막조성물을 제공한다.  According to another embodiment, an organic film composition including the polymer described above and a solvent is provided.
상기 용매는 상기 중합체에 대한 충분한 용해성 또는 분산성을 가지는 것이면 특별히 한정되지 않으나， 예컨대 프로필렌글리콜， 프로필렌글리콜 디아세테이트， 메록시 프로판디올, 디에틸렌글리콜， 디에틸렌글리콜 부틸에테르， 트리 (에틸렌글리콜)모노메될에테르， 프로필렌글리콜 모노메틸에테르， 프로필렌글리콜 모노메틸에테르 아세테이트， 사이클로핵사논， 에틸락테이트， 감마-부티로락톤， Ν ,Ν- 디메틸포름아미드， Ν , Ν-디메틸아세트아미드, 메틸피를리돈， 메틸피를리디논， 아세틸아세톤및 에틸 3-에톡시프로피오네이트에서 선택되는 적어도 하나를 포함할 수 있다. The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, for example, propylene glycol, Propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclonucleanone, ethyl lactate At least one selected from gamma-butyrolactone, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, methylpyridone, methylpyridinone, acetylacetone and ethyl 3-ethoxypropionate It may include.
상기 중합체는 상기 유기막 조성물의 총 함량에 대하여 약 0. 1 내지 50 중량 %， 약 0 . 1 내지 30 중량 %, 또는 약 0 . 1 내지 15 중량 %로 포함될 수 있다. 상기 범위로 중합체가 포함됨으로써 유기막의 두께， 표면 거칠기 및 평탄화 정도를 조절할 수 있다.  The polymer is about 0.1% to 50% by weight, based on the total content of the organic film composition, about 0. 1 to 30 weight percent, or about 0. It may be included in 1 to 15% by weight. By including the polymer in the above range it is possible to control the thickness, surface roughness and degree of planarization of the organic film.
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， 알킬벤젠설폰산 염， 알킬피리디늄 염， 폴리에틸렌글리콜， 제 4 암모늄 염 등을 사용할 수 있으나 이에 한정되는 것은 아니다.  The surfactant may be, for example, fluoroalkyl-based compounds, alkylbenzenesulfonic acid salts, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts and the like, but is not limited thereto.
상기 가교제는 예컨대 멜라민계， 치환요소계， 또는 이들 폴리머계 등을 들 수 있다. 바람직하게는， 적어도 2개의 가교 형성 치환기를 갖는 가교제로, 예를 들면， 메록시메틸화 글리코루릴， 부특시메틸화 글리코루릴， 메톡시메틸화 멜라민， 부록시메틸화 멜라민， 메톡시메틸화 벤조구아나민， 부톡시메틸화 벤조구아나민， 메록시메틸화요소， 부톡시메틸화요소， 메록시메틸화 티오요소， 또는 부특시메틸화 티오요소 등의 화합물을 사용할 수 있다.  The crosslinking agent may be, for example, melamine type, substituted element type, or these polymer type. Preferably, a crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoryl, subspecific methylated glycoryl, methoxymethylated melamine, appendoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or subspecific methylated thiourea can be used.
또한， 상기 가교제로는 내열성이 높은 가교제를 사용할 수 있다. 내열성이 높은 가교제로는 분자 내에 방향족 고리 (예를 들면 벤젠 고리， 나프탈렌 고리)을 가지는 가교 형성 치환기를 함유하는 화합물을 사용할 수 있다.  In addition, a crosslinking agent having high heat resistance may be used as the crosslinking agent. As a crosslinking agent with high heat resistance, the compound containing the bridge | crosslinking formation substituent which has an aromatic ring (for example, a benzene ring, a naphthalene ring) in a molecule | numerator can be used.
상기 열산발생제는 예컨대 Ρ-를루엔술폰산, 트리플루오로메탄술폰산, 피리디늄 Ρ—를루엔술폰산， 살리실산, 술포살리실산， 구연산， 안식향산， 하이드록시안식향산， 나프탈렌카르본산 등의 산성 화합물 또는 /및 2，4，4，6- 테트라브로모시클로헥사디에논， 벤조인토실레이트， 2-니트로벤질토실레이트， 그 밖에 유기술폰산알킬에스테르 등을 사용할 수 있으나 이에 한정되는 것은 아니다. The thermal acid generator is, for example, an acidic compound such as Ρ-luluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium Ρ—lurusulsulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and / or 2 ， 4，4，6- Tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other alkyl sulfonic acid alkyl esters may be used, but is not limited thereto.
상기 첨가제는 상기 유기막 조성물 100 중량부에 대하여 약 0.001 내지 40중량부로 포함될 수 있다. 상기 범위로 포함함으로써 유기막 조성물의 광학적 특성을 변경시키지 않으면서 용해도를 향상시킬 수 있다. 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, 평탄화 막， 회생막， 층진제， 등 전자 디바이스에 사용되는 유기 박막을 포함할 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 in the said range, solubility can be improved without changing the optical characteristic of an organic film composition. According to another embodiment, an organic film prepared using the organic film composition described above is provided. The organic layer may be in the form of the organic layer composition, for example, coated on a substrate and then cured through a heat treatment process, and may include, for example, an organic thin film used in an electronic device such as a hard mask layer, a planarization layer, a regenerative layer, a layer release agent, and the like. can do.
이하 상술한 유기막 조성물을 사용하여 패턴을 형성하는 방법에 대하여 도 1를 참고하여 설명한다.  Hereinafter, a method of forming a pattern using the organic film composition described above will be described with reference to FIG. 1.
