KR20070122250A - Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof - Google Patents
Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof Download PDFInfo
- Publication number
- KR20070122250A KR20070122250A KR1020060057559A KR20060057559A KR20070122250A KR 20070122250 A KR20070122250 A KR 20070122250A KR 1020060057559 A KR1020060057559 A KR 1020060057559A KR 20060057559 A KR20060057559 A KR 20060057559A KR 20070122250 A KR20070122250 A KR 20070122250A
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- hard mask
- weight
- parts
- underlayer film
- Prior art date
Links
Images
Classifications
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—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
Landscapes
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Architecture (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
도 1은 산화막 상에 산화막 가공용 하층막-레지스트 하층막용 하드마스크-레지스트로 이루어진 다층막의 단면을 도시한 개략도이다.1 is a schematic diagram showing a cross section of a multilayer film formed of an underlayer film-resist for an oxide film processing-hard mask-resist for an underlayer film on an oxide film.
본 발명은 레지스트 하층막용 하드마스크 조성물 및 이를 이용한 반도체 집적회로 디바이스의 제조방법에 관한 것이다. 보다 구체적으로 우수한 막특성과 저장안정성을 가지며 하드마스크 특성이 우수하여 재료층에 훌륭한 패턴을 전사할 수 있고, 노광 후 현상시 발생하는 레지듀(residue)의 양을 최소화 할 레지스트의 하층막용 조성물에 관한 것이다.The present invention relates to a hard mask composition for a resist underlayer film and a method for manufacturing a semiconductor integrated circuit device using the same. More specifically, it has excellent film characteristics and storage stability, and has excellent hard mask characteristics, so that it can transfer a good pattern to a material layer, and to a composition for a lower layer film of a resist that will minimize the amount of residue generated during development after exposure. It is about.
대부분의 리소그래피(lithography) 공정은 레지스트 재료층과 기판간의 반사성을 최소화시키는데, 반사방지코팅재료(ARC; anti-reflective coating)를 사용하여 해상도를 증가시킨다. 그러나 이러한 ARC 재료들은 층들의 유사한 기본조성으로 인하여 이미지가 새겨진 레지스트층에 대해 나쁜 에치선택성(etch selectivity)을 나타낸다. 그러므로, 패터닝 후 ARC의 에칭중에 많은 레지스트층도 소모되어, 후속 에칭 단계 중에 추가의 패터닝이 필요하게 되었다.Most lithography processes minimize the reflectivity between the layer of resist material and the substrate, using an anti-reflective coating (ARC) to increase the resolution. However, these ARC materials exhibit poor etch selectivity for the imaged resist layer due to the similar basic composition of the layers. Therefore, many resist layers were also consumed during the etching of ARC after patterning, requiring further patterning during subsequent etching steps.
또한, 일부 리소그래피 기술의 경우, 사용된 레지스트 재료는 레지스트 재료 아래에 놓인 층에 소정의 패턴을 효과적으로 전사할 수 있을 정도로 높은, 후속 에칭 단계에 대한 내성을 갖지 않는다. 따라서, 예를 들면, 레지스트 물질이 극히 얇게 사용되는 경우, 에칭하고자 하는 기판이 두꺼운 경우, 에칭 깊이가 깊게 요구되는 경우, 소정의 기판층에 대해 특정한 에칭제를 사용하는 것이 필요한 경우, 또는 상기 경우의 임의의 조합들에서 레지스트 하층막용 하드마스크가 사용되어져 왔다. In addition, for some lithography techniques, the resist material used is not resistant to subsequent etching steps, which is high enough to effectively transfer the desired pattern to the layer underlying the resist material. Thus, for example, when the resist material is used extremely thin, when the substrate to be etched is thick, when the etching depth is required deeply, when it is necessary to use a specific etchant for a given substrate layer, or in the case In any combination of the following, a hard mask for resist underlayer film has been used.
레지스트 하층막용 하드마스크는 패터닝된 레지스트와 패터닝하고자 하는 기판 간의 중간층 역할을 한다. 레지스트 하층막용 하드마스크는 패터닝된 레지스트의 패턴을 기판으로 전사한다. 그러므로, 레지스트 하층막용 하드마스크층은 패턴을 전사하는 데 요구되는 에칭 공정을 견딜 수 있어야 한다.The hard mask for the resist underlayer film serves as an intermediate layer between the patterned resist and the substrate to be patterned. The hard mask for resist underlayer film transfers the pattern of the patterned resist to a substrate. Therefore, the hard mask layer for resist underlayer film must be able to withstand the etching process required to transfer the pattern.
