WO2014104496A1 - Monomère, composition de masque dur comprenant le monomère et procédé de formation de motif par utilisation de la composition de masque dur - Google Patents

Monomère, composition de masque dur comprenant le monomère et procédé de formation de motif par utilisation de la composition de masque dur Download PDF

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WO2014104496A1
WO2014104496A1 PCT/KR2013/004903 KR2013004903W WO2014104496A1 WO 2014104496 A1 WO2014104496 A1 WO 2014104496A1 KR 2013004903 W KR2013004903 W KR 2013004903W WO 2014104496 A1 WO2014104496 A1 WO 2014104496A1
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group
formula
substituted
unsubstituted
hard mask
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PCT/KR2013/004903
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English (en)
Korean (ko)
Inventor
김윤준
권효영
김혜정
이충헌
조연진
최유정
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제일모직 주식회사
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Priority claimed from KR1020120153750A external-priority patent/KR101590810B1/ko
Priority claimed from KR1020120153751A external-priority patent/KR101590809B1/ko
Priority claimed from KR1020130017054A external-priority patent/KR101693612B1/ko
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Priority to CN201380059507.8A priority Critical patent/CN104812729B/zh
Priority to US14/441,241 priority patent/US9556094B2/en
Publication of WO2014104496A1 publication Critical patent/WO2014104496A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings

Definitions

  • It relates to a monomer, a hard mask composition comprising the monomer, and a pattern formation method using the hard mask composition.
  • 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 a layer called a hardmask layer between the material layer to be etched and the photoresist layer.
  • 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 requires properties such as heat resistance and etching resistance to withstand multiple etching processes.
  • the hard mask layer is formed by a spin on coating method instead of the chemical vapor deposition method.
  • the spin-on coating method is not only easy to process but can also improve gap-fill and planarization properties.
  • the spin-on coating method may use a hard mask composition having solubility in a solvent.
  • One embodiment provides a monomer for a hard mask composition that can secure solvent solubility, gap-fill characteristics, and planarization characteristics while also satisfying chemical resistance, heat resistance, and etching resistance.
  • Another embodiment provides a hardmask composition comprising the monomer.
  • Another embodiment provides a method of forming a pattern using the hard mask composition.
  • a monomer for a hard mask composition represented by Chemical Formula 1 is provided.
  • a 1 to A 3 are each independently an aliphatic ring group or an aromatic ring group
  • X 1 to X 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,
  • L 1 and L 2 are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group
  • n is an integer from 1 to 5
  • n is an integer of 1-3.
  • a 1 to A 3 may be each independently a substituted or unsubstituted ring group selected from Group 1 below.
  • Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, substituted or unsubstituted C2 to C20 alkenylene group, substituted or unsubstituted C2 to C20 alkynylene group, C ⁇ O, NR a , oxygen (O), sulfur (S) or these and a combination in which R a is hydrogen, substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
  • At least one of A 1 to A 3 may be a polycyclic aromatic group.
  • a 1 and A 3 may each independently be a benzene group, a naphthalene group, a biphenyl group or a pyrene group, and the A 2 may be a pyrene group, a perylene group, a benzoperylene group or a coronene group.
  • the monomer for the hard mask composition may be represented by the following formula (2) or (3).
  • a 1 to A 3 are each independently an aliphatic ring group or an aromatic ring group
  • X 1 to X 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof.
  • the monomer for the hard mask composition may be represented by one selected from the group consisting of the following formula 4 to 14.
  • the monomer may have a molecular weight of about 500 to 5,000.
  • a hard mask composition including a monomer and a solvent represented by Formula 1 is provided.
  • a 1 to A 3 are each independently an aliphatic ring group or an aromatic ring group
  • X 1 to X 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,
  • L 1 and L 2 are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group
  • n is an integer from 1 to 5
  • n is an integer of 1-3.
  • the monomer may be represented by Formula 2 or 3.
  • the monomer may include at least one monomer represented by one selected from the group consisting of Chemical Formulas 4 to 14.
  • the monomer may have a molecular weight of about 500 to 5,000.
  • the monomer may be included in about 0.1 to 50% by weight based on the total content of the hard mask composition.