도 1은 일 구현예에 따른 패턴 형성 방법을 설명하는 흐름도이다. 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 충 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.  1 is a flowchart illustrating a pattern forming method according to an embodiment. According to one or more exemplary embodiments, a pattern forming method includes forming a material layer on a substrate (S1), applying an organic film composition including the polymer and a solvent on the material layer (S2), and heat treating the organic film composition. Forming a hard mask layer (S3), 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), and exposing the photoresist layer. And developing to form a photoresist pattern (S6), selectively removing the silicon-containing thin film layer and the hardmask layer using the photoresist pattern and exposing a portion of the material layer (S7), and Etching (S8) the exposed portion of the material layer.
상기 기판은 예컨대 실리콘웨이퍼， 유리 기판 또는 고분자 기판일 수 있다.  The substrate may be, for example, a silicon wafer, a glass substrate or a polymer substrate.
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 있다. 상기 유기막 조성물은 전술한 바와 같으며, 용액 형태로 제조되어 스핀-온 코팅방법으로 도포될 수 있다. 이 때 상기 유기막 조성물의 도포 두께는 특별히 한정되지 않으나， 예컨대 약 50 내지 ΙΟ ,ΟΟΟΑ 두께로 도포될 수 있다. The material layer is a material to be finally patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer can be formed, for example, by chemical vapor deposition. The organic film composition is as described above, it may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the organic film composition is not particularly limited, and for example, may be applied to a thickness of about 50 to ΙΟ, ΟΟΟΑΑ.
상기 유기막 조성물을 열처리하는 단계는 예컨대 약 100 내지 The heat treatment of the organic film composition is, for example, about 100 to about 100
700oC에서 약 10초 내지 1시간 동안 수행할 수 있다. At 700 ° C. for about 10 seconds to 1 hour.
상기 실리콘 함유 박막층은 예컨대 SiCN, SiOC, SiON, SiOCN, SiC, SiO및 /또는 SiN등의 물질로 형성할 수 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 층 (bottom ant i-ref lect ive coat ing, BARC)을 더 형성할 수도 있다.  In addition, a bottom anti-reflective layer (BARC) may be further formed on the silicon-containing thin film layer before the forming of the photoresist layer.
상기 포토레지스트 층을 노광하는 단계는 예컨대 ArF, KrF 또는 EUV 등을 사용하여 수행할 수 있다. 또한 노광 후 약 100 내지 700oC에서 열처리 공정을 수행할 수 있다. Exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. In addition, the heat treatment may be performed at about 100 to 700 ° C. after the exposure.
상기 재료 층의 노출된 부분을 식각하는 단계는 식각 가스를 사용한 건식 식각으로 수행할 수 있으며， 식각 가스는 예컨대 CHF3ᅳ CF4 ) Cl2 ) BC13 및 이들의 흔합 가스를 사용할 수 있다. Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may use, for example, CHF 3 ) CF 4) Cl 2) BC1 3 and combinations thereof.
상기 식각된 재료 층은 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. 이하 실시예를 통하여 상술한 본 발명의 구현예를 보다 상세하게 설명한다. 다만 하기의 실시예는 단지 설명의 목적을 위한 것이며 본 발명의 범위를 제한하는 것은 아니다.  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 insulation pattern, or the like, and may be applied to, for example, various patterns in a semiconductor integrated circuit device. Through the following examples will be described in more detail the embodiment of the present invention. However, the following examples are merely for illustrative purposes and do not limit the scope of the present invention.
【발명의 실시를 위한 형태】  [Form for implementation of invention]
합성예  Synthesis Example
합성예 1  Synthesis Example 1
기계교반기와 넁각관을 구비한 500ml 2구 플라스크에 1-나프를 (1- naphthol ) 61.5g (0.43몰) . 인돌 ( Indole) 50.0g (0.43몰)， 1- 나프타알데히드 (1-napht aldehyde) 133g (0.85몰)， 및 메탄설포닐산 (Methanesulfonic acid) 41. Og (0.43몰) 을 285.9g의 1,4-다이옥산 (1,4- Dioxane)에 담고 잘 저어준 후에 온도를 100°C로 올려 24시간 동안 교반하였다. 반웅 종료 후 내부 은도를 60~70°C로 낮춘 다음 테트라하이드로퓨란 300g을 넣어 화합물이 굳지 않게 만들고 난 후에 7%의 소듐바이카보네이트 수용액 (Sodium bicarbonate)으로 화합물의 pH를 5~6까지 되게 만든다. 그리고 나서 에틸아세테이트 1000ml를 부어 계속 교반한 후에 분별깔때기를 이용하여, 유기층만 추출해 낸다. 다시 물을 500ml를 분별깔때기에 넣고 흔들어서 남아있는 산과 소듐염을 제거하는 과정을 3번 이상 반복하고 난 후에 유기층을 최종적으로 추출해 낸다. 이어서， 유기용액을 증발기로 농축하였고， 얻어진 화합물에 테트라하이드로퓨란 1L을 첨가하여 용액을 얻었다. 61.5 g (0.43 mol) 1-naphthol (1-naphthol) in a 500 ml two-necked flask equipped with a mechanical stirrer and a square tube. 50.0 g (0.43 mole) Indole, 133 g (0.85 mole) 1-napht aldehyde, and methanesulfonyl acid (Methanesulfonic acid) 41. Og (0.43 mol) was added to 285.9g of 1,4-dioxane (1,4-Dioxane) and stirred well, the temperature was raised to 100 ° C and stirred for 24 hours. After completion of the reaction, the internal silver is lowered to 60-70 ° C, and then 300 g of tetrahydrofuran is added to make the compound not hardened. Then, the pH of the compound is increased to 5-6 with 7% aqueous sodium bicarbonate solution. Then, 1000 ml of ethyl acetate was poured and stirring continued, and then the organic layer was extracted using a separatory funnel. Then, 500 ml of water is added to a separatory funnel, shaken to remove the remaining acid and sodium salt three or more times, and the organic layer is finally extracted. Subsequently, the organic solution was concentrated by an evaporator, and 1 L of tetrahydrofuran was added to the obtained compound to obtain a solution.
