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WO2016129927A1 - Hard-mask composition comprising solution processable carbon allotropes, method for manufacturing hard-mask using same, and hard-mask - Google Patents

Hard-mask composition comprising solution processable carbon allotropes, method for manufacturing hard-mask using same, and hard-mask Download PDF

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Publication number
WO2016129927A1
WO2016129927A1 PCT/KR2016/001379 KR2016001379W WO2016129927A1 WO 2016129927 A1 WO2016129927 A1 WO 2016129927A1 KR 2016001379 W KR2016001379 W KR 2016001379W WO 2016129927 A1 WO2016129927 A1 WO 2016129927A1
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hard mask
carbon allotrope
hard
carbon
mask
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PCT/KR2016/001379
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French (fr)
Korean (ko)
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양승윤
이승현
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부산대학교 산학협력단
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Priority claimed from KR1020150028083A external-priority patent/KR20160100172A/en
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Publication of WO2016129927A1 publication Critical patent/WO2016129927A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials

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  • the present invention relates to a hard mask composition comprising a solution processable carbon allotrope, a method for producing a hard mask using the composition, and a hard mask.
  • an amorphous carbon layer is deposited through chemical vapor deposition, a micropattern is formed using PR on it, and a pattern is formed using this hard mask.
  • ACL hard masks have high etch resistance and etch selectivity, but when gas is deposited in the form of particles during the CVD process, it is a cause of defects later and it is not easy to find them when the particles are located inside.
  • the deposition of ACL is carried out in a vacuum state, the productivity is lowered, and expensive equipment is required, so the process advantages are low.
  • SOC spin-on-carbon hard mask
  • ACL ACL
  • SOC spin-on-carbon hard mask
  • SOC is a material developed to improve the disadvantages of ACL. It is a method of manufacturing a film by dispersing or dissolving high content of hydrocarbon and polymer in an organic solvent and then spin coating.
  • SOC is less etch-resistant than ACL and can be manufactured using coating equipment of existing semiconductor lines, but has a relatively high surface roughness.
  • An object of the present invention is to improve the above-mentioned problems of the hard mask and to provide an organic hard mask capable of solution processing as a highly etch resistant organic hard mask.
  • the present invention provides a hard mask composition
  • a hard mask composition comprising a polymer binder, a carbon allotrope, and an organic solvent.
  • the polymer binder has a property of dissolving well in an organic solvent as a component for the solution process of the hard mask composition, for example, polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylene , Polyamide, polyamideimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether ketone, polyphthalamide, polyether nitrile, polyether sulfone, polybenzimidazole, polyka Bodyimide, Polysiloxane, Polymethylmethacrylate, Polymethacrylate, Nitrile Rubber, Acrylic Rubber, Polyethylene Tetrafluoride, Epoxy Resin, Phenolic Resin, Melamine Resin, Urea Resin, Polybutene, Polypentene, Ethylene-propylene Copolymer , Ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-
  • the polymer binder may be a crystalline polymer including a crystalline portion, and the crystalline polymer refers to a polymer including a crystalline portion in part or all.
  • the hard mask produced by using a high crystallinity polymer has a etch resistance to florin-based plasma.
  • the carbon allotrope may be any one of graphene, graphene oxide, carbon black, carbon nanotubes, and fullerenes.
  • the carbon allotrope may have a length in one direction of 500 nm or less.
  • a two-dimensional carbon allotrope such as graphene or graphene oxide as the carbon allotrope
  • a plurality of virtual straight lines along the in-plane direction exist in the two-dimensional carbon allotrope.
  • the maximum distance among the linear distances between two points where each of the virtual straight lines intersects the outline of the two-dimensional carbon allotrope may be 500 nm or less.
  • the length in the extending direction of the long axis may be 500 nm or less.
  • a coating film having a uniform thickness of 200 nm to 400 nm may be formed by using a carbon allotrope having a length in one direction of 500 nm or less.
  • the thickness of 300 nm which is the thickness of the hard mask used in the production site, may be uniformly formed.
  • the carbon allotrope may be a carbon allotrope grafted with a functional group for enhancing dispersibility in an organic solvent or enhancing interaction with a polymer binder.
  • the functional group may include an alkyl group, a phenyl group, a phenyl group or an aromatic ring group including at least one alkyl group as a substituent.
  • a phenyl group including at least one alkyl group as a substituent means a functional group in which at least one of hydrogens in the phenyl group is substituted with an alkyl group.
  • an "aromatic ring group” includes an aryl group or a heteroaryl group.
  • the grafted carbon allotrope can have a high affinity with an organic solvent and / or a polymeric binder, and thus can be more dispersed.
  • the hard mask composition may further include a surfactant to easily disperse the carbon allotrope in the organic solvent.
  • the present invention provides a hard mask manufacturing method comprising preparing a solution in which a polymer binder is dissolved in an organic solvent and a carbon allotrope is dispersed in the organic solvent, and evaporating the solvent of the solution.
  • the solution may further include a surfactant to easily disperse the carbon allotrope in the organic solvent.
  • the present invention provides a hard mask comprising a crystalline polymer or carbon allotrope comprising a crystalline portion.
  • the carbon allotrope may be any one of graphene, graphene oxide, carbon black, carbon nanotubes, or fullerene, and may be the grafted carbon allotrope described above.