예를 들어, 실리콘 산화막 등의 기판을 가공할 때, 레지스트 패턴을 마스크로 사용하지만, 회로의 미세화로 레지스트의 두께가 얇아졌기 때문에 레지스트의 마스크로서의 역할이 힘들게 되어, 손상을 주지 않고 산화막을 가공하는 것이 곤란하게 되었다. 이를 해결하기 위해서, 레지스트 패턴을 우선 산화막 가공용 하층막에 전사한 후, 이 막을 마스크로서 산화막에 드라이 에칭 가공하는 공정이 취해진다. 산화막 가공용 하층막이란 하층 반사막을 겸하면서 반사방지막의 하층에 형성되는 막을 뜻한다. 이 공정에서는 레지스트와 산화막 가공용 하층막의 에칭속도가 비슷하기 때문에 레지스트와 상기 하층막사이에 이 하층막을 가공할 수 있는 마스 크를 형성할 필요가 있다. 즉, 산화막 상에 산화막 가공용 하층막-하층막 가공용 마스크(레지스트 하층막용 하드마스크)-레지스트로 이루어진 다층막이 구성되게 된다 (도 1 참조).For example, when processing a substrate such as a silicon oxide film, a resist pattern is used as a mask, but since the thickness of the resist becomes thin due to the miniaturization of the circuit, the role of the resist mask becomes difficult, and the oxide film is processed without damage. It became difficult. In order to solve this problem, a process of first transferring a resist pattern to an underlayer film for oxide film processing and then performing dry etching processing on the oxide film as a mask as a mask is performed. The underlayer film for oxide film processing means a film formed under the antireflection film while also serving as a lower reflection film. In this step, since the etching rate of the resist and the underlayer film for processing an oxide film is similar, it is necessary to form a mask for processing the underlayer film between the resist and the underlayer film. That is, a multilayer film made of an oxide film processing underlayer film-underlayer film processing mask (resist underlayer film hard mask) -resist is formed on the oxide film (see FIG. 1).
일본특허공개 제2000-0077018호에서는 상기와 같은 효과를 얻고자 RaSi(OR)4-a 등의 실란화합물의 축합 생성물을 레지스트 하층막용 물질로 사용하고 있다. 그러나, 실란화합물의 경우 존재하는 Si-OH가 친핵성반응(nucleophilic reaction)을 할 수 있고, 또 산성이기 때문에 레지스트와 반응하여 노광 후 세척 시 레지듀가 패턴에 남아 있을 염려가 있었다. In Japanese Patent Laid-Open No. 2000-0077018, a condensation product of a silane compound such as R a Si (OR) 4-a is used as a material for resist underlayer film in order to obtain the same effect as described above. However, in the case of the silane compound, since the present Si-OH can undergo a nucleophilic reaction and is acidic, there is a concern that the residue may remain in the pattern during the post-exposure cleaning by reacting with the resist.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 우수한 막특성과 저장안정성을 가지며 하드마스크 특성이 우수하여 재료층에 훌륭한 패턴을 전사할 수 있는 레지스트 하층막용 하드마스크 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, to provide a hard mask composition for a resist underlayer film capable of transferring an excellent pattern to the material layer having excellent film properties and storage stability and excellent hard mask properties. The purpose.
특히, 본 발명에 의해 하드마스크를 제조할 경우 노광 후 현상시 발생하는 레지듀(residue)의 양을 최소화시킬 수 있는 레지스트 하층막용 하드마스크 조성물을 제공하는 것을 목적으로 한다.In particular, an object of the present invention is to provide a hard mask composition for a resist underlayer film capable of minimizing the amount of residue generated during development after exposure.
또한 본 발명은 상기 레지스트 하층막용 하드마스크 조성물을 사용하여 반도체 집적회로 디바이스를 제조하는 제조방법 및 그 제조방법에 의해 제조된 디바이스를 제공하는 것을 또 다른 목적으로 한다.Another object of the present invention is to provide a manufacturing method for manufacturing a semiconductor integrated circuit device using the hard mask composition for resist underlayer film, and a device manufactured by the manufacturing method.
본 발명은 산 촉매 하에서 하기 화학식 1, 2 및 3으로 표시되는 화합물들로부터 생성되는 유기실란계 중합물; 유기염기 또는 유기염기의 유도체; 및 용매를 포함하는 레지스트 하층막용 하드마스크 조성물을 제공한다. The present invention is an organosilane-based polymer produced from the compounds represented by the formula (1), (2) and (3) under an acid catalyst; Organic bases or derivatives of organic bases; And it provides a hard mask composition for a resist underlayer film containing a solvent.
[화학식 1][Formula 1]
[RO]3Si-[CH2]nPh[RO] 3 Si- [CH 2 ] n Ph
(Ph는 페닐, n은 0~2, R은 메틸 또는 에틸)(Ph is phenyl, n is 0-2, R is methyl or ethyl)
[화학식 2][Formula 2]
[RO]3Si-H[RO] 3 Si-H
(R은 메틸 또는 에틸)(R is methyl or ethyl)
[화학식 3][Formula 3]
[RO]3Si-CH3 [RO] 3 Si-CH 3
(R은 메틸 또는 에틸)(R is methyl or ethyl)
상기 유기실란계 중합물의 일 실시예로서 하기 화학식 4, 5 및 6으로 나타내어 지는 가수분해물들의 축중합물일 수 있다.As an example of the organosilane polymer, it may be a condensation product of hydrolyzates represented by the following Chemical Formulas 4, 5, and 6.
[화학식 4][Formula 4]
Ph[CH2]nSi[OH]3 (Ph는 페닐기, n은 0~2)Ph [CH 2 ] n Si [OH] 3 (Ph is phenyl group, n is 0 ~ 2)
[화학식 5][Formula 5]
HSi[OH]3 HSi [OH] 3
[화학식 6][Formula 6]
CH3Si[OH]3 CH 3 Si [OH] 3
상기 축중합물의 일실시예로는 하기 화학식 7로 나타내어 지는 화합물일 수 있다.One embodiment of the condensation polymer may be a compound represented by the following formula (7).