상기 용액을 교반되고 있는 핵산 5L가 들어있는 비커에 천천히 적가하여 침전을 형성하여 화학식 la에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  The solution was slowly added dropwise to a beaker containing 5 L of the nucleic acid being stirred to form a precipitate to obtain a polymer including the structural units represented by the formula la.
겔 투과 크로마토그래피 (Gel permeation chromatography: GPC)를 사용하여 얻어진 중합체의 중량평균분자량 (Mw) 및 다분산도 (Polydispersity, PD)를 측정한 결과， 중량평균분자량 (Mw)은 1,890이고， 다분산도 (Polydispersity, PD)는 1.35 였다.  The weight average molecular weight (Mw) and the polydispersity (PD) of the polymer obtained by gel permeation chromatography (GPC) were measured, and the weight average molecular weight (Mw) was 1,890. (Polydispersity, PD) was 1.35.
la]  la]
Figure imgf000020_0001
Figure imgf000020_0001
합성예 1에서 인돌 대신 1H-벤조인돌 (ΙΗ-Benzo indole)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 2a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Except for using 1H-benzoindole (ΙΗ-Benzo indole) instead of indole in Synthesis Example 1 A polymer including the structural units represented by the formula (2a) was obtained using the same method.
얻어진 중합체의 중량평균분자량 (Mw)은 3, 100이고， 다분산도 (Polydispersity, PD)는 1.43 였다. 2a] The weight average molecular weight (Mw) of the obtained polymer was 3,100, and polydispersity (PD) was 1.43. 2a]
Figure imgf000021_0001
Figure imgf000021_0001
합성예 3  Synthesis Example 3
합성예 1에서 인돌 대신 1^111'ᅳ3，3'ᅳ바이인돌 (1Η,1Η'-3,3'- bi indole)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 3a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Except that 1 ^ 111 'ᅳ 3,3' ᅳ biindole (1Η, 1Η'-3,3'-bi indole) was used instead of indole in Synthesis Example 1, the structural units represented by Chemical Formula 3a were used by the same method. A polymer was obtained.
얻어진 중합체의 중량평균분자량 (Mw)은 2 ,140이고， 다분산도 (Polydispersity, PD)는 1.32 였다.  The weight average molecular weight (Mw) of the obtained polymer was 2,140, and polydispersity (PD) was 1.32.
3a]  3a]
Figure imgf000021_0002
Figure imgf000021_0002
합성예 4 Synthesis Example 4
합성예 1에서 인돌 대신 1H-다이벤조 [e,g]인돌 (1H- dibenzo[e,g] indole)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 4a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Except for using 1H-dibenzo [e, g] indole (1H- dibenzo [e, g] indole) instead of indole in Synthesis Example 1 using the same method to obtain a polymer containing the structural units represented by the formula (4a).
얻어진 중합체의 중량평균분자량 (Mw)은 2 ,470이고, 다분산도 (Polydispersity,PD)는 1.29 였다. The weight average molecular weight (Mw) of the obtained polymer was 2,470, and polydispersity (PD) was 1.29.
[화학식 4a] [Formula 4a]
Figure imgf000022_0001
Figure imgf000022_0001
합성예 5  Synthesis Example 5
합성예 1에서 1—나프를 대신 페난트렌 -9-올 (Phenanthrenᅳ 9-ol )을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 5a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  A polymer comprising the structural units shown in Chemical Formula 5a was obtained using the same method as in Synthesis Example 1, except that 1-nap was used instead of phenanthren-9-ol (Phenanthren® 9-ol).
얻어진 중합체의 중량평균분자량 (Mw)은 1，760이고, 다분산도 (Polydi spersi ty, PD)는 1.43 였다.  The weight average molecular weight (Mw) of the obtained polymer was 1,760, and polydispersity (Polydi spersi ty, PD) was 1.43.
Figure imgf000022_0002
Figure imgf000022_0002
합성예 6  Synthesis Example 6
합성예 5에서 1-나프타알데히드 대신 9-페난트렌 카바알데히드 (9- phenanthrene carbaldehyde)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 6a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Except for using 9-phenanthrene carbaldehyde (9-phenanthrene carbaldehyde) instead of 1- naphthaaldehyde in Synthesis Example 5 using the same method to obtain a polymer comprising the structural units shown in the formula (6a).
얻어진 중합체의 중량평균분자량 (Mw)은 2，410이고， 다분산도 (Polydi spersi ty, PD)는 1.55였다.  The weight average molecular weight (Mw) of the obtained polymer was 2,410, and polydispersity (Polydi spersi ty, PD) was 1.55.
Figure imgf000022_0003
합성예 7
Figure imgf000022_0003
Synthesis Example 7
합성예 6에서 페난트렌 -9-을 대신에 1-하이드록시파이렌 ( 1— hydroxypyrene)을 사용하고， 9-페난트렌 카바랑데히드 대신 파이렌 -1- 카바알데히드 (Pyrene-1-carbaldehyde)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 7a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  In Synthesis Example 1, 1-hydroxypyrene was used instead of phenanthrene-9-, and pyrene-1-carbaldehyde was used instead of 9-phenanthrene carbarandaldehyde. Except for the use of the same method to obtain a polymer comprising the structural units represented by the formula (7a).