  • the hard mask may have a uniform thickness of 200 nm to 400 nm, wherein the carbon allotrope may have a length in one direction of 500 nm or less.
  • the carbon allotrope is oriented in one direction along its long axis, and increasing the orientation in the organic mask of the carbon allotrope can increase the etching resistance to the florin-based plasma of the organic mask.
  • the hard mask of the present invention can provide a uniform hard mask with low surface roughness easily and inexpensively in a solution process.
  • the hard mask of the present invention has a roughness of several tens to several tens of nanometers or less, and has high resistance to plasma of a gas containing florin-based gas (SF 6 or CF 4 ).
  • a gas containing florin-based gas SF 6 or CF 4
  • 1 is a diagram illustrating preparation of an AAO for a pattern of a hard mask and transfer thereof.
  • FIG. 2 is a diagram illustrating an etching process according to an etching for a pattern of a hard mask and a hard mask pattern of an etched layer.
  • the hard mask of the present invention may be a crystalline hard mask having a crystalline portion.
  • FIG. 4 is a diagram illustrating that the carbon allotrope is oriented in a predetermined direction in the hard mask of the present invention.
  • An oxidized carbon material is prepared, and an organic compound including a functional group such as an alkyl group or a phenyl group capable of increasing solubility in an organic solvent is grafted onto the oxidized carbon material.
  • the surface functionalization of graphene, a kind of carbon allotrope, for graphite surface functionalization first, graphite flake and sodium nitrate are added to sulfuric acid, and then cooled at 0 ° C. Mix well, and then add potassium permanganate.
  • the prepared solution may be diluted with water and treated with hydrogen peroxide at a concentration of 3% to obtain graphite oxide.
  • the graphite oxide is dried, 50 mg of dried graphite oxide is placed in a round flask, and 5 mL of anhydrous dimethylformamide (DMF) is added, followed by stirring in a nitrogen atmosphere to prepare a suspension. 2 mmol of organic isocyante is added to the thus prepared suspension and stirred for about 24 hours. When a slurry is formed, the mixture is added to 50 mL of methylene chloride and solidified. After filtering, additionally wash with 50 mL of methyl chloride and dry.
  • DMF dimethylformamide
  • Graphite oxide which has undergone the above process, is functionalized in a phenyl isocyanate group and easily dissolved in DMF, and graphene dispersed in DMF after sonication for 10 hours at 0.1% (w / v) concentration ( graphene) solution can be obtained.
  • functionalized graphite oxide is easy to other polar solvents such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) and hexamethylphosphoramide (HMPA) in addition to DMF. Can be distributed.
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • HMPA hexamethylphosphoramide
  • a polymer binder is dissolved in an organic solvent, and a carbon mask or surface functionalized carbon allotrope according to grafting is dispersed or dissolved in the organic solvent to prepare a hard mask composition solution.
  • the prepared hard mask composition solution is prepared on a layer to be etched (eg SiO 2 or Si) by a solution process such as spin coating to prepare a hard mask layer having a uniform thickness.
  • polystyrene (PS) is dissolved in a 10-30% fraction of the graphene weight, and PS and surface-modified graphene are dispersed to prepare a solution using a spin coater.
  • the hard mask film may be prepared by forming a film with a thickness of 200 nm to 300 nm and annealing at 200 ° C. for 10 hours to remove residual solvent and reduce graphene.
  • polymers ex. Polypropylene (PP), plyvinylalcohol (PVA), polyvinylchloride (PVC)
  • PP Polypropylene
  • PVA plyvinylalcohol
  • PVC polyvinylchloride
  • an anodized aluminum oxide (AAO) film having cylindrical nanopores was prepared by anodizing aluminum, and only a AAO layer was separated from aluminum by applying a voltage in a solvent, and the prepared hardmask film Transfer to the phase.
  • AAO anodized aluminum oxide
  • a cylindrical nano hole pattern corresponding to the AAO pattern is formed in the hard mask by oxygen plasma.
  • the AAO is removed and the etched layer exposed by the pattern of the hard mask is etched by a florin-based (CF 4 ) plasma.
  • the hard mask composition solution is heated to a temperature higher than the melting point of the crystalline polymer after manufacturing the hard mask film by a solution process, and then, according to the control of the cooling rate, To form a crystal structure, such as.
  • a material capable of forming a crystal structure such as a liquid crystal material, may be used to form the crystal structure.
  • a film prepared by a solution process of a carbon allotrope and a polymer binder may be used as a solvent to give fluidity to the polymer binder (e.g., For example, a gaseous solvent) and then a flow to give a carbon allotrope, as shown in FIG.

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Abstract

The present invention relates to: a hard-mask composition for an organic hard mask which has high etching resistance and is solution processable, the hard-mask composition comprising a polymer binder, carbon allotropes and an organic solvent; a method for manufacturing such a hard-mask; and a hard-mask.

Description

용액 공정 가능한 탄소 동소체를 포함하는 하드 마스크 조성물, 이 조성물을 이용하여 하드마스크를 제조하는 방법 및 하드마스크Hard mask composition comprising a solution processable carbon allotrope, method for preparing hard mask using the composition, and hard mask
본 발명은 용액 공정 가능한 탄소 동소체를 포함하는 하드 마스크 조성물, 이 조성물을 이용하여 하드마스크를 제조하는 방법 및 하드마스크에 관한 것이다.The present invention relates to a hard mask composition comprising a solution processable carbon allotrope, a method for producing a hard mask using the composition, and a hard mask.