[화학식 7][Formula 7]
(m은 0~2이고, x,y,z는 각각 0.05~0.9이며, x+y+z = 1임.)(m is 0 ~ 2, x, y, z are 0.05 ~ 0.9 and x + y + z = 1)
상기 산 촉매는 질산 (nitric acid), 황산(sulfuric acid), 염산(hydrochloric acid), p-톨루엔 술폰산 수화물(p-toluenesulfonic acid monohydrate), 디에틸설페이트(diethylsulfate)로 이루어진 군에서 1종 이상 선택되는 것일 수 있다.The acid catalyst is nitric acid (nitric acid), sulfuric acid (sulfuric acid), HCl (hydrochloric acid), p - toluenesulfonic acid hydrate (p -toluenesulfonic acid monohydrate), diethyl sulfate (diethylsulfate) is at least one selected from the group consisting of It may be.
상기 유기염기는 1,8-비스(디메틸아미노)나프탈렌(1,8-bis(dimethylamino)naphthalene), 1,3-비스(아미노프로필)테트라메틸디실록산(1,3- bis(aminopropyl)tetramethyldisiloxane), 말단이 아미노프로필로 치환된 폴리디메틸실록산(aminopropyl terminated polydimethylsiloxane) 및 유기 아민 계열로 이루어진 군에서 1종 이상 선택되는 것일 수 있다.The organic base is 1,8-bis (dimethylamino) naphthalene (1,8-bis (dimethylamino) naphthalene), 1,3-bis (aminopropyl) tetramethyldisiloxane (1,3-bis (aminopropyl) tetramethyldisiloxane) The terminal may be one or more selected from the group consisting of aminopropyl-terminated polydimethylsiloxane (aminopropyl terminated polydimethylsiloxane) and organic amine series.
상기 유기염기의 유도체는 유기 아민의 질소원자를 터셔리부틸옥시카르보닐(tert-butyloxycarbonyl)기로 보호한 카바메이트(carbamate)일 수 있다.The derivative of the organic base may be a carbamate in which the nitrogen atom of the organic amine is protected with a tert-butyloxycarbonyl group.
상기 유기 실란계 중합물은 상기 화학식 1로 표시되는 화합물, 상기 화학식 2로 표시되는 화합물과 상기 화학식 3으로 표시되는 화합물의 합 100 중량부를 기준으로 할 때, 상기 화학식 1로 표시되는 화합물 5 내지 90중량부, 상기 화학식 2로 표시되는 화합물 5 내지 90중량부 및 상기 화학식 3로 표시되는 화합물 5내지 90중량부의 혼합물을 0.001중량부 내지 5중량부의 산 촉매와 100 내지 900중량부의 용매 하에서 반응시켜 생성된 것일 수 있다.The organic silane-based polymer is 5 to 90 weight of the compound represented by the formula (1), based on 100 parts by weight of the sum of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3) Part, 5 to 90 parts by weight of the compound represented by Formula 2 and 5 to 90 parts by weight of the mixture represented by Formula 3 are produced by reacting with 0.001 parts by weight to 5 parts by weight of an acid catalyst and 100 to 900 parts by weight of a solvent It may be.
상기 유기 실란계 중합물은 전체 하드마스크 조성물 100중량부에 대하여 1 내지 50중량부 포함될 수 있다. The organic silane-based polymer may include 1 to 50 parts by weight based on 100 parts by weight of the total hard mask composition.
상기 유기염기 또는 그의 유도체는 유기 실란계 중합물 100중량부에 대하여 0.001 내지 5중량부 포함될 수 있다. The organic base or derivative thereof may be included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the organic silane-based polymer.
상기 하드마스크 조성물은 가교제, 라디칼 안정제, 계면활성제로 이루어진 군에서 1종 이상 선택된 첨가제를 더 포함할 수 있다.The hard mask composition may further include at least one additive selected from the group consisting of a crosslinking agent, a radical stabilizer, and a surfactant.
상기 하드마스크 조성물은 피리디늄 p-톨루엔술포네이트(pyridinium p-toluenesulfonate), 아미도설포베타인-16(amidosulfobetain-16), 암모늄 (-)-캠퍼-10-술폰산염((-)-camphor-10-sulfonic acid ammonium salt), 암모늄 포메이 트(ammonium formate), 트리에틸암모늄 포메이트(triethylammonium formate), 트리메틸암모늄 포메이트 (trimethyammonium formate), 테트라메틸암모늄 포메이트 (tetramethylammonium formate), 피리디늄 포메이트 (pyridinium formate)로 이루어진 군에서 선택되는 하나 이상의 화합물을 더 포함할 수 있다. The hardmask composition is pyridinium p-toluenesulfonate (pyridinium p -toluenesulfonate), amino Dorsal Phoebe others -16 (amidosulfobetain-16), ammonium (-) - camphor-10-sulfonate ((-) - camphor-10 -sulfonic acid ammonium salt, ammonium formate, triethylammonium formate, trimethyammonium formate, tetramethylammonium formate, pyridinium formate formate) may further comprise one or more compounds selected from the group consisting of.