얻어진 중합체의 중량평균분자량 (Mw)은 1 , 570이고， 다분산도 (Polydi spersi ty, PD)는 1.26였다.  The weight average molecular weight (Mw) of the obtained polymer was 1,570, and polydispersity (Polydi spersi ty, PD) was 1.26.
Figure imgf000023_0001
Figure imgf000023_0001
합성예 7에서 인돌 대신 1H-벤조인돌 (lH-Benzoindole)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 8a에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Except for using 1H-benzoindole (lH-Benzoindole) instead of indole in Synthesis Example 7 to obtain a polymer comprising the structural units represented by the formula (8a).
얻어진 중합체의 중량평균분자량 (Mw)은 1 , 940이고， 다분산도 (Polydi spersi ty, PD)는 1.35였다.  The weight average molecular weight (Mw) of the obtained polymer was 1,940, and polydispersity (Polydi spersi ty, PD) was 1.35.
Figure imgf000023_0002
Figure imgf000023_0002
합성예 9  Synthesis Example 9
합성예 7에서 인돌 대신 1-페닐 -1H-인돌 (1-Phenyl-1H- indole)을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 구조단위들을 포함하는 중합체를 얻었다. In Synthesis Example 1, 1-phenyl-1H-indole was substituted for indole. The same method was used except that the polymer including the structural structural units was obtained.
얻어진 중합체의 중량평균분자량 (Mw)은  The weight average molecular weight (Mw) of the obtained polymer
다분산도 (Polydi spersi ty, PD)는 1.31였다. Polydispersity (PD) was 1.31.
Figure imgf000024_0001
Figure imgf000024_0001
합성예 10  Synthesis Example 10
기계교반기를 구비한 500ml 2구 플라스크에 합성예 1에서 얻은 중합체 27.0g과 디메틸포름아마이드 (Dimethyl formamide) 200g를 넣어 교반한다. 중합체가 다 녹는 것을 확인 한 후에， 플라스크를 얼음으로 채워진 넁각 수조에 넣고 교반한다. 그리고 나서 소듐하이드라이드 (Sodium hydr ide) 6g을 천천히 플라스크에 적가하고 교반한다. 교반 30분 후에 프로파질브로마이드 (Propargyr bromide) 17.8g을 천천히 투입하고 8시간 동안 교반하였다. 반웅 종료 후 플라스크 내부에 에탄올 50ml을 천천히 투입하고， 10분 경과 후 2L 비커에 담겨 교반되고 있는 물 1.5L에 반웅액을 천천히 투입한다. 완전히 투입한 후에 2시간 동안 교반을 진행한다. 침전이 형성된 고체를 여과하여 수분을 제거한 후에 물 500ml와 에탄올 200ml가 흔합된 용액으로 씻어주는 과정을 3번 이상 반복하고 고체를 건조하여 화학식 10a에 나타낸 구조단위를 포함하는 중합체를 얻었다.  Into a 500 ml two-necked flask equipped with a mechanical stirrer, 27.0 g of the polymer obtained in Synthesis Example 1 and 200 g of dimethyl formamide were added and stirred. After confirming that the polymer has melted, the flask is placed in an ice bath filled with ice and stirred. Then 6 g of sodium hydride is slowly added dropwise to the flask and stirred. After 30 minutes of stirring, 17.8 g of propargyl bromide was slowly added thereto and stirred for 8 hours. After completion of the reaction, 50 ml of ethanol was slowly added into the flask, and after 10 minutes, the reaction solution was slowly added to 1.5 L of stirred water in a 2 L beaker. After complete addition, stirring is performed for 2 hours. The precipitate was formed by filtration to remove moisture, and then washed with a solution containing 500 ml of water and 200 ml of ethanol three or more times. The solid was dried to obtain a polymer including the structural unit represented by Formula 10a.
얻어진 중합체의 증량평균분자량 (Mw)은 1 , 920이고， 다분산도 (Polydi spersi ty, PD)는 1.34 였다.  The increase average molecular weight (Mw) of the obtained polymer was 1,920, and polydispersity (Polydi spersi ty, PD) was 1.34.
[화학식 10a] [Formula 10a]
Figure imgf000025_0001
비교합성예 1
Figure imgf000025_0001
Comparative Synthesis Example 1
500ml 플라스크에 1-하이드록시안트라센 20g (0. 103 몰)， 및 파라포름 알데히드 3.08g (0. 103 몰)을 순차적으로 넣고 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) 42 g에 녹인 후， 파라 를루엔설포닉 액시드 0.4 g (0.002 몰)을 투입한 후， 90 내지 120oC에서 5 내지 10 시간 정도 교반하였다. 1시간 간격으로 상기 중합반응물로부터 시료를 취하여， 그 시료의 중량평균 분자량이 3 , 000 내지 4， 200 때 반웅을 완료하여 화학식 A에 나타낸 구조단위를 포함하는 중합체를 얻었다. Into a 500 ml flask, 20 g (0.103 mol) of 1-hydroxyanthracene, and 3.08 g (0.103 mol) of paraformaldehyde were sequentially added and dissolved in 42 g of propylene glycol monomethyl ether acetate (PGMEA), followed by paraluene 0.4 g (0.002 mol) of sulfonic acid was added thereto, followed by stirring at 90 to 120 ° C. for about 5 to 10 hours. Samples were taken from the polymerization reaction at 1 hour intervals, and reaction was completed when the weight average molecular weight of the sample was 3,000 to 4,200 to obtain a polymer including the structural unit represented by the formula (A).
