WO2016129927A1 - Composition de masque dur comprenant des allotropes du carbone pouvant être mis en œuvre en solution, procédé de fabrication de masque dur utilisant cette dernière et masque dur - Google Patents
Composition de masque dur comprenant des allotropes du carbone pouvant être mis en œuvre en solution, procédé de fabrication de masque dur utilisant cette dernière et masque dur Download PDFInfo
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- 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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- 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
Definitions
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Drying Of Semiconductors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
La présente invention se rapporte : à une composition de masque dur pour un masque dur organique qui a une grande résistance à la gravure et qui peut être mise en œuvre en solution, la composition de masque dur comprenant un liant polymère, des allotropes du carbone et un solvant organique ; à un procédé de fabrication d'un tel masque dur ; et à un masque dur.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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KR20150022214 | 2015-02-13 | ||
KR10-2015-0022214 | 2015-02-13 | ||
KR10-2015-0028083 | 2015-02-27 | ||
KR1020150028083A KR20160100172A (ko) | 2015-02-13 | 2015-02-27 | 용액 공정 가능한 탄소 동소체를 포함하는 하드 마스크 조성물, 이 조성물을 이용하여 하드마스크를 제조하는 방법 및 하드마스크 |
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WO2016129927A1 true WO2016129927A1 (fr) | 2016-08-18 |
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PCT/KR2016/001379 WO2016129927A1 (fr) | 2015-02-13 | 2016-02-11 | Composition de masque dur comprenant des allotropes du carbone pouvant être mis en œuvre en solution, procédé de fabrication de masque dur utilisant cette dernière et masque dur |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107337861A (zh) * | 2017-09-05 | 2017-11-10 | 多凌新材料科技股份有限公司 | 具有抗溶剂性的石墨烯‑丁基橡胶材料、其制法和应用 |
EP3343592A1 (fr) * | 2016-12-27 | 2018-07-04 | Samsung Electronics Co., Ltd. | Composition de masque dur, procédé de formation d'un motif utilisant la composition de masque dur et masque dur formé à partir de la composition de masque dur |
CN110651003A (zh) * | 2017-05-16 | 2020-01-03 | 株式会社钟化 | 薄膜制造用涂料、以及薄膜的制造方法 |
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 |
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WO2013117908A1 (fr) * | 2012-02-10 | 2013-08-15 | The University Of Birmingham | Matériau de masque dur déposé par rotation |
KR20150002953A (ko) * | 2013-06-27 | 2015-01-08 | 제일모직주식회사 | 하드마스크 조성물, 이를 사용한 패턴 형성 방법 및 상기 패턴을 포함하는 반도체 집적회로 디바이스 |
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JPH11274470A (ja) * | 1998-03-26 | 1999-10-08 | Nec Corp | 単一電子素子の製造方法 |
JP2004333805A (ja) * | 2003-05-07 | 2004-11-25 | Fuji Xerox Co Ltd | レジスト組成物 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3343592A1 (fr) * | 2016-12-27 | 2018-07-04 | Samsung Electronics Co., Ltd. | Composition de masque dur, procédé de formation d'un motif utilisant la composition de masque dur et masque dur formé à partir de la composition de masque dur |
US10424490B2 (en) | 2016-12-27 | 2019-09-24 | Samsung Electronics Co., Ltd. | Hardmask composition, method of forming pattern using the hardmask composition, and hardmask formed from the hardmask composition |
CN110651003A (zh) * | 2017-05-16 | 2020-01-03 | 株式会社钟化 | 薄膜制造用涂料、以及薄膜的制造方法 |
CN110651003B (zh) * | 2017-05-16 | 2021-10-26 | 株式会社钟化 | 薄膜制造用涂料、以及薄膜的制造方法 |
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 |
CN107337861A (zh) * | 2017-09-05 | 2017-11-10 | 多凌新材料科技股份有限公司 | 具有抗溶剂性的石墨烯‑丁基橡胶材料、其制法和应用 |
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