상기 하드마스크 조성물은 피리디늄 p-톨루엔술포네이트(pyridinium p-toluenesulfonate), 아미도설포베타인-16(amidosulfobetain-16), 암모늄 (-)-캠퍼-10-술폰산염((-)-camphor-10-sulfonic acid ammonium salt) 등 유기염기의 술폰산염이나 암모늄 포메이트(ammonium formate), 트리에틸암모늄 포메이트(triethylammonium formate), 트리메틸암모늄 포메이트 (trimethyammonium formate), 테트라메틸암모늄 포메이트 (tetramethylammonium formate), 피리디늄 포메이트 (pyridinium formate) 로 이루어진 군에서 선택되는 하나 이상의 화합물 뿐만 아니라 추가로 가교제, 라디칼 안정제, 계면활성제로 이루어진 군에서 1종 이상 선택된 첨가제를 더 포함할 수 있다.The hardmask composition is pyridinium p-toluenesulfonate (pyridinium p -toluenesulfonate), amino Dorsal Phoebe others -16 (amidosulfobetain-16), ammonium (-) - camphor-10-sulfonate ((-) - camphor-10 sulfonic acid salts of organic bases such as sulfonic acid ammonium salt, ammonium formate, triethylammonium formate, trimethyammonium formate, tetramethylammonium formate, It may further include at least one compound selected from the group consisting of pyridinium formate, as well as at least one additive selected from the group consisting of crosslinking agents, radical stabilizers, and surfactants.
또한, 본 발명은 (a) 기판 상에 재료 층을 제공하는 단계; (b) 상기 재료 층 위로 유기물로 이루어진 하드마스크 층을 형성시키는 단계; (c) 상기 유기물로 이루어진 하드마스크 층 위로 상기 본 발명의 레지스트 하층막용 하드마스크 조성물을 코팅하여 반사방지 하드마스크 층을 형성시키는 단계; (d) 상기 반사방지 하드마스크 층 위로 방사선-민감성 이미지화 층을 형성시키는 단계; (e) 상기 방사선-민감성 이미지화 층을 패턴 방식으로 방사선에 노출시킴으로써 상기 방사선-민감성 이미지화 층 내에서 방사선-노출된 영역의 패턴을 생성시키는 단계;(f) 상기 방사 선-민감성 이미지화 층 및 상기 반사방지 하드마스크 층의 부분을 선택적으로 제거하여 상기 유기물로 이루어진 하드마스크 층의 부분을 노출시키는 단계; (g) 패턴화된 반사방지 하드마스크 층 및 상기 유기물로 이루어진 하드마스크 층의 부분을 선택적으로 제거하여 재료층의 부분을 노출시키는 단계; 및 (h) 재료층의 노출된 부분을 에칭함으로써 패턴화된 재료 형상을 형성시키는 단계를 포함하는 것을 특징으로 하는 반도체 집적회로 디바이스의 제조방법을 제공한다.In addition, the present invention provides a method for preparing a substrate comprising: (a) providing a layer of material on a substrate; (b) forming a hardmask layer of organic material over the material layer; (c) coating the hard mask composition for a resist underlayer film of the present invention on the hard mask layer made of the organic material to form an antireflective hard mask layer; (d) forming a radiation-sensitive imaging layer over the antireflective hardmask layer; (e) generating a pattern of radiation-exposed areas within the radiation-sensitive imaging layer by exposing the radiation-sensitive imaging layer to radiation in a patterned manner; (f) the radiation-sensitive imaging layer and the reflection Selectively removing portions of the preventive hardmask layer to expose portions of the hardmask layer of organic material; (g) selectively removing portions of the patterned antireflective hardmask layer and the organic hardmask layer to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer.
또한 본 발명은 상기 제조방법에 의해 제조되어 지는 것을 특징으로 하는 반도체 집적회로 디바이스를 제공한다.The present invention also provides a semiconductor integrated circuit device which is manufactured by the above manufacturing method.
이하 본 발명을 보다 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 레지스트 하층막용 하드마스크 조성물은 산 촉매 하에서 하기 화학식 1, 2 및 3으로 표시되는 화합물들로부터 생성되는 유기실란계 중합물; 유기염기 또는 유기염기의 유도체; 및 용매를 포함한다.The hard mask composition for a resist underlayer film of the present invention is an organosilane-based polymer produced from compounds represented by the following Chemical Formulas 1, 2, and 3 under an acid catalyst; Organic bases or derivatives of organic bases; And solvents.
[화학식 1][Formula 1]
[RO]3Si-[CH2]nPh[RO] 3 Si- [CH 2 ] n Ph
(Ph는 페닐, n은 0~2, R은 메틸 또는 에틸)(Ph is phenyl, n is 0-2, R is methyl or ethyl)
[화학식 2][Formula 2]
[RO]3Si-H[RO] 3 Si-H
(R은 메틸 또는 에틸)(R is methyl or ethyl)
[화학식 3][Formula 3]
[RO]3Si-CH3 [RO] 3 Si-CH 3
(R은 메틸 또는 에틸)(R is methyl or ethyl)
상기 유기실란계 중합물은 상기 화학식 1로 표시되는 화합물, 상기 화학식 2로 표시되는 화합물과 상기 화학식 3으로 표시되는 화합물의 합 100 중량부를 기준으로 할 때, 상기 화학식 1로 표시되는 화합물 5 내지 90중량부와 상기 화학식 2로 표시되는 화합물 5 내지 90중량부 및 상기 화학식 3으로 표시되는 화합물 5 내지 90중량부의 혼합물을 0.001중량부 내지 5중량부의 산촉매와 100 내지 900중량부의 용매 하에서 반응시켜 얻을 수 있다.The organosilane-based polymer is 5 to 90 weight of the compound represented by Formula 1 based on 100 parts by weight of the sum of the compound represented by Formula 1, the compound represented by Formula 2, and the compound represented by Formula 3 Part and a mixture of 5 to 90 parts by weight of the compound represented by Formula 2 and 5 to 90 parts by weight of the compound represented by Formula 3 can be obtained by reacting with 0.001 parts by weight to 5 parts by weight of an acid catalyst and 100 to 900 parts by weight of a solvent. .