얻어진 중합체의 중량평균분자량 (Mw)은 3， 200이고， 다분산도 (Polydi spers i ty, PD)는 1.85였다.  The weight average molecular weight (Mw) of the obtained polymer was 3,200, and polydispersity (Polydi spers i ty, PD) was 1.85.
Figure imgf000025_0002
Figure imgf000025_0002
비교합성예 2  Comparative Synthesis Example 2
500ml 플라스크에 Indole 33g (0.23몰)， 1-나프탈데하이드 ( 1- Indole 33g (0.23 mol), 1-naphthalaldehyde (1-
■ Naphthaldehyde) 35.9g (0.23 몰)을 순차적으로 넣고 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) 200 g에 녹인 후， 파라 를루엔설포닉 액시드 1 g (0.005 몰)을 투입한 후， 90 내지 120oC에서 8 시간 정도 교반하였다. 1시간 간격으로 상기 중합반웅물로부터 시료를 취하여， 그 시료의 중량평균 분자량이 3 , 000 내지 4, 000 때 반웅을 완료하여 화학식 B에 나타낸 구조단위를 포함하는 중합체를 얻었다. 얻어진 중합체의 중량평균분자량 (Mw)은 1， 520이고， 다분산도 (Polydispersity, PD)는 1.72였다. ■ Naphthaldehyde) into a 35.9g (0.23 mol) was added sequentially a propylene glycol monomethyl ether acetate (PGMEA) was dissolved in 200 g, the para-toluene sulphonic Acid 1 g (0.005 mol) of 90 to 120 o Stir at C for 8 hours. Samples were taken from the polymerization reaction product at 1 hour intervals, and reaction was completed when the weight average molecular weight of the sample was 3,000 to 4, 000 to obtain a polymer including the structural unit represented by the formula (B). The weight average molecular weight (Mw) of the obtained polymer was 1,520, and polydispersity (PD) was 1.72.
[화학식 B] "  [Formula B] "
Figure imgf000026_0001
비교합성예 3
Figure imgf000026_0001
Comparative Synthesis Example 3
합성예 1에서 인돌 대신 카바졸을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 C에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Except for using carbazole instead of indole in Synthesis Example 1 using the same method to obtain a polymer comprising the structural units represented by the formula (C).
얻어진 중합체의 중량평균분자량 (Mw)은 2,680이고， 다분산도 (Polydispersity, PD)는 1.56였다.  The weight average molecular weight (Mw) of the obtained polymer was 2,680, and polydispersity (PD) was 1.56.
C]  C]
Figure imgf000026_0002
Figure imgf000026_0002
비교합성예 4  Comparative Synthesis Example 4
합성예 4에서 인돌 대신 1，3-다이하이드로인도로 [2,3-b]카바졸 (1,3- dihydroindolo[2,3-b]carbazole을 사용한 것을 제외하고 같은 방법을 사용하여 화학식 D에 나타낸 구조단위들을 포함하는 중합체를 얻었다.  Synthesis Example 4 was synthesized using the same method as in Synthesis Example 4, except that [2,3-b] carbazole (1,3-dihydroindolo [2,3-b] carbazole was used as 1,3-dihydroindo instead of indole. A polymer was obtained comprising the structural units indicated.
얻어진 중합체의 중량평균분자량 (Mw)은 4， 620이고， 다분산도 (Polydispersity, PD)는 1.73였다.  The weight average molecular weight (Mw) of the obtained polymer was 4,620, and polydispersity (PD) was 1.73.
[화학식 D] [Formula D]
Figure imgf000027_0001
하드마스크조성물의 제조
Figure imgf000027_0001
Preparation of Hard Mask Compositions
실시예 1  Example 1
합성예 1에서 얻은 중합체를 프로필렌글리콜모노메틸에테르아세테이트 (propylene glycol monomethyl ether acetate , PGMEA)와 사이클로핵사논 (cyclohexanone) (7 : 3(v/v) )의 흔합 용매에 녹인 후 0. 1 의 테플론 필터로 여과하여 하드마스크 조성물을 제조하였다. 목적하고자 하는 두께에 따라 상기 중합체의 중량은 상기 하드마스크 조성물의 총중량에 대하여 5.0 중량 ¾> 내지 20.0 중량 %로 조절하였다.  The polymer obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), followed by 0.1 Teflon. Filtration with a filter produced a hardmask composition. According to the desired thickness, the weight of the polymer was adjusted to 5.0 to 30.0 wt% based on the total weight of the hard mask composition.
실시예 2  Example 2
합성예 1에서 얻은 중합체 대신 합성예 2에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 초성물을 제조하였다.  A hardmask supernatant was prepared in the same manner as in Example 1, except that the compound 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 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 3 was used instead of the compound obtained in Synthesis Example 1.
실시예 4  Example 4
합성예 1에서 얻은 중합체 대신 합성예 4에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1.
실시예 5  Example 5
합성예 1에서 얻은 중합체 대신 합성예 5에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다. ' The compound obtained in Synthesis Example 5 was used instead of the polymer obtained in Synthesis Example 1. Except that a hard mask composition was prepared in the same manner as in Example 1. '
실시예 6  Example 6
합성예 1에서 얻은 중합체 대신 합성예 6에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 6 was used instead of the polymer obtained in Synthesis Example 1.
실시예 7  Example 7
합성예 1에서 얻은 중합체 대신 합성예 7에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 7 was used instead of the polymer obtained in Synthesis Example 1.
실시예 8  Example 8
합성예 1에서 얻은 중합체 대신 합성예 8에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 8 was used instead of the polymer obtained in Synthesis Example 1.
실시예 9  Example 9
합성예 1에서 얻은 중합체 대신 합성예 9에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 9 was used instead of the polymer obtained in Synthesis Example 1.