2000년대 초반 미세패턴기술의 발달과 함께 매년 집적도를 2배 증가시키는 기술혁신을 이루었지만 10나노 이하의 미세패턴 제작의 어려움과 10 나노이하의 간격에서 발생되는 간섭현상으로 인해 기존 미세패턴 공정으로는 집적도를 더 이상 올리기 힘든 상황에 봉착하였고 테라급 메모리 개발에도 한계를 보여주었다. In the early 2000s, with the development of micropattern technology, we achieved technological innovation that doubled the density every year.However, due to the difficulty of producing micropatterns of less than 10 nanometers and the interference occurring at intervals of less than 10 nanometers, It has encountered a situation where it is difficult to increase the density anymore, and it has shown limitations in developing tera-class memory.
이를 극복하기 위해 최근 신개념의 3차원 수직구조 메모리 개발이 이루어졌는데, 공정기술만 뒷 받침된다면 회로기판을 필요한 만큼 쌓아올릴 수 있기 때문에 집적도를 높이는데 사실상 한계가 없어 꿈의 테라급 메모리 개발이 실현될 것으로 기대를 모으고 있다. 결국, 적층 수를 높이는 것이 고용량의 실현과 맞물려 있고 이를 위해서는 고종횡비의 에칭기술이 선행되어야 한다.In order to overcome this, a new concept of 3D vertical structure memory has been developed. If only process technology is supported, the circuit boards can be stacked as needed, so there is virtually no limit to increase the density. I am looking forward to it. As a result, increasing the number of laminations is coupled with the realization of high capacity, which requires a high aspect ratio etching technique.
종래에는 화학증기증착을 통해 비결정성 탄소층(amorphous carbon layer(ACL))을 증착하고 그 위에 PR을 이용해 미세패턴을 만든 다음 이 하드마스크를 이용하여 패턴을 형성하고 있다. ACL 하드마스크는 높은 에칭 내성과 에칭 선택성을 가지고 있지만, CVD 공정 중 가스가 입자형태로 뭉쳐 증착되면 이후 결함의 원인이 되며 뭉친 입자들이 내부에 위치하는 경우 검사과정에서 찾아내기 또한 쉽지 않다. 뿐만 아니라 ACL의 증착은 진공상태에서 진행되어 생산성이 떨어지며 고가의 장비가 필요하여 공정상의 이점이 낮다.Conventionally, an amorphous carbon layer (ACL) is deposited through chemical vapor deposition, a micropattern is formed using PR on it, and a pattern is formed using this hard mask. ACL hard masks have high etch resistance and etch selectivity, but when gas is deposited in the form of particles during the CVD process, it is a cause of defects later and it is not easy to find them when the particles are located inside. In addition, the deposition of ACL is carried out in a vacuum state, the productivity is lowered, and expensive equipment is required, so the process advantages are low.
SOC(Spin-on-carbon) 하드마스크는 ACL의 단점을 개선하기 위해 개발된 물질로 높은 함량의 탄화수소체와 고분자를 유기 용매에 분산 또는 용해시킨 후 스핀 코팅하여 필름을 제조하는 방법이다. 그러나, SOC는 ACL에 비해 내에칭성이 떨어지고, 기존의 반도체라인의 코팅장비를 활용하여 제조가 가능하지만 표면 거칠기가 비교적 높은 특성을 가진다.SOC (Spin-on-carbon) hard mask is a material developed to improve the disadvantages of ACL. It is a method of manufacturing a film by dispersing or dissolving high content of hydrocarbon and polymer in an organic solvent and then spin coating. However, SOC is less etch-resistant than ACL and can be manufactured using coating equipment of existing semiconductor lines, but has a relatively high surface roughness.
본 발명은 상기한 하드 마스크의 문제점을 개선하고, 고 내에칭성 유기 하드마스크로서, 용액공정 가능한 유기 하드 마스크를 제공함을 목적으로 한다.An object of the present invention is to improve the above-mentioned problems of the hard mask and to provide an organic hard mask capable of solution processing as a highly etch resistant organic hard mask.
일 측면으로서, 본 발명은 고분자 바인더, 탄소동소체 및 유기용매를 포함하는 하드 마스크 조성물을 제공한다. In one aspect, the present invention provides a hard mask composition comprising a polymer binder, a carbon allotrope, and an organic solvent.
상기 고분자 바인더는 상기 하드 마스크 조성물의 용액 공정을 위한 성분으로서, 유기 용매에 잘 용해 되는 성질을 가지며, 예를 들어, 폴리에스테르, 폴리카보네이트, 폴리비닐알코올, 폴리비닐부티랄, 폴리아세탈, 폴리아릴레이트, 폴리아마이드, 폴리아미드이미드, 폴리에테르이미드, 폴리페닐렌에테르, 폴리페닐렌설파이드, 폴리에테르설폰, 폴리에테르케톤, 폴리프탈아마이드, 폴리에테르니트릴, 폴리에테르설폰, 폴리벤즈이미다졸, 폴리카보디이미드, 폴리실록산, 폴리메틸메타크릴레이트, 폴리메타크릴아마이드, 니트릴고무, 아크릴 고무, 폴리에틸렌테트라플루오라이드, 에폭시 수지, 페놀 수지, 멜라민 수지, 우레아 수지, 폴리부텐, 폴리펜텐, 에틸렌-프로필렌 공중합체, 에틸렌-부텐-디엔 공중합체, 폴리부타디엔, 폴리이소프렌, 에틸렌-프로필렌-디엔 공중합체, 부틸고무, 폴리메틸펜텐, 폴리스티렌, 스티렌-부타디엔 공중합체, 수첨스티렌-부타디엔 공중합체, 수첨폴리이소프렌 및 수첨폴리부타디엔으로 구성된 군에서 선택되는 1종 이상인 고분자일 수 있다.The polymer binder has a property of dissolving well in an organic solvent as a component for the solution process of the hard mask composition, for example, polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylene , Polyamide, polyamideimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether ketone, polyphthalamide, polyether nitrile, polyether sulfone, polybenzimidazole, polyka Bodyimide, Polysiloxane, Polymethylmethacrylate, Polymethacrylate, Nitrile Rubber, Acrylic Rubber, Polyethylene Tetrafluoride, Epoxy Resin, Phenolic Resin, Melamine Resin, Urea Resin, Polybutene, Polypentene, Ethylene-propylene Copolymer , Ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-pro Alkylene-it can be a butadiene copolymer, a hydrogenated poly-polymer at least one member selected from the group consisting of polyisoprene and hydrogenated polybutadiene-diene copolymer, butyl rubber, polymethylpentene, polystyrene, styrene-butadiene copolymer, hydrogenated styrene.
상기 고분자 바인더는 결정성 부분을 포함하는 결정성 고분자일 수 있으며, 상기 결정성 고분자는 일부 또는 전부에 결정성 부분을 포함하는 고분자를 의미한다. 결정도가 높은 고분자를 사용함에 의해 제조된 하드 마스크는 플로린계 플라즈마에 내에칭성을 갖는다.The polymer binder may be a crystalline polymer including a crystalline portion, and the crystalline polymer refers to a polymer including a crystalline portion in part or all. The hard mask produced by using a high crystallinity polymer has a etch resistance to florin-based plasma.
상기 탄소 동소체는 그래핀, 그래핀 옥사이드, 카본블랙, 탄소나노튜브 및 풀러렌 중 어느 하나일 수 있다.The carbon allotrope may be any one of graphene, graphene oxide, carbon black, carbon nanotubes, and fullerenes.
하드 마스크 조성물을 균일한 두께로 코팅하기 위해서, 상기 탄소 동소체는 일 방향의 길이가 500 nm 이하일 수 있다. 일례로, 상기 탄소 동소체로서 그래핀이나 그래핀 옥사이드과 같은 2차원 탄소 동소체를 이용하는 경우, 2차원 탄소 동소체에는 면내 방향을 따르는 복수개의 가상 직선들이 존재한다. 상기 가상 직선들 각각이 2차원 탄소 동소체의 외곽선과 교차하는 2개의 지점 사이의 직선거리들 중에서 최대 거리가 500 nm 이하일 수 있다. 상기 탄소 동소체로서 탄소나노튜브와 같이 1차원 탄소 동소체를 이용하는 경우, 장축의 연장 방향으로의 길이가 500 nm 이하일 수 있다. 상기와 같이 일 방향으로의 길이가 500 nm 이하인 탄소 동소체를 이용함으로써 200 nm 내지 400 nm의 균일한 두께의 코팅막을 형성할 수 있다. 예를 들어, 생산현장에서 사용하는 하드마스크의 두께인 300 nm의 두께를 균일하게 형성할 수 있다.In order to coat the hard mask composition with a uniform thickness, the carbon allotrope may have a length in one direction of 500 nm or less. For example, when using a two-dimensional carbon allotrope such as graphene or graphene oxide as the carbon allotrope, a plurality of virtual straight lines along the in-plane direction exist in the two-dimensional carbon allotrope. The maximum distance among the linear distances between two points where each of the virtual straight lines intersects the outline of the two-dimensional carbon allotrope may be 500 nm or less. When using a one-dimensional carbon allotrope, such as carbon nanotubes, as the carbon allotrope, the length in the extending direction of the long axis may be 500 nm or less. As described above, a coating film having a uniform thickness of 200 nm to 400 nm may be formed by using a carbon allotrope having a length in one direction of 500 nm or less. For example, the thickness of 300 nm, which is the thickness of the hard mask used in the production site, may be uniformly formed.
상기 탄소 동소체는, 유기 용매에의 분산성을 높이고, 또는 고분자 바인더와의 상호작용을 높이기 위한 작용기가 그래프팅된(grafting) 탄소 동소체일 수 있다. 여기서, 상기 작용기는 알킬기, 페닐기, 치환기로서 적어도 하나의 알킬기를 포함하는 페닐기 또는 아로마틱 고리기를 포함할 수 있다. 이때, “치환기로서 적어도 하나의 알킬기를 포함하는 페닐기”는, 페닐기의 수소들 중에서 적어도 1개가 알킬기로 치환된 작용기를 의미한다. 또한, “아로마틱 고리기”는 아릴기(aryl group) 또는 헤테로아릴기(hetero aryl group)을 포함한다.The carbon allotrope may be a carbon allotrope grafted with a functional group for enhancing dispersibility in an organic solvent or enhancing interaction with a polymer binder. Here, the functional group may include an alkyl group, a phenyl group, a phenyl group or an aromatic ring group including at least one alkyl group as a substituent. In this case, “a phenyl group including at least one alkyl group as a substituent” means a functional group in which at least one of hydrogens in the phenyl group is substituted with an alkyl group. In addition, an "aromatic ring group" includes an aryl group or a heteroaryl group.
이러한 작용기를 가지지 않는 탄소 동소체에 비해 이와 같이 그래프팅된 탄소 동소체는 유기 용매 및/또는 고분자 바인더와 친화성이 높아져 더욱 잘 분산될 수 있다. Compared with the carbon allotrope which does not have such a functional group, the grafted carbon allotrope can have a high affinity with an organic solvent and / or a polymeric binder, and thus can be more dispersed.
상기 하드 마스크 조성물은 상기 유기 용매에 상기 탄소 동소체가 용이하게 분산되도록 하는 계면 활성제를 더 포함할 수 있다.The hard mask composition may further include a surfactant to easily disperse the carbon allotrope in the organic solvent.
다른 측면으로서, 본 발명은, 고분자 바인더가 유기 용매에 용해되고 상기 유기 용매 내에 탄소동소체가 분산된 용액을 준비하고, 상기 용액의 용매를 증발시킴을 포함하는 하드 마스크 제조 방법을 제공한다.In another aspect, the present invention provides a hard mask manufacturing method comprising preparing a solution in which a polymer binder is dissolved in an organic solvent and a carbon allotrope is dispersed in the organic solvent, and evaporating the solvent of the solution.
이때, 상기 용액은 상기 유기 용매에 상기 탄소 동소체가 용이하게 분산되도록 하는 계면 활성제를 더 포함할 수 있다.In this case, the solution may further include a surfactant to easily disperse the carbon allotrope in the organic solvent.
또 다른 측면으로서, 본 발명은 하드 마스크는 결정성 부분을 포함하는 결정성 고분자 또는 탄소동소체를 포함하는 하드 마스크를 제공한다.As another aspect, the present invention provides a hard mask comprising a crystalline polymer or carbon allotrope comprising a crystalline portion.
여기서, 상기 탄소 동소체는 그래핀, 그래핀 옥사이드, 카본블랙, 탄소나노튜브 또는 풀러렌 중 어느 하나일 수 있고, 상기 설명한 그래프팅된(grafting) 탄소 동소체일 수 있다.Here, the carbon allotrope may be any one of graphene, graphene oxide, carbon black, carbon nanotubes, or fullerene, and may be the grafted carbon allotrope described above.
일 실시예에서, 상기 하드 마스크는 200 nm 내지 400 nm의 균일한 두께를 가질 수 있고, 이때, 상기 탄소 동소체는 일 방향의 길이가 500 nm 이하일 수 있다.In one embodiment, the hard mask may have a uniform thickness of 200 nm to 400 nm, wherein the carbon allotrope may have a length in one direction of 500 nm or less.
바람직하게, 상기 탄소 동소체는 이의 장축에 따라 일 방향으로 배향되어 있음을 특징으로 하고, 탄소 동소체의 유기 마스크 내의 배향성을 높임은 유기 마스크의 플로린계 플라즈마에 내에칭성을 높여줄 수 있다.Preferably, the carbon allotrope is oriented in one direction along its long axis, and increasing the orientation in the organic mask of the carbon allotrope can increase the etching resistance to the florin-based plasma of the organic mask.
본 발명의 하드 마스크는 용액 공정으로 쉽고 저렴하게 표면 거칠가가 낮고, 균일한 하드 마스크를 제공할 수 있다.The hard mask of the present invention can provide a uniform hard mask with low surface roughness easily and inexpensively in a solution process.
본 발명의 하드 마스크는 거칠기가 수 내지 수십 나노 이하이며, 플로린계 가스(SF6 또는 CF4)를 포함하는 가스의 플라즈마에 높은 내에칭성을 가진다.The hard mask of the present invention has a roughness of several tens to several tens of nanometers or less, and has high resistance to plasma of a gas containing florin-based gas (SF 6 or CF 4 ).
도 1은 하드마스크의 패턴을 위한 AAO의 준비 및 이의 전사를 예시하는 도면이다.1 is a diagram illustrating preparation of an AAO for a pattern of a hard mask and transfer thereof.
도 2는 하드마스크의 패턴을 위한 식각과 피식각층의 하드마스크 패턴에 따른 식각 공정을 예시하는 도면이다.FIG. 2 is a diagram illustrating an etching process according to an etching for a pattern of a hard mask and a hard mask pattern of an etched layer.
도 3은 본 발명의 하드 마스크가 결정성 부분을 가진 결정성 하드마스크일 수 있음을 예시하는 도면이다.3 is a diagram illustrating that the hard mask of the present invention may be a crystalline hard mask having a crystalline portion.
도 4는 탄소동소체가 본 발명의 하드 마스크 내에 일정 방향으로 배향되어 있음을 예시하는 도면이다.4 is a diagram illustrating that the carbon allotrope is oriented in a predetermined direction in the hard mask of the present invention.
1. One. 탄소동소체의Carbon allotrope 그래프팅에Grafting 따른 표면 기능화 Surface functionalization
탄소동소체를 포함하는 하드마스크 필름을 제조하기 위해, 탄소동소체 물질을 용매에 분산시키거나 용해시킬 수 있어야 한다. 산화된 카본물질을 준비하고, 유기 용매에서 용해도를 높일 수 있는 알킬기 또는 페닐기와 같은 작용기를 포함하는 유기화합물을 상기 산화된 카본물질에 그래프팅 시킨다.In order to produce a hardmask film comprising a carbon allotrope, it must be possible to disperse or dissolve the carbon allotrope material in a solvent. An oxidized carbon material is prepared, and an organic compound including a functional group such as an alkyl group or a phenyl group capable of increasing solubility in an organic solvent is grafted onto the oxidized carbon material.
탄소동소체의 일종인 그래핀의 표면 기능화를 예로 들면, 그래핀의 표면 기능화를 위해서 먼저, 그라파이트 플레이크(graphite flake)와 질산나트륨(sodium nitrate)을 황산(sulfuric acid)에 넣은 후, 0℃에서 냉각된 용기에 넣어 잘 섞어 준 다음 과망간산칼륨(potassium permanganate)를 넣는다. 준비된 용액을 물로 희석시킨 다음 3% 농도의 과산화수소(hydrogen peroxide) 처리를 하여 산화그라파이트(graphite oxide)를 얻을 수 있다.For example, the surface functionalization of graphene, a kind of carbon allotrope, for graphite surface functionalization, first, graphite flake and sodium nitrate are added to sulfuric acid, and then cooled at 0 ° C. Mix well, and then add potassium permanganate. The prepared solution may be diluted with water and treated with hydrogen peroxide at a concentration of 3% to obtain graphite oxide.
이어서, 산화그라파이트를 건조시키고, 건조된 산화그라파이트 50 mg을 둥근 플라스크에 넣고 무수디메틸포름아미드(anhydrous dimethylformamide(DMF)) 5 mL를 추가한 다음, 질소 분위기에서 교반하여 서스펜션(suspension)을 제조한다. 이렇게 제조된 서스펜션에 유기 이소시아네이트(organic isocyante) 2 mmol을 첨가하고 약 24 시간동안 교반시키며, 슬러리가 형성되면 혼합물에 메틸렌클로라이드(methylene chloride) 50 mL에 넣고 응고시킨다. 필터링을 한 후, 추가적으로 메틸클로라이드 50 mL을 이용하여 세척 후 건조 한다.Then, the graphite oxide is dried, 50 mg of dried graphite oxide is placed in a round flask, and 5 mL of anhydrous dimethylformamide (DMF) is added, followed by stirring in a nitrogen atmosphere to prepare a suspension. 2 mmol of organic isocyante is added to the thus prepared suspension and stirred for about 24 hours. When a slurry is formed, the mixture is added to 50 mL of methylene chloride and solidified. After filtering, additionally wash with 50 mL of methyl chloride and dry.
상기와 같은 공정을 거친 산화그라파이트는 페닐 이소시아네이트기(phenyl isocyanate group)에 기능화되어 DMF에 쉽게 용해되고, 0.1%(w/v) 농도에서 10시간의 초음파 처리 과정을 거치면 DMF에 분산된 그라핀(graphene) 용액을 얻을 수 있다. 이때, 기능화된 산화그라파이트는 DMF 이외에도 N-메틸피롤리딘(N-methylpyrrolidone, NMP), 디메틸 술폭사이드(dimethyl sulfoxide, DMSO), 헥사메틸포스포아미드(hexamethylphosphoramide, HMPA) 등의 다른 극성용매에도 용이하게 분산될 수 있다.Graphite oxide, which has undergone the above process, is functionalized in a phenyl isocyanate group and easily dissolved in DMF, and graphene dispersed in DMF after sonication for 10 hours at 0.1% (w / v) concentration ( graphene) solution can be obtained. At this time, functionalized graphite oxide is easy to other polar solvents such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) and hexamethylphosphoramide (HMPA) in addition to DMF. Can be distributed.
2. 하드마스크 제조2. Hardmask Manufacturing
용액 공정으로 하드마스크 필름을 제조하기 위해, 유기 용매에 고분자 바인더를 용해시키고, 탄소 동소체 또는 그래프팅에 따른 표면 기능화된 탄소동소체를 상기 유기 용매에 분산 또는 용해시켜 하드마스크 조성물 용액을 준비한다.In order to prepare a hard mask film by a solution process, a polymer binder is dissolved in an organic solvent, and a carbon mask or surface functionalized carbon allotrope according to grafting is dispersed or dissolved in the organic solvent to prepare a hard mask composition solution.
준비된 하드마스크 조성물 용액을 피식각층(예를 들어, SiO2 또는 Si)에 스핀 코팅과 같은 용액 공정에 의해 균일한 두께의 하드마스크 층을 제조한다.The prepared hard mask composition solution is prepared on a layer to be etched (eg SiO 2 or Si) by a solution process such as spin coating to prepare a hard mask layer having a uniform thickness.
일례로, 그라핀이 DMF 분산된에 용액에, 그라핀 중량의 10 내지 30% 분율로 폴리스티렌(polystyrene, PS)을 용해시키고, PS와 표면개질된 그래핀이 분산되어 용액을 스핀코터를 이용하여 200 nm 내지 300 nm의 두께로 성막시키고 200℃에서 10시간 동안 어닐링(annealing)하여 잔류 용매의 제거와 그래핀의 환원을 실시함으로써 하드 마스크 필름을 제조할 수 있다. 이때, PS 이외에도 DMF에 용해되는 고분자(ex.polypropylene(PP), plyvinylalcohol(PVA), polyvinylchloride(PVC))를 이용할 수도 있다.For example, in a solution in which graphene is dispersed in DMF, polystyrene (PS) is dissolved in a 10-30% fraction of the graphene weight, and PS and surface-modified graphene are dispersed to prepare a solution using a spin coater. The hard mask film may be prepared by forming a film with a thickness of 200 nm to 300 nm and annealing at 200 ° C. for 10 hours to remove residual solvent and reduce graphene. In this case, in addition to PS, polymers (ex. Polypropylene (PP), plyvinylalcohol (PVA), polyvinylchloride (PVC)) dissolved in DMF may be used.
3. 3. 하드마스크의Hardmask 패턴화 및  Patterning and 피식각층Etched layer 식각Etching
도 1에서 참조되는 바와 같이, 알루미늄의 양극산화에 의해 원통형 나노 구멍을 가지는 AAO(anodized aluminum oxide) 필름을 준비하고, 용매 내에서 전압을 인가하여 AAO 층만을 알루미늄으로부터 분리하고 준비된 이를 준비된 하드마스크 필름 상에 전사 시킨다.As shown in FIG. 1, an anodized aluminum oxide (AAO) film having cylindrical nanopores was prepared by anodizing aluminum, and only a AAO layer was separated from aluminum by applying a voltage in a solvent, and the prepared hardmask film Transfer to the phase.
도2에서 참조되는 바와 같이, 산소 플라즈마에 의해 AAO 패턴에 대응하는 원통형 나노 구멍 패턴을 하드마스크에 형성한다. AAO를 제거하고 하드마스크의 패턴에 의해 노출된 피식각층을 플로린계(CF4) 플라즈마에 의해 식각한다.As referred to in Fig. 2, a cylindrical nano hole pattern corresponding to the AAO pattern is formed in the hard mask by oxygen plasma. The AAO is removed and the etched layer exposed by the pattern of the hard mask is etched by a florin-based (CF 4 ) plasma.
4. 4. 하드마스크의Hardmask 결정성 향상 Improved crystallinity
결정성 고분자를 포함하는 하드 마스크를 제조하기 위해서, 하드마스크 조성물 용액을 용액 공정에 의해 하드 마스크 필름 제조 후 결정성 고분자의 녹는점보다 높은 온도로 가열시킨 후 냉각 속도의 제어에 따라, 도3에서와 같은, 결정 구조를 형성한다.In order to manufacture a hard mask including a crystalline polymer, the hard mask composition solution is heated to a temperature higher than the melting point of the crystalline polymer after manufacturing the hard mask film by a solution process, and then, according to the control of the cooling rate, To form a crystal structure, such as.
다른 방법으로서, 고분자 바인더로서, 결정 구조를 만들 수 있는 물질, 예컨대 액정 물질를 사용하여 결정 구조를 형성할 수 있다.Alternatively, as the polymer binder, a material capable of forming a crystal structure, such as a liquid crystal material, may be used to form the crystal structure.
5. 탄소 동소체의 5. Carbon allotropes 하드마스크Hard mask 내의 배향 Orientation
하드 마스크 내에서 장축에 따라 일 방향으로 배향되는 구조의 탄소 동소체를 하드 마스크를 제조하기 위해서, 탄소동소체와 고분자 바인더의 용액 공정에 의해 제조된 필름을 고분자 바인더에 유동성을 줄 수 있는 용매(예를 들어 기상 용매)에 노출 시킨 후 흐름을 주어, 도 4에서와 같은, 탄소 동소체를 배향시킬 수 있다.In order to produce a hard mask of a carbon allotrope of a structure oriented in one direction along a major axis in the hard mask, a film prepared by a solution process of a carbon allotrope and a polymer binder may be used as a solvent to give fluidity to the polymer binder (e.g., For example, a gaseous solvent) and then a flow to give a carbon allotrope, as shown in FIG.

Claims (16)

  1. 고분자 바인더, 탄소동소체 및 유기용매를 포함하는 하드 마스크 조성물.A hard mask composition comprising a polymer binder, a carbon allotrope, and an organic solvent.
  2. 제1항에 있어서,The method of claim 1,
    상기 고분자 바인더는The polymer binder is
    폴리에스테르, 폴리카보네이트, 폴리비닐알코올, 폴리비닐부티랄, 폴리아세탈, 폴리아릴레이트, 폴리아마이드, 폴리아미드이미드, 폴리에테르이미드, 폴리페닐렌에테르, 폴리페닐렌설파이드, 폴리에테르설폰, 폴리에테르케톤, 폴리프탈아마이드, 폴리에테르니트릴, 폴리에테르설폰, 폴리벤즈이미다졸, 폴리카보디이미드, 폴리실록산, 폴리메틸메타크릴레이트, 폴리메타크릴아마이드, 니트릴고무, 아크릴 고무, 폴리에틸렌테트라플루오라이드, 에폭시 수지, 페놀 수지, 멜라민 수지, 우레아 수지, 폴리부텐, 폴리펜텐, 에틸렌-프로필렌 공중합체, 에틸렌-부텐-디엔 공중합체, 폴리부타디엔, 폴리이소프렌, 에틸렌-프로필렌-디엔 공중합체, 부틸고무, 폴리메틸펜텐, 폴리스티렌, 스티렌-부타디엔 공중합체, 수첨스티렌-부타디엔 공중합체, 수첨폴리이소프렌 및 수첨폴리부타디엔으로 구성된 군에서 선택되는 1종 이상인,Polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylate, polyamide, polyamideimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyether ketone , Polyphthalamide, polyethernitrile, polyethersulfone, polybenzimidazole, polycarbodiimide, polysiloxane, polymethylmethacrylate, polymethacrylamide, nitrile rubber, acrylic rubber, polyethylenetetrafluoride, epoxy resin, Phenolic resin, melamine resin, urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene, Polystyrene, Styrene-Butadiene Copolymer, Hydrogenated Styrene-Butadiene Copolymer, Hydrogenated Polyisop At least one member selected from the group consisting of styrene and hydrogenated polybutadiene,
    하드 마스크 조성물.Hard mask composition.