  • a material layer on a substrate applying the hardmask composition on the material layer, heat treating the hardmask composition to form a hardmask layer, and silicon on the hardmask layer.
  • Forming a containing thin film layer forming a photoresist layer on the silicon containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern and the silicon containing thin film layer and the Selectively removing the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer.
  • Applying the hard mask composition may be performed by a spin-on coating method.
  • Solubility in solvents, gap-fill and planarization properties can be satisfied while also providing heat and etch resistance.
  • 'substituted' means that a hydrogen atom in a compound is a halogen atom (F, Cl, Br, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl groups, C2 to C20 alkenyl groups, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group,
  • hetero means containing 1 to 3 heteroatoms selected from N, O, S and P.
  • Monomers for the hard mask composition according to one embodiment may be represented by the formula (1).
  • a 1 to A 3 is a ring having one or more rings substituted or unsubstituted, each independently may be an aliphatic ring group or an aromatic ring group,
  • X 1 to X 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,
  • L 1 and L 2 are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group
  • n is an integer from 1 to 5
  • n is an integer of 1-3.
  • the monomer may have rigid properties by including an aliphatic ring group or an aromatic ring group each having one or two or more rings in the core and the substituent.
  • the monomer may be effectively formed by a spin-on coating method by further improving solubility by a plurality of functional groups (X 1 to X 3 ) included in each substituent, as well as spin-on on a lower layer having a predetermined pattern.
  • the gap-fill properties and planarization properties that can fill the gap between patterns when formed by the coating method are also excellent.
  • X 1 and X 2 may be amplified cross-linking based on the condensation reaction with the functional group represented by X 3 can exhibit excellent crosslinking properties. Accordingly, the monomer may be crosslinked into a high molecular weight polymer in a short time even after heat treatment at a relatively low temperature, thereby exhibiting the properties required in a hard mask layer such as excellent mechanical properties, heat resistance, chemical resistance, and etching resistance.
  • a 1 to A 3 may be each independently a substituted or unsubstituted ring group selected from Group 1 below.
  • Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, substituted or unsubstituted C2 to C20 alkenylene group, substituted or unsubstituted C2 to C20 alkynylene group, C ⁇ O, NR a , oxygen (O), sulfur (S) or these and a combination in which R a is hydrogen, substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
  • each ring is not particularly limited, and each ring may be substituted or unsubstituted.
  • the ring listed in Group 1 is a substituted ring, it may be substituted with, for example, a C1 to C20 alkyl group, a halogen atom, a hydroxy group or the like, but the substituent is not limited.
  • a 1 to A 3 may be, for example, a substituted or unsubstituted aromatic group, and may be, for example, a benzene group, a naphthalene group, a biphenyl group, a pyrene group, a perylene group, a benzoperylene group, a coronene group, or a combination thereof.
  • the A 1 to A 3 may be, for example, an aromatic group substituted with a hydroxy group.
  • a 2 when A 2 is a pyrene group, it may be represented by the following Formula A.
  • the number of functional groups is not particularly limited, and in Chemical Formula A, k may be an integer of 0 to 8.
  • At least one of A 1 to A 3 may be a polycyclic aromatic group, for example, a pyrene group, a perylene group, a benzoperylene group, a coronene group, or a combination thereof.
  • a 1 and A 3 may be each independently a benzene group, a naphthalene group, a biphenyl group or a pyrene group, and the A 2 may be a pyrene group, a perylene group, a benzoperylene group or a coronene group.
  • the monomer may be represented by, for example, the following Chemical Formula 2 or 3.
  • a 1 to A 3 are each independently an aliphatic ring group or an aromatic ring group
  • X 1 to X 3 are each independently hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof.
  • the monomer may control physical properties such as solubility by adjusting the number of substituents.
  • the monomer may be, for example, a compound of a multipaired dendritic structure having three or more multiple substituents with an aliphatic ring group or an aromatic ring group having one or more rings as a core.
  • the monomer may be represented by any one selected from, for example, the following Chemical Formulas 1-1 to 1-9.
  • La, Lb, Lc, Ld, L'a, L'b, L'c and L'd are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group,
  • xa and xb are each independently an integer of 0 to 5
  • xc and xd are each independently an integer of 0 to 8,
  • ya and yb are each independently an integer of 0 to 8
  • yc and yd are each independently an integer of 0-7.