실시예 10  Example 10
합성예 1에서 얻은 중합체 대신 합성예 10에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 10 was used instead of the polymer obtained in Synthesis Example 1.
비교예 1  Comparative Example 1
합성예 1에서 얻은 중합체 대신 비교합성예 1에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound 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 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다. 비교예 3 A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1. Comparative Example 3
합성예 1에서 얻은 중합체 대신 비교합성예 3에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다.  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.
비교예 4  Comparative Example 4
합성예 1에서 얻은 중합체 대신 비교합성예 4에서 얻은 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 하드마스크 조성물을 제조하였다. ¾ >  A hardmask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1. ¾>
평가 1 : 내식각성  Evaluation 1: corrosion resistance
실리콘 웨이퍼 위에 실시예 1 내지 10과 비교예 1 내지 4에 따른 하드마스크 조성물을 4, 000A 두께로 스핀—온 코팅한 후 핫플레이트 위에서 240°C로 1분간 열처리하여 박막을 형성하였다. The hard mask compositions according to Examples 1 to 10 and Comparative Examples 1 to 4 were spin-on coated on the silicon wafer to a thickness of 4,000 A, and then heat-treated at 240 ° C. on a hot plate for 1 minute to form a thin film.
이어서 상기 박막의 두께를 측정하였다. 이어서 상기 박막에 Subsequently, the thickness of the thin film was measured. Then on the thin film
CHF3/CF4흔합 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 ,CHF 3 / CF 4 heunhap gas and N 2/0 2 heunhap then using dry etching gas, each for 100 seconds and 60 seconds to re-measure the thickness of thin films. From the thickness and etching time of the thin film before and after dry etching, the etching rate (bulk etch rate,
BER)을 계산하였다. BER) was calculated.
[계산식 1]  [Calculation 1]
(초기 박막두께 - 식각 후 박막 두께) /식각 시간 ( A/s)  (Initial thin film thickness-thin film thickness after etching) / Etching time (A / s)
그 결과는 표 1과 같다.  The results are shown in Table 1.
[표 1]  TABLE 1
Figure imgf000029_0001
실시예 4 24.6 24.9 실시예 5 26.2 24.8 실시예 6 25.4 23. 1 실시예 7 22.9 22.7 실시예 8 22.5 22.4 실시예 9 22.3 21.9 실시예 10 26.9 25.0 비교예 1 29.4 28.4 비교예 2 28.7 29.5 비교예 3 30.2 27.7 비교예 4 29.4 27.5 상기 열처리 온도 및 시간을 400 °C 및 2분으로 각각 변경하여 식각율을 다시 계산하였다. 그 결과는 표 2와 같다.
Figure imgf000029_0001
Example 4 24.6 24.9 Example 5 26.2 24.8 Example 6 25.4 23. 1 Example 7 22.9 22.7 Example 8 22.5 22.4 Example 9 22.3 21.9 Example 10 26.9 25.0 Comparative Example 1 29.4 28.4 Comparative Example 2 28.7 29.5 Comparative Example 3 30.2 27.7 Comparative Example 4 29.4 27.5 The etch rate was recalculated by changing the heat treatment temperature and time to 400 ° C. and 2 minutes, respectively. The results are shown in Table 2.
[표 2] TABLE 2
Figure imgf000030_0001
실시예 9 23.3 21.5 실시예 10 28. 1 23.9 비교예 1 31. 1 27.0 비교예 2 30.2 26.6 비교예 3 31.4 26.4 비교예 4 30.7 25.5 표 1 및 2를 참고하면， 실시예 1 내지 10에 따른 하드마스크 조성물로부터 형성된 박막은 비교예 1 내지 4에 따른 하드마스크 조성물로부터 형성된 박막과 비교하여 식각 가스에 대한 충분한 내식각성이 있어서 벌크 에치 특성이 향상됨을 확인할 수 있다. 평가 2: 막밀도
Figure imgf000030_0001
Example 9 23.3 21.5 Example 10 28. 1 23.9 Comparative Example 1 31. 1 27.0 Comparative Example 2 30.2 26.6 Comparative Example 3 31.4 26.4 Comparative Example 4 30.7 25.5 Referring to Tables 1 and 2, the hardware according to Examples 1 to 10 Compared with the thin film formed from the hard mask compositions according to Comparative Examples 1 to 4, the thin film formed from the mask composition may have sufficient etching resistance against the etching gas, thereby improving bulk etch characteristics. Evaluation 2: film density
실리콘 웨이퍼 위에 실시예 1 내지 10와 비교예 1 내지 4에 따른 하드마스크 조성물을 스핀-온 코팅하고 핫 플레이트 위에서 240°C에서 1분간 열처리하여 두께 1 ,000 A의 박막을 형성하였다. A hard mask composition according to Examples 1 to 10 and Comparative Examples 1 to 4 was spin-on coated on a silicon wafer and heat-treated at 240 ° C. for 1 minute on a hot plate to form a thin film having a thickness of 1,000 A. FIG.
상기 박막의 막 밀도를 PANalyt i cal社의 X-선 회절분석 (X-ray di f fract ion) 장비를 이용하여 측정하였다.  The film density of the thin film was measured using an X-ray diffraction analysis (X-ray diffraction ion) equipment of PANalyt i cal.
그 결과는 표 3과 같다.  The results are shown in Table 3.