상기 반응에서 산촉매 하에서 화학식 1, 화학식 2 및 화학식 3으로 표시되는 화합물로부터 하기 화학식 4, 화학식 5 및 화학식 6으로 표시되는 가수분해물들이 각각 생성될 수 있으며, 이들의 축합중합반응으로 상기 유기 실란계 중합물이 얻어질 수 있다. In the reaction, hydrolyzates represented by the following Chemical Formulas 4, 5, and 6 may be generated from the compounds represented by Chemical Formulas 1, 2, and 3, respectively, under the acid catalyst, and the organic silane-based polymers may be formed by their condensation polymerization. This can be obtained.
[화학식 4][Formula 4]
Ph[CH2]nSi[OH]3 (Ph는 페닐기, n은 0~2)Ph [CH 2 ] n Si [OH] 3 (Ph is phenyl group, n is 0 ~ 2)
[화학식 5][Formula 5]
HSi[OH]3 HSi [OH] 3
[화학식 6][Formula 6]
CH3Si[OH]3 CH 3 Si [OH] 3
상기 화학식 4, 화학식 5 및 화학식 6으로 나타내어지는 가수분해물들의 축합중합반응으로 형성되는 상기 유기 실란계 중합물로는 하기 화학식 7로 나타내어지는 축중합물을 예로 들 수 있다.Examples of the organosilane-based polymer formed by the condensation polymerization reaction of the hydrolyzates represented by Formulas 4, 5, and 6 may be represented by the following formula (7).
[화학식 7][Formula 7]
(m은 0~2이고, x,y,z는 각각 0.05~0.9 이며, x+y+z = 1임.)(m is 0 ~ 2, x, y, z are 0.05 ~ 0.9 and x + y + z = 1).
상기 화학식 1의 화합물이 포함하는 페닐그룹이 DUV(Deep UV) 영역에서 흡수스펙트럼을 나타내는 점을 활용하여 반사방지 특성이 높은 재료를 제공할 수 있다. 이 경우 Ph-기의 농도비를 조절함으로써 특정 파장에서 원하는 흡수도와 굴절률을 가진 하드마스크 조성물을 제공할 수 있다. 화학식 1, 2, 3으로 표시되는 화합물들의 반응시 중량비는 세 화합물의 합이 100중량부라 할 때 상기 화학식 1로 표시되는 화합물은 5 내지 90중량부를 사용하는 것이 바람직하다. 5중량부 미만으로 사 용할 경우 흡광도 저하의 문제가 있으며, 90중량부를 초과하여 사용할 경우에는 Si 함량 저하로 충분한 에치선택비를 확보할 수 없다는 문제점이 발생하게 된다. 또한, 적절한 반사방지 특성을 갖기 위해서는 화학식 1의 상대적인 량을 조절하면 된다. 예를 들자면, 10중량부일때 193nm에서 k(흡수도)값이 0.2정도 얻어진다. The phenyl group included in the compound of Formula 1 may provide a material having high anti-reflective property by utilizing the point that the absorption spectrum is shown in the deep UV region. In this case, by adjusting the concentration ratio of the Ph-group, it is possible to provide a hard mask composition having a desired absorbance and refractive index at a specific wavelength. When the weight ratio of the compounds represented by the formulas (1), (2) and (3) is 100 parts by weight, the compound represented by the formula (1) is preferably used in an amount of 5 to 90 parts by weight. If the amount is less than 5 parts by weight, there is a problem of lowering the absorbance, and if it is used in excess of 90 parts by weight, there is a problem that a sufficient etch selectivity cannot be secured due to the Si content decrease. In addition, in order to have appropriate antireflection properties, the relative amount of Chemical Formula 1 may be adjusted. For example, at 10 parts by weight, a k (absorbance) value of about 0.2 is obtained at 193 nm.
상기 화학식 2 화합물의 상대적 투입량을 늘리면 Si함량을 높일 수가 있다. Si 함량을 조절함에 따라 상부 포토레지스트 층 및 하부 유기물로 이루어진 하드마스크 층 사이의 에치선택비를 부여할 수 있다. 화학식 1, 2, 3으로 표시되는 화합물들의 반응시 중량비는 세개의 합이 100중량부라 할 때 상기 화학식 2로 표시되는 화합물은 5 내지 90중량부를 사용하는 것이 바람직하다. 5중량부 미만으로 사용할 경우 Si 함량 저하로 충분한 에치선택비를 확보할 수 없고, 90중량부를 초과하여 사용할 경우에는 저장안정성 저하의 문제점이 발생하게 된다.Increasing the relative input amount of the compound of Formula 2 may increase the Si content. By controlling the Si content, an etch selectivity between the upper photoresist layer and the hard mask layer composed of the lower organic material may be imparted. When the weight ratio of the compounds represented by the formulas (1), (2) and (3) is 100 parts by weight, the compound represented by the formula (2) is preferably used in an amount of 5 to 90 parts by weight. If the amount is less than 5 parts by weight, it is not possible to secure a sufficient etch selectivity due to the Si content decrease, and when used in excess of 90 parts by weight, a problem of deterioration in storage stability occurs.