  • La, Lb, Lc, Ld, Le, Lf, Lg, Lh, L'a, L'b, L'c, L'd, L'e, L'f, L'g and L'h are each independent A single bond or a substituted or unsubstituted C1 to C6 alkylene group,
  • xa, xb, yc, yd, ze and zf are each independently integers from 0 to 5,
  • Tg and Th are each independently an integer of 0-9.
  • La, Lb, Lc, Ld, Le, Lf, Lg, Lh, Li, L'a, L'b, L'c, L'd, L'e, L'f, L'g, L'h and L'i is each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group,
  • xa, yb, zc, xd ye, zf, xg, yh and zi are each independently integers of 0 to 5.
  • the monomer may be represented by one selected from the group consisting of the following Chemical Formulas 4 to 14, for example.
  • the monomer may have a molecular weight of about 500 to 5,000. By having a molecular weight in the above range, the monomer having a high carbon content has excellent solubility in a solvent and a good thin film by spin-on coating can be obtained.
  • the hardmask composition according to one embodiment includes the monomer and the solvent described above.
  • the monomer is as described above, one monomer may be included alone or two or more monomers may be mixed and included.
  • the solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the monomer, and for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) mono At least one selected from methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, "methylpyrrolidone, acetylacetone" and ethyl 3-ethoxypropionate It may include one.
  • the monomer may be included in about 0.1 to 50% by weight based on the total content of the hard mask composition. By including the monomer in the above range can be coated with a thin film of the desired thickness.
  • the hardmask composition may further include a surfactant.
  • the surfactant may be, for example, alkylbenzenesulfonic acid salt, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt and the like, but is not limited thereto.
  • the surfactant may be included in an amount of about 0.001 to 3 parts by weight based on 100 parts by weight of the hard mask composition. By including in the above range, solubility can be ensured without changing the optical properties of the hard mask composition.
  • a method of forming a pattern includes providing a material layer on a substrate, applying a hardmask composition including the monomer and the solvent to the material layer, and heat treating the hardmask composition to form a hardmask layer. Forming a photoresist layer on the hard mask layer; forming a photoresist layer on the silicon mask 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.
  • 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 hard mask composition may be prepared in a solution form and applied by a spin-on coating method.
  • the coating thickness of the hard mask composition is not particularly limited, but may be applied, for example, to a thickness of about 50 to 50,000 kPa.
  • Heat treating the hard mask composition may be performed, for example, at about 100 to 500 ° C. for about 10 seconds to 10 minutes.
  • the monomer may cause self-crosslinking and / or mutual crosslinking reaction.
  • the silicon-containing thin film layer may be made of silicon nitride or silicon oxide, for example.
  • a bottom anti-reflective coating may be further formed on the silicon-containing thin film layer.
  • Exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV.
  • a heat treatment process may be performed at about 100 to 500 ° C. after exposure.
  • Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, which may use, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 and mixtures thereof.
  • an etching gas which may use, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 and mixtures 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 in various patterns in a semiconductor integrated circuit device.
  • Synthesis was carried out in the same manner as in Synthesis Example 1 except that 22.07 g of methoxy naphthoyl chloride was added to the reactor instead of methoxy benzoyl chloride to obtain a monomer represented by the following Chemical Formula 5a.
  • a solution was prepared by adding 40.4 g (0.1345 mol) of coronene, 22.94 g (0.1345 mol) of 4-methoxybenzoyl chloride and 731 g of 1,2-dichloroethane to the flask. Subsequently, 17.9 g (0.1345 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. Upon completion of the reaction, methanol was added and the precipitate formed was filtered and dried to obtain a compound.
  • Second step remove the methyl group demethylation ) reaction
  • a compound represented by the following Chemical Formula 8b was obtained in the same manner as in Synthesis Example 1 except for reacting with 2.34 g (0.01151 mol) of isophthaloyl chloride instead of terephthaloyl chloride in the first step of Synthesis Example 5.
  • a solution was prepared by adding 20.0 g (0.07239 mol) of benzoperylene, 12.4 g (0.07239 mol) of 4-methoxybenzoyl chloride and 378 g of 1,2-dichloroethane to the flask. Subsequently, 9.65 g (0.07239 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. Upon completion of the reaction, methanol was added and the precipitate formed was filtered and dried to obtain a compound.
  • Second step remove the methyl group demethylation ) reaction
  • the solution was prepared by adding 18.5 g (0.07330 mol) of perylene, 12.5 g (0.07330 mol) of 4-methoxybenzoyl chloride and 367 g of 1,2-dichloroethane to the flask. 9.77 g (0.07330 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. Upon completion of the reaction, methanol was added and the precipitate formed was filtered and dried to obtain a compound.
  • Second step remove the methyl group demethylation ) reaction
  • a solution was prepared by adding 10.0 g (0.03329 mol) of coronene, 8.81 g (0.03329 mol) of 1-pyrenecarbonyl chloride and 209 g of 1,2-dichloroethane to the flask. Subsequently, 4.44 g (0.03329 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. Upon completion of the reaction, methanol was added and the precipitate formed was filtered and dried to obtain a compound.
  • a solution was prepared by adding 10 g (0.0494 mol) of pyrene, 8.43 g (0.0494 mol) of 4-methoxybenzoyl chloride and 100.11 g of 1,2-dichloroethane to the flask. Subsequently, 6.59 g (0.0494 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 2 hours. Upon completion of the reaction, methanol was added to the solution, and the precipitate formed was filtered and dried to obtain a compound.
  • the solution was then prepared by adding 15.46 g (0.0460 mol) of the compound obtained above, 4.07 g (0.0153 mol) of 1,3,5-benzenetricarboxylic acid chloride and 102.62 g of 1,2-dichloroethane to the flask. Subsequently, 6.13 g (0.0460 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 6 hours. After the reaction was completed, methanol was added to the solution, and the precipitate formed was filtered and dried.
  • Second step remove the methyl group demethylation ) reaction
  • a solution was prepared by adding 11.84 g (0.0105 mol) of the compound obtained above and 40 g of tetrahydrofuran to the flask. Subsequently, an aqueous solution of 7.98 g (0.2108 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 24 hours. Upon completion of the reaction, the mixture was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Chemical Formula 12a.
  • a solution was prepared by adding 10 g (0.0333 mol) of coronene, 5.68 g (0.0333 mol) of 4-methoxybenzoyl chloride and 80.48 g of 1,2-dichloroethane to the flask. 4.44 g (0.0333 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 4 hours. After the reaction was completed, methanol was added and the precipitate formed was filtered and dried.
  • a solution was prepared by adding 12.00 g (0.0276 mol) of the compound obtained above, 2.44 g (0.0092 mol) of 1,3,5-benzenetricarboxylic acid chloride and 72.51 g of 1,2-dichloroethane to the flask. 3.68 g (0.0276 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, methanol was added and the precipitate formed was filtered and dried.
  • a solution was prepared by adding 9.84 g (0.0067 mol) of the compound obtained above and 30 g of tetrahydrofuran to the flask. An aqueous solution of 5.06 g (0.1337 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 24 hours. Upon completion of the reaction, the mixture was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Chemical Formula 13a.
  • the solution was prepared by adding 15 g (0.0595 mol) of perylene, 13.12 g (0.0595 mol) of 6-methoxynaphthalene-2-carbonylchloride and 144.18 g of 1,2-dichloroethane to the flask. Subsequently, 7.93 g (0.0595 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 5 hours. After the reaction was completed, methanol was added and the precipitate formed was filtered and dried.
  • a solution was prepared by adding 22.80 g (0.0522 mol) of the compound obtained above, 4.62 g (0.0174 mol) of 1,3,5-benzenetricarboxylic acid chloride and 137.55 g of 1,2-dichloroethane to the flask. Subsequently, 6.96 g (0.0522 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, methanol was added and the precipitate formed was filtered and dried.
  • a solution was prepared by adding 10.50 g (0.0074 mol) of the compound obtained above and 22 g of tetrahydrofuran to the flask. An aqueous solution of 8.37 g (0.2213 mol) of sodium borohydride was slowly added to the solution and stirred at 50 ° C. for 24 hours. Upon completion of the reaction, the mixture was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Chemical Formula 14a.
  • a 500 ml three-necked flask equipped with a thermometer, a condenser and a mechanical stirrer was prepared and immersed in an oil thermostat at 90 ° C to 100 ° C. It was stirred using a stirring magnet while maintaining a constant temperature. Subsequently, 28.83 g (0.2 mol) of 1-naphthol, 30.56 g (0.14 mol) of hydroxy pyrene and 12.0 g (0.34 mol) of paraformaldehyde were added to the three necked flask, and 0.38 g (2 mmol) of p-toluene sulfonic acid monohydrate. Was dissolved in 162 g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was added to the three neck flask and stirred for 5 to 12 hours to carry out the reaction.
  • PGMEA propylene glycol monomethyl ether acetate
  • Samples were taken from the polymerization reactant at 1 hour intervals, and the weight average molecular weight of the sample was measured to complete the reaction when the weight average molecular weight was 1,800 to 2,000.
  • the reaction was cooled to room temperature, and then the reaction was added to 40 g of distilled water and 400 g of methanol, followed by vigorous stirring. The supernatant was removed, and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), followed by vigorous stirring using 320 g of methanol, followed by standing (primary). The supernatant obtained at this time was removed again and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (secondary).
  • the first and second processes were referred to as one-time purification processes, and this purification process was carried out three times in total.
  • the purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer represented by the following formula (16).
  • the weight average molecular weight of the polymer was 1,870, and the degree of dispersion was 1.19.
  • This solution was placed in a separatory funnel, and n-heptane was added to remove the monomer and the low molecular weight to obtain a polymer represented by the following formula (18).
  • the weight average molecular weight of the polymer was 12,000, and the degree of dispersion was 2.04.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the monomers obtained in Synthesis Examples 2 to 12 were used instead of the monomers obtained in Synthesis Example 1, respectively.
  • a hardmask composition was prepared in the same manner as in Example 1, except that the compounds obtained in Comparative Synthesis Examples 1 to 4 were used instead of the compounds obtained in Synthesis Example 1.
  • the baking process was performed and then the V-SEM equipment was used. The gap-fill characteristics and planarization characteristics were observed.
  • the gap-fill characteristics were determined by the presence of voids by observing the pattern cross section with an electron scanning microscope (SEM), and the planarization characteristics were quantified by Equation 1 below.
  • the flattening characteristics are excellent as the difference between h1 and h2 is not large, so the smaller the number, the better the flattening characteristics.
  • the gap-fill characteristics were determined by the presence of voids by observing a pattern cross section of 40 nm in width and 500 nm in depth, and the planarization characteristics were quantified by Equation 1 by observing a pattern cross section of 180 nm in width and 500 nm in depth. .
  • Example 5 void no 6.5%
  • Example 6 void no 5.8%
  • Example 7 void no 7.8%
  • Example 8 void no 6.8%
  • Example 9 void no 7.5% Comparative
  • Example 3 void occurs 17.4%
  • the patterned silicon wafer was spin-on coated with a hard mask composition (compound content: 10.0 wt%) according to Examples 10 to 12 and heat-treated at 400 ° C. for 120 seconds, followed by a field emission electron scanning microscope (FE-SEM). The equipment was used to observe gap-fill characteristics and planarization characteristics.
  • a hard mask composition compound content: 10.0 wt% according to Examples 10 to 12 and heat-treated at 400 ° C. for 120 seconds, followed by a field emission electron scanning microscope (FE-SEM). The equipment was used to observe gap-fill characteristics and planarization characteristics.
  • the gap-fill characteristics were determined by the presence or absence of voids by observing the pattern cross section with FE-SEM, and the planarization property was calculated by Equation 1 by measuring the thickness of the hard mask layer from the image of the pattern cross section observed by FE-SEM. Digitized.
  • the thin film formed from the hard mask composition according to Examples 10 to 12 has a good degree of planarization and no voids are observed to show excellent gap-fill characteristics.
  • the film was prebaked at 180 ° C. for 60 seconds at a thickness of about 800 ⁇ s and then at 400 ° C. Out gas produced upon baking for 120 seconds was measured using QCM (Quartz Crystal Microbalace).