[표 3]  TABLE 3
Figure imgf000031_0001
실시예 8 1.38
Figure imgf000031_0001
Example 8 1.38
실시예 9 1.39  Example 9 1.39
실시예 10 1.36  Example 10 1.36
비교예 1 1. 19  Comparative Example 1 1. 19
비교예 2 1.20  Comparative Example 2 1.20
비교예 3 1.25  Comparative Example 3 1.25
비교예 4 1.24 표 3을 참고하면， 실시예 1 내지 10에 따른 하드마스크 조성물로부터 형성된 박막이 비교예 1 내지 4에 따른 박막과 비교하여 높은 수준의 막 밀도를 가짐을 알 수 있다.  Comparative Example 4 1.24 Referring to Table 3, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 10 has a high level of film density compared with the thin films according to Comparative Examples 1 to 4.
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.  Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims

【청구의 범위】 [Range of request]
【청구항 1】  [Claim 1]
하기 화학식 1로 표현되는 구조단위， 그리고  The structural unit represented by the formula (1), and
하기 화학식 2로 표현되는 구조단위  Structural unit represented by the formula (2)
를 포함하는 중합체：  Polymer containing:
[화학
Figure imgf000033_0001
[chemistry
Figure imgf000033_0001
[화학식 2]
Figure imgf000033_0002
[Formula 2]
Figure imgf000033_0002
상기 화학식 1 및 2에서，  In Chemical Formulas 1 and 2,
A1은 하기 화학식 X로 표현되는 모이어티이고， A 1 is a moiety represented by the following formula (X),
A2는 치환 또는 비치환된 C6 내지 C30의 방향족 고리로서 상기 A1과 다른 A 2 is a substituted or unsubstituted C 6 to C 30 aromatic ring which is different from A 1.
구조를 가지고， B1 및 B2는 각각 독립적으로 치환 또는 비치환된 C6 내지 C30의 방향족 고리이고， Having a structure, B 1 and B 2 are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
*은 연결지점이다:  * Is the connection point:
[화학식 X] [Formula X]
Figure imgf000033_0003
상기 화학식 X에서，
Figure imgf000033_0003
In Chemical Formula X,
Ar은 치환 또는 비치환된 사각 고리 , 치환 또는 비치환된 오각 고리， 치환 또는 비치환된 육각 고리, 또는 이들의 융합 고리 ( fused r ing)이고， Ar is a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof,
Ra는 수소， 히드록시기， 할로겐 기， 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 조합이고, R a is hydrogen, hydroxy group, halogen group, substituted or unsubstituted C1 to C30 Alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
Za는 각각 독립적으로 히드록시기， 할로겐 기, 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 조합이고， Z a is each independently 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 A C30 alkynyl group 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 a combination thereof,
m은 0또는 1이다. m is 0 or 1;
[청구항 2】  [Claim 2]
제 1항에서,  In claim 1,
상기 화학식 1 및 2에서 B1 및 B2는 각각 하기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나인 중합체: In Formulas 1 and 2, B 1 and B 2 are each any one of substituted or unsubstituted moieties listed in Group 1 below:
[그룹 1] [Group 1]
Figure imgf000035_0001
Figure imgf000035_0001
【청구항 3]  [Claim 3]
제 1항에서,  In claim 1,
상기 화학식 1에서 A1은 하기 그룹 2에 나열된 모이어티들 중 어느 하나인 중합체： In Formula 1, A 1 is any one of the moieties listed in Group 2 below:
[그룹 2] [Group 2]
Figure imgf000036_0001
상기 그룹 2에서，
Figure imgf000036_0001
In group 2 above,
R1 및 R2는 각각 독립적으로 수소， 히드록시기， 할로겐 기, 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 조합이다: R 1 and R 2 are each independently hydrogen, hydroxy group, halogen group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or Unsubstituted C2 to A 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 a combination thereof:
단, 상기 그룹 2에서， 각 모이어티 내의 수소는 각각 독립적으로 히드록시기， 할로겐 기， 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. However, in Group 2, hydrogen in each moiety is each independently 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 groups, substituted or unsubstituted C2 to C30 alkynyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, or these It is substituted by a combination of or unsubstituted.
[청구항 4】 [Claim 4]
거 U항에서,  In U,
상기 화학식 2에서 A2는 하기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나인 중합체: In Formula 2, A 2 is any one of the substituted or unsubstituted moieties listed in Group 1 below:
[그룹 1] [Group 1]
Figure imgf000038_0001
Figure imgf000038_0001
【청구항 5]  [Claim 5]
제 4항에서，  In paragraph 4,
상기 A2는 적어도 하나의 히드록시기에 의해 치환된 것인 중합체. Wherein A 2 is substituted by at least one hydroxy group.
【청구항 6】  [Claim 6]
제 1항에서,  In claim 1,
상기 화학식 1 및 2에서 B1 및 B2는 치환또는 비치환된 C6 내지 C30 방향족 고리로서 서로 동일한 구조를 가지는 중합체 . In Formulas 1 and 2, B 1 and B 2 are substituted or unsubstituted C6 to C30 aromatic rings, polymers having the same structure with each other.
【청구항 7】  [Claim 7]
제 1항에서，  In paragraph 1,
중량평균분자량이 1,000 내지 200,000인 중합체. A polymer having a weight average molecular weight of 1,000 to 200,000.
【청구항 8】  [Claim 8]
하기 화학식 1로 표현되는 구조단위， 그리고 하기 화학식 2로 표현되는 구조단위를 포함하는 중합체， 그리고 용매 A structural unit represented by the formula (1), And a polymer comprising a structural unit represented by the formula (2), And menstruum
를 포함하는 유기막 조성물: Organic film composition comprising:
[화학식 1]  [Formula 1]
B1 B 1
[화학식 2]
Figure imgf000039_0001
[Formula 2]
Figure imgf000039_0001
상기 화학식 1 및 2에서， In Chemical Formulas 1 and 2,
A1은 하기 화학식 X로 표현되는 모이어티이고， A 1 is a moiety represented by the following formula (X),
A2는 치환또는 비치환된 C6 내지 C30의 방향족 고리로서 상기 A1과 다른 구조를 가지고， A 2 is a substituted or unsubstituted C 6 to C 30 aromatic ring having a structure different from that of A 1 ,
B1 및 B2는 각각 독립적으로 치환 또는 비치환된 C6 내지 C30의 방향족 고리이고, B 1 and B 2 are each independently a substituted or unsubstituted C6 to C30 aromatic ring,
*은 연결지점이다:  * Is the connection point:
[화학식 X]  [Formula X]
Figure imgf000039_0002
상기 화학식 X에서，,
Figure imgf000039_0002
In Chemical Formula X ,
Ar은 치환 또는 비치환된 사각 고리 , 치환 또는 비치환된 오각 고리， 치환 또는 비치환된 육각 고리， 또는 이들의 융합 고리 ( fused r ing)이고，  Ar is a substituted or unsubstituted square ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof,
Ra는 수소， 히드록시기， 할로겐 기, 치환 또는 비치환된 C1 내지 C30 알콕시기， 치환또는 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 조합이고， R a is hydrogen, 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 Alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 Heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
Za는 각각 독립적으로 히드록시기， 할로겐 기， 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 조합이고， Z a is each independently 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 alkynyl group substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
m은 0 또는 1이다. m is 0 or 1;
【청구항ᅳ 9】  [Claim port 9]
거 18항에서，  From clause 18
상기 화학식 1에서 A1은 하기 그룹 2에 나열된 모이어티들 중 어느 하나인 유기막조성물: In the general formula 1 A 1 is an organic film composition of any one of the moieties listed in Group 2:
[그룹 2] [Group 2]
Figure imgf000041_0001
상기 그룹 2에서，
Figure imgf000041_0001
In group 2 above,
R1 및 R2는 각각 독립적으로 수소， 히드록시기， 할로겐 기， 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 조합이다: R 1 and R 2 are each independently hydrogen, 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 A 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 a combination thereof:
단， 상기 그룹 2에서, 각 모이어티 내의 수소는 각각 독립적으로 히드록시기 할로겐 기， 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. However, in Group 2, hydrogen in each moiety is each independently a hydroxy group 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 alke 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 a It is substituted by a combination or unsubstituted.
【청구항 10】  [Claim 10]
제 8항에서， - 상기 화학식 2에서 A2는 하기 그룹 1에 나열된 치환 또는 비치환된 모이어티들 중 어느 하나인 유기막 조성물: The organic film composition of claim 8, wherein A 2 in Chemical Formula 2 is any one of substituted or unsubstituted moieties listed in Group 1 below:
[그룹 1] [Group 1]
Figure imgf000043_0001
Figure imgf000043_0001
Figure imgf000043_0002
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000043_0003
【청구항 11】  [Claim 11]
제 10항에서，  In paragraph 10,
상기 A2는 적어도 하나의 히드록시기에 의해 치환된 것인 유기막 조성물. The A 2 is an organic film composition is substituted by at least one hydroxyl group.
【청구항 12】 [Claim 12]
게 8항에서，  In crab 8,
상기 화학식 1 및 2에서 B1 및 B2는 치환 또는 비치환된 C6 내지 C30 방향족 고리로서 서로 동일한 구조를 가지는 유기막 조성물. In Chemical Formulas 1 and 2, B 1 and B 2 are substituted or unsubstituted C6 to C30 aromatic rings, which have the same structure as each other.
【청구항 13】  [Claim 13]
게 8항에서,  In crab 8,
상기 중합체의 중량평균분자량이 1 , 000 내지 200， 000인 유기막 조성물. An organic film composition having a weight average molecular weight of the polymer of 1,000 to 200, 000.
【청구항 14】 [Claim 14]
제 8항에서，  In claim 8,
상기 중합체는 상기 유기막 조성물의 총 함량에 대하여 0. 1 중량 % 내지 30 중량 %로 포함되어 있는 유기막 조성물. The polymer is 0.1 to 30% by weight based on the total content of the organic film composition Organic film composition contained by weight%.
【청구항 15]  [Claim 15]
기판 위에 재료 층을 제공하는 단계，  Providing a layer of material over the substrate ，
상기 재료 층 위에 게 8항 내지 제 14항 중 어느 한 항에 따른 유기막 조성물을 적용하는 단계 , Applying an organic film composition according to any one of claims 8 to 14 on the material layer,
상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계， 상기 하드마스크 층 위에 실리콘 함유 박막충을 형성하는 단계, Heat-treating the organic film composition to form a hard mask layer, forming a silicon-containing thin film on the hard mask layer,
상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계， 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하는 단계 Forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form 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 the silicon-containing thin film layer and the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
상기 재료 층의 노출된 부분을 식각하는 단계 Etching the exposed portion of the material layer
를 포함하는 패턴 형성 방법 . Pattern forming method comprising a.
【청구항 16】  [Claim 16]
제 15항에서'  In claim 15
상기 유기막 조성물을 적용하는 단계는 스핀-온 코팅 방법으로 수행하는 패턴 형성 방법. Applying the organic film composition is a pattern formation method performed by a spin-on coating method.
【청구항 17】  [Claim 17]
제 15항에서，  In claim 15,
상기 포토레지스트 층을 형성하는 단계 전에 바닥 반사 방지 층 (BARC)을 형성하는 단계를 더 포함하는 패턴 형성 방법. And forming a bottom antireflective layer (BARC) before forming the photoresist layer.
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