상기 화학식 3 화합물의 상대적 투입량을 늘리면 저장안정성을 높일 수 있다. 화학식 1, 2, 3으로 표시되는 화합물들의 반응시 중량비는 세개의 합이 100중량부라 할 때 상기 화학식 3으로 표시되는 화합물은 5 내지 90중량부를 사용하는 것이 바람직하다. 5중량부 미만으로 사용할 경우 저장안정성에 문제가 생기며, 90중량부를 초과하여 사용할 경우에는 흡광도 저하의 문제가 발생하게 된다.Increasing the relative dose of the compound of Formula 3 may increase storage stability. When the weight ratio of the compounds represented by the formulas (1), (2) and (3) is 100 parts by weight, the compound represented by the formula (3) is preferably used in an amount of 5 to 90 parts by weight. If it is used less than 5 parts by weight, there is a problem in the storage stability, when used in excess of 90 parts by weight will cause a problem of lowering the absorbance.
상기 산 촉매는 질산 (nitric acid), 황산(sulfuric acid), 염산(hydrochloric acid) 등 무기산이나, p-톨루엔 술폰산 수화물(p-toluenesulfonic acid monohydrate), 디에틸설페이트(diethylsulfate) 등 유기 술폰산의 알킬 에스테르류로 이루어진 군에서 1종 이상 선택된 것을 사용하는 것이 바람직하다.The acid catalyst is nitric acid (nitric acid), sulfuric acid (sulfuric acid), HCl (hydrochloric acid) or an inorganic acid such as, p - toluenesulfonic acid hydrate (p -toluenesulfonic acid monohydrate), diethyl sulfate (diethylsulfate) such as organic sulfonic acid alkyl esters It is preferable to use one or more selected from the group consisting of.
상기 산촉매는 그 종류, 투입량 및 투입방법을 조절하여 수지 합성 시 가수분해 혹은 축합반응을 적절히 제어할 수 있으며, 상기 유기 실란계 중합물 생성 반응에서는 0.001 내지 5중량부 사용할 수 있다. 0.001 중량부 미만으로 사용한다면, 반응속도가 현저하게 느려지는 문제가 발생하고, 5중량부를 초과하여 사용할 경우에는 반응속도가 너무 빨라서 원하는 분자량의 축합중합물을 얻지 못하는 문제가 발생하게 된다.The acid catalyst may appropriately control the hydrolysis or condensation reaction during the synthesis of the resin by adjusting the type, the amount and the addition method thereof, and 0.001 to 5 parts by weight may be used in the organic silane-based polymer production reaction. If it is used less than 0.001 parts by weight, a problem that the reaction rate is remarkably slow occurs, and when used in excess of 5 parts by weight, the reaction rate is too fast to obtain a problem of obtaining a condensation polymer of the desired molecular weight.
상기 유기 실란계 중합물은 전체 하드마스크 조성물 100중량부에 대해 1~50 중량부 포함하는 것이 바람직하며, 보다 바람직하게는 1~30중량부를 포함한다. 1중량부 미만으로 사용하거나 50중량부를 초과하여 사용하는 경우에는 코팅이 불량하게 되는 문제가 발생한다.It is preferable that the said organic silane type polymer contains 1-50 weight part with respect to 100 weight part of total hardmask compositions, More preferably, it contains 1-30 weight part. If the amount is less than 1 part by weight or more than 50 parts by weight, a problem occurs in that the coating is poor.
상기 유기염기로는 1,8-비스(디메틸아미노)나프탈렌(1,8-bis(dimethylamino)naphthalene), 1,3-비스(아미노프로필)테트라메틸디실록산(1,3-bis(aminopropyl)tetramethyldisiloxane), 말단이 아미노프로필로 치환된 폴리디메틸실록산(aminopropyl terminated polydimethylsiloxane) 및 유기 아민 계열로 이루어진 군에서 1종 이상 선택하여 사용할 수 있다. Examples of the organic base include 1,8-bis (dimethylamino) naphthalene (1,8-bis (dimethylamino) naphthalene), 1,3-bis (aminopropyl) tetramethyldisiloxane (1,3-bis (aminopropyl) tetramethyldisiloxane ), One or more selected from the group consisting of aminopropyl terminated polydimethylsiloxane substituted with aminopropyl terminal and organic amine series can be used.
또한 상기 유기 염기의 유도체로는 상기 유기 아민의 질소원자를 터셔리부틸옥시카르보닐(tert-butyloxycarbonyl)기로 보호한 카바메이트(carbamate)인 것이 바람직하다. 상기 유기 염기의 유도체가 가지고 있는 터셔리부틸카바메이트(tert-butylcarbamate)기는 고온에서 부탄(butane)과 이산화탄소(carbon dioxide)를 만들 어 내면서 본래의 아민을 재생성한다.In addition, the derivative of the organic base is preferably carbamate in which the nitrogen atom of the organic amine is protected by a tert-butyloxycarbonyl group. The tert-butylcarbamate group of the derivative of the organic base regenerates the original amine while producing butane and carbon dioxide at high temperature.
상기 유기염기 또는 유기 염기의 유도체는 상기 유기 실란계 중합물 100중량부에 대해 0.001~5중량부를 포함하는 것이 바람직하다. 0.001 중량부 미만으로 사용한다면, 레지듀의 양을 최소화하는 효과를 얻지 못하며, 5중량부를 초과하여 사용할 경우에는 레지듀는 남지 않지만, 그 정도를 벗어나 언더컷 (undercut)이 생기게 된다.The organic base or derivative of the organic base preferably contains 0.001 to 5 parts by weight based on 100 parts by weight of the organosilane-based polymer. If the amount is less than 0.001 parts by weight, the effect of minimizing the amount of residue is not obtained. If the amount is used more than 5 parts by weight, the residue is not left, but an undercut is generated.
본 발명의 상기 조성물에서 용매는 단독 또는 2종 이상을 혼합하여 사용할 수 있으며, 2 종 이상을 혼합하여 사용할 경우에 적어도 하나는 고비등 용매를 사용한다. 고비등 용매는 보이드(void)를 방지하며, 필름을 저속도로 건조화함으로써 평탄성을 향상시킨다. 여기서, "고비등 용매"란 본 발명 조성물의 코팅, 건조 및 경화시의 온도보다 좀 더 낮은 온도 근처에서 휘발하는 용매를 의미한다. 사용 가능한 용매의 구체예로는 PGMEA(Propylene glycol methyl ether acetate), 에틸락테이트(Ethyl lactate)등을 들 수 있다.In the composition of the present invention, the solvent may be used alone or in combination of two or more, at least one of the high boiling solvent when used in combination of two or more. High boiling solvents prevent voids and improve flatness by drying the film at low speed. Here, "high boiling solvent" means a solvent that volatilates near a temperature lower than the temperature at the time of coating, drying and curing the composition of the present invention. Specific examples of the solvent that can be used include PGMEA (Propylene glycol methyl ether acetate), ethyl lactate (Ethyl lactate) and the like.
본 발명에서는 필요에 따라 상기 조성물에 가교제, 라디칼 안정제, 계면활성제 등을 추가로 1 또는 2 이상 포함할 수 있다. In the present invention, if necessary, the composition may further include one or two or more crosslinking agents, radical stabilizers, surfactants, and the like.
또한, 본 발명에서는 상기 조성물에 피리디늄 p-톨루엔술포네이트(pyridinium p-toluenesulfonate), 아미도설포베타인-16(amidosulfobetain-16), 암모늄 (-)-캠퍼-10-술폰산염((-)-camphor-10-sulfonic acid ammonium salt) 등 유기염기의 술폰산염이나 암모늄 포메이트(ammonium formate), 트리에틸암모늄 포메이트(triethylammonium formate), 트리메틸암모늄 포메이트 (trimethyammonium formate), 테트라메틸암모늄 포메이트 (tetramethylammonium formate), 피리디늄 포메이트 (pyridinium formate) 등 유기 염기의 포름산염으로 이루어진 군에서 하나 이상 선택되는 화합물을 더 포함할 수 있다. 상기 화합물(가교촉매; crosslinking catalyst)은 수지의 가교를 촉진시켜 내에칭성과 내용제성을 향상시키는 역할을 한다. 상기 화합물은 상기 유기실란계 중합물 100 중량부를 기준으로 할 때, 0.0001내지 0.01 중량부 사용하는 것이 바람직하다. 0.0001중량부 미만으로 사용할 경우에는 상기효과를 볼 수 없으며, 0.01중량부를 초과하여 사용할 경우에는 저장안정성이 떨어지게 된다.In the present invention, the composition of pyridinium p-toluenesulfonate (pyridinium p -toluenesulfonate), amino Dorsal Phoebe others -16 (amidosulfobetain-16), ammonium (-) - camphor-10-sulfonate ((-) - sulfonic acid salts of organic bases such as camphor-10-sulfonic acid ammonium salt, ammonium formate, triethylammonium formate, trimethyammonium formate, tetramethylammonium formate Formate), pyridinium formate (pyridinium formate) may further include a compound selected from the group consisting of formate of an organic base. The compound (crosslinking catalyst) serves to promote crosslinking of the resin to improve the etch resistance and solvent resistance. The compound is preferably 0.0001 to 0.01 parts by weight based on 100 parts by weight of the organosilane-based polymer. When used in less than 0.0001 parts by weight can not see the effect, when used in excess of 0.01 parts by weight is less storage stability.
또한, 상기 하드마스크 조성물은 피리디늄 p-톨루엔술포네이트(pyridinium p-toluenesulfonate), 아미도설포베타인-16(amidosulfobetain-16), 암모늄 (-)-캠퍼-10-술폰산염((-)-camphor-10-sulfonic acid ammonium salt) 등 유기염기의 술폰산염이나 암모늄 포메이트(ammonium formate), 트리에틸암모늄 포메이트(triethylammonium formate), 트리메틸암모늄 포메이트 (trimethyammonium formate), 테트라메틸암모늄 포메이트 (tetramethylammonium formate), 피리디늄 포메이트 (pyridinium formate) 등 유기 염기의 포름산염으로 이루어진 군에서 선택되는 하나 이상의 화합물 뿐만 아니라 추가로 가교제, 라디칼 안정제, 계면활성제 등의 첨가제를 1 또는 2 이상 더 포함할 수 있다.In addition, the hard mask composition is pyridinium p-toluenesulfonate (pyridinium p -toluenesulfonate), amino Dorsal Phoebe others -16 (amidosulfobetain-16), ammonium (-) - camphor-10-sulfonate ((-) - camphor Sulfonic acid salts of organic bases such as -10-sulfonic acid ammonium salt, ammonium formate, triethylammonium formate, trimethyammonium formate, tetramethylammonium formate ), Pyridinium formate (pyridinium formate) such as at least one compound selected from the group consisting of organic base, and may further include one or two or more additives such as crosslinking agents, radical stabilizers, surfactants.