  • the hard mask composition according to Examples 1 to 4 can be seen that outgas of less than 60ng while being baked at a high temperature (400 °C) can be stably performed a high temperature process. On the contrary, it can be seen that the hard mask compositions according to Comparative Examples 1 and 2 are not suitable for the high temperature process because the amount of outgas generated is relatively high.
  • a thin film was formed by heat treatment at 240 ° C. for 1 minute on a hot plate.
  • the thickness of the initial thin film was measured with a thin film thickness meter of K-MAC.
  • the thin film was heat treated again at 400 ° C. for 2 minutes, and then the thickness of the thin film was measured. Then, the thin film thickness reduction rate was calculated according to the following Equation 2.
  • Thin film thickness reduction rate (film thickness after baking at 240 °C-thin film thickness after baking at 400 °C) / thin film thickness after baking at 240 °C X 100 (%)
  • Example 5 Thin film thickness reduction rate (%) Out gas volume (ng) Example 5 -5.75 24 Example 6 -5.87 20 Example 7 -8.82 25 Example 8 -9.98 37 Example 9 -10.32 52 Comparative Example 3 -34.08 180
  • the hard mask composition according to Examples 5 to 9 has a smaller thickness reduction rate after heat treatment at 400 ° C. compared with the thin film formed from the hard mask composition according to Comparative Example 3.
  • the hard mask composition according to Examples 5 to 9 can be stably performed at a high temperature because the amount of outgas generated during baking at a high temperature (400 ° C.) is small.
  • the hard mask composition according to Comparative Example 3 has a relatively large amount of outgas generation and is not suitable for high temperature processes.
  • the hard mask composition according to Examples 5 to 9 has a high crosslinking degree of the thin film as compared with the hard mask composition according to Comparative Example 3 and has high heat resistance even at a high temperature of 400 ° C.
  • Example 10 -4.39 21
  • Example 11 -3.96 32
  • Example 12 -4.31 24
  • the thin film formed from the hard mask composition according to Examples 10 to 12 has a low thickness reduction rate and a low outgassing at high temperature, and from this, it can be seen that the heat resistance is high.
  • the hard mask composition (compound content: 13% by weight) according to Examples 5 to 12 and Comparative Example 4 on the silicon wafer was heat-treated at 400 °C for 2 minutes on a hot plate to form a thin film. Subsequently, the thickness of the thin film was measured. Subsequently, the thin film was dry-etched using N 2 / O 2 mixed gas and CF x gas for 60 seconds and 100 seconds, respectively, and the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated by the following equation 3 from the thickness and etching time of the thin film before and after dry etching.
  • BER bulk etch rate
  • the thin film formed from the hard mask composition according to Examples 5 to 12 had a low etching rate because of sufficient etching resistance to the etching gas compared to the thin film formed from the hard mask composition according to Comparative Example 4. Can be.
  • a 3000 (thick silicon oxide (SiO 2 ) layer was formed on the silicon wafer by chemical vapor deposition. Subsequently, after spin-on coating the hard mask composition (compound content: 15 wt%) according to Examples 5 to 12 and Comparative Examples 3 and 4 on the silicon oxide layer, the hard mask layer was heat-treated at 400 ° C. for 2 minutes on a hot plate. Formed. Subsequently, a silicon nitride (SiN) layer was formed on the hard mask layer by chemical vapor deposition. Then, a KrF photoresist was coated on the silicon nitride layer, heat treated at 110 ° C.
  • SiN silicon nitride
  • TMAH tetramethylammonium hydroxide
  • the cross section of the pattern of the hard mask layer and the silicon oxide layer was observed using an electron scanning microscope (SEM).
  • the hard mask layer formed from the hard mask composition according to Examples 5 to 12 and the silicon oxide layer thereunder are all patterned in a vertical shape, whereas the hard mask layer formed from the hard mask composition according to Comparative Examples 3 and 4 was used. It can be seen that the mask layer is patterned in a tapered shape. From this, when the hard mask composition according to Examples 5 to 12 was used, the material layer was formed in a good pattern due to better etching resistance than that of the hard mask compositions according to Comparative Examples 3 and 4, and is located below the hard mask layer. It can also be seen that it is formed in a good pattern.
  • the refractive index (n) and extinction coefficient (k) of the hard mask layer were measured.
  • the refractive index and the extinction coefficient were measured using an Ellipsometer (manufactured by J.A. Woollam) while irradiating light with a wavelength of 193 nm to 633 nm.
  • the hard mask layer formed of the hard mask composition according to Examples 1 to 4 has a refractive index (n) and an absorption coefficient (k) suitable for use as a hard mask layer, such as 193 nm. It can be seen that it is also applicable to the hard mask layer even in the pattern process using a low light source.
  • the extinction coefficient (k) at 633 nm has a low value of 0.1 or less, so it can be applied to a thick hard mask of about 10,000 ⁇ to 50,000 ⁇ . Can be.
  • the extinction coefficient (k) at 633 nm has a high value of more than 0.1, so that the hard mask composition according to Comparative Examples 1 and 2 is applied to a process requiring a thick hard mask such as a metal pattern. It is difficult to see.
  • the hard mask composition according to Examples 1 to 4 has a high solubility, thereby increasing the maximum solid content to form a thick film.
  • the hard mask composition according to Comparative Example 1 has a low maximum solids content due to relatively low solubility, so that the thickness of the formed film is thin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne un monomère pour une composition de masque dur qui est représenté dans la formule chimique 1, la composition de masque dur comprenant le monomère et un procédé de formation d'un motif par utilisation de la composition de masque dur. Dans la formule chimique 1, les définitions de A1-A3, X1-X3, L1, L2, n et m sont identiques à celles mentionnées dans la description.
PCT/KR2013/004903 2012-12-26 2013-06-04 Monomère, composition de masque dur comprenant le monomère et procédé de formation de motif par utilisation de la composition de masque dur WO2014104496A1 (fr)

Priority Applications (2)

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CN201380059507.8A CN104812729B (zh) 2012-12-26 2013-06-04 单体、包含此单体的硬屏蔽组成物及使用此硬屏蔽组成物形成图案的方法
US14/441,241 US9556094B2 (en) 2012-12-26 2013-06-04 Monomer, hardmask composition including monomer, and method for forming pattern by using hardmask composition

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KR1020120153750A KR101590810B1 (ko) 2012-12-26 2012-12-26 모노머, 상기 모노머를 포함하는 하드마스크 조성물 및 상기 하드마스크 조성물을 사용하는 패턴형성방법
KR10-2012-0153752 2012-12-26
KR1020120153751A KR101590809B1 (ko) 2012-12-26 2012-12-26 하드마스크 조성물용 모노머, 상기 모노머를 포함하는 하드마스크 조성물 및 상기 하드마스크 조성물을 사용하는 패턴형성방법
KR10-2012-0153751 2012-12-26
KR10-2012-0153750 2012-12-26
KR20120153752 2012-12-26
KR10-2013-0017054 2013-02-18
KR1020130017054A KR101693612B1 (ko) 2012-12-26 2013-02-18 하드마스크 조성물용 모노머, 상기 모노머를 포함하는 하드마스크 조성물 및 상기 하드마스크 조성물을 사용하는 패턴형성방법

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US10777412B2 (en) 2017-07-14 2020-09-15 Samsung Electronics Co., Ltd. Hardmask composition, method of preparing the same, and method of forming patterned layer by using the hardmask composition
TWI724702B (zh) * 2018-12-21 2021-04-11 南韓商三星Ｓｄｉ股份有限公司 硬罩幕組成物、硬罩幕層以及形成圖案的方法

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US9862668B2 (en) * 2014-11-24 2018-01-09 Samsung Sdi Co., Ltd. Monomer, polymer, organic layer composition, organic layer, and method of forming patterns
KR101806329B1 (ko) * 2014-11-24 2017-12-07 삼성에스디아이 주식회사 모노머, 중합체, 유기막 조성물, 유기막, 및 패턴형성방법

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US10777412B2 (en) 2017-07-14 2020-09-15 Samsung Electronics Co., Ltd. Hardmask composition, method of preparing the same, and method of forming patterned layer by using the hardmask composition
TWI724702B (zh) * 2018-12-21 2021-04-11 南韓商三星Ｓｄｉ股份有限公司 硬罩幕組成物、硬罩幕層以及形成圖案的方法
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