  3. 제1항에 있어서,The method of claim 1,
    상기 고분자 바인더는 결정성 부분을 포함하는 결정성 고분자인,The polymer binder is a crystalline polymer containing a crystalline portion,
    하드 마스크 조성물.Hard mask composition.
  4. 제1항에 있어서,The method of claim 1,
    상기 탄소 동소체는The carbon allotrope is
    그래핀, 그래핀 옥사이드, 카본블랙, 탄소나노튜브 및 풀러렌 중 어느 하나인,One of graphene, graphene oxide, carbon black, carbon nanotube and fullerene,
    하드 마스크 조성물.Hard mask composition.
  5. 제1항에 있어서,The method of claim 1,
    상기 탄소 동소체는The carbon allotrope is
    유기 용매에 가용성을 가지는 작용기에 의해 그래프팅된(grafting) 탄소 동소체임을 특징으로 하는,Characterized in that it is a carbon allograft grafted by a functional group soluble in an organic solvent,
    하드 마스크 조성물.Hard mask composition.
  6. 제5항에 있어서,The method of claim 5,
    상기 작용기는 알킬기, 페닐기, 치환기로서 알킬기를 포함하는 페닐기 또는 아로마틱 고리기를 포함하는,The functional group includes an alkyl group, a phenyl group, a phenyl group containing an alkyl group as a substituent or an aromatic ring group,
    하드 마스크 조성물.Hard mask composition.
  7. 제1항에 있어서,The method of claim 1,
    상기 탄소 동소체는 일 방향으로의 길이가 500 nm 이하인 것을 특징으로 하는,The carbon allotrope is characterized in that the length in one direction is 500 nm or less,
    하드 마스크 조성물.Hard mask composition.
  8. 제1항에 있어서,The method of claim 1,
    상기 유기 용매에 상기 탄소 동소체가 용이하게 분산되도록 하는 계면 활성제를 더 포함하는,Further comprising a surfactant to easily disperse the carbon allotrope in the organic solvent,
    하드 마스크 조성물.Hard mask composition.
  9. 고분자 바인더가 유기 용매에 용해되고 상기 유기 용매 내에 탄소동소체가 분산된 용액을 준비하고,Preparing a solution in which a polymer binder is dissolved in an organic solvent and a carbon allotrope is dispersed in the organic solvent,
    상기 용액의 용매를 증발시킴을 포함하는Evaporating the solvent of the solution
    하드 마스크 제조 방법.Hard mask manufacturing method.
  10. 제9항에 있어서,The method of claim 9,
    상기 용액은 탄소동소체가 유기용매에 용이하게 분산되도록 하는 계면활성제를 더 포함하는,The solution further includes a surfactant to easily disperse the carbon allotrope in the organic solvent,
    하드 마크스 제조 방법.Hard mark manufacturing method.
  11. 하드 마스크는 결정성 부분을 포함하는 결정성 고분자 또는 탄소 동소체를 포함하는 하드 마스크.The hard mask comprises a crystalline polymer or carbon allotrope comprising a crystalline portion.
  12. 제11항에 있어서,The method of claim 11,
    상기 탄소 동소체는 그래핀, 그래핀 옥사이드, 카본블랙, 탄소나노튜브 또는 풀러렌 중 어느 하나인,The carbon allotrope is any one of graphene, graphene oxide, carbon black, carbon nanotube or fullerene,
    하드 마스크.Hard mask.
  13. 제11항에 있어서,The method of claim 11,
    상기 탄소 동소체는 이의 장축에 따라 일 방향으로 배향되어 있음을 특징으로 하는,The carbon allotrope is characterized in that it is oriented in one direction along its long axis,
    하드 마스크.Hard mask.
  14. 제11항에 있어서,The method of claim 11,
    상기 하드 마스크는, 플로린 계열의 플라즈마에 내식성을 가짐을 특징으로 하는,The hard mask, characterized in that having a corrosion resistance to the plasma of the Florin-based,
    하드 마스크.Hard mask.
  15. 제11항에 있어서,The method of claim 11,
    200 nm 내지 400 nm의 균일한 두께를 갖는 하드 마스크.Hard mask having a uniform thickness of 200 nm to 400 nm.
  16. 제15항에 있어서,The method of claim 15,
    상기 탄소 동소체의 일 방향으로의 길이가 500 nm 이하인 것을 특징으로 하는 하드 마스크.The length of the carbon allotrope in one direction is 500 nm or less, The hard mask characterized by the above-mentioned.
PCT/KR2016/001379 2015-02-13 2016-02-11 Hard-mask composition comprising solution processable carbon allotropes, method for manufacturing hard-mask using same, and hard-mask WO2016129927A1 (en)

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