한편, 본 발명은 (a) 기판 상에 재료 층을 제공하는 단계; (b) 상기 재료 층 위로 유기물로 이루어진 하드마스크 층을 형성시키는 단계; (c) 상기 유기물로 이 루어진 하드마스크 층 위로 상기 본 발명의 레지스트 하층막용 하드마스크 조성물을 코팅하여 반사방지 하드마스크 층을 형성시키는 단계; (d) 상기 반사방지 하드마스크 층 위로 방사선-민감성 이미지화 층을 형성시키는 단계; (e) 상기 방사선-민감성 이미지화 층을 패턴 방식으로 방사선에 노출시킴으로써 상기 방사선-민감성 이미지화 층 내에서 방사선-노출된 영역의 패턴을 생성시키는 단계;(f) 상기 방사선-민감성 이미지화 층 및 상기 반사방지 하드마스크 층의 부분을 선택적으로 제거하여 상기 유기물로 이루어진 하드마스크 층의 부분을 노출시키는 단계; (g) 패턴화된 반사방지 하드마스크 층 및 상기 유기물로 이루어진 하드마스크 층의 부분을 선택적으로 제거하여 재료층의 부분을 노출시키는 단계; 및 (h) 재료층의 노출된 부분을 에칭함으로써 패턴화된 재료 형상을 형성시키는 단계를 포함하는 것을 특징으로 하는 반도체 집적회로 디바이스의 제조방법을 제공한다.On the other hand, the present invention comprises the steps of (a) providing a layer of material on a substrate; (b) forming a hardmask layer of organic material over the material layer; (c) coating the hard mask composition for a resist underlayer film of the present invention on the hard mask layer formed of the organic material to form an antireflective hard mask layer; (d) forming a radiation-sensitive imaging layer over the antireflective hardmask layer; (e) generating a pattern of radiation-exposed areas within the radiation-sensitive imaging layer by exposing the radiation-sensitive imaging layer to radiation in a patterned manner; (f) the radiation-sensitive imaging layer and the antireflection Selectively removing portions of the hardmask layer to expose portions of the hardmask layer of organic material; (g) selectively removing portions of the patterned antireflective hardmask layer and the organic hardmask layer to expose portions of the material layer; And (h) forming a patterned material shape by etching the exposed portion of the material layer.
상기 발명은 패터닝된 재료층 구조물, 예컨대 금속 와이어링 라인, 접촉공 또는 바이어스, 절연색션, 예컨대 다마스크 트렌치 또는 셀로우 트렌치 절연, 커패시터 구조물용 트렌치, 예컨대 집적 회로 장치의 설계에 사용될 수도 있는 것들을 형성하는데 사용할 수 있다. 상기 발명은 산화물, 질화물, 폴리실리콘 및 크롬의 패터닝된 층을 형성하는 것에 관하여 특히 유용하다.The invention forms patterned material layer structures, such as metal wiring lines, contact holes or vias, insulation sections such as damask trench or shallow trench isolation, trenches for capacitor structures, such as those that may be used in the design of integrated circuit devices. Can be used to The invention is particularly useful with regard to forming patterned layers of oxides, nitrides, polysilicones and chromium.
또한, 본 발명에서는 상기 제조방법에 의해 형성되는 것을 특징으로 하는 반도체 집적회로 디바이스가 제공된다.In addition, the present invention provides a semiconductor integrated circuit device, which is formed by the above manufacturing method.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
[비교예][Comparative Example]
기계교반기, 냉각관, 적가 깔대기, 질소가스 도입관을 구비한 10ℓ의 4구 플라스크에 메틸트리메톡시실란(methyltrimethoxysilane) 1750g과 페닐트리메톡시실란(phenyltrimethoxysilane) 340g과 트리메톡시실란(trimethoxysilane) 313g을 PGMEA 5,600g에 용해시킨 후 1,000 ppm 질산 수용액 925g을 용액에 첨가하였다. 그 후, 60℃에서 1시간 반응시킨 후, 음압을 가하여 생성된 메탄올(methanol)을 제거하였다. 50℃로 반응온도를 유지하면서, 반응을 1 주일 동안 진행시켰다. 반응 후, 헥산(hexanes)을 가하여 침전으로 떨어진 하기 화학식8로 나타내어 지는 폴리머를 걸러 내어 원하는 샘플을 얻었다.In a 10 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a dropping funnel, and a nitrogen gas introduction tube, 1750 g of methyltrimethoxysilane, 340 g of phenyltrimethoxysilane, and 313 g of trimethoxysilane Was dissolved in 5,600 g of PGMEA, and then 925 g of 1,000 ppm aqueous nitric acid solution was added to the solution. Thereafter, the reaction was carried out at 60 ° C. for 1 hour, and then negative pressure was applied to remove the generated methanol. The reaction was run for 1 week while maintaining the reaction temperature at 50 ° C. After the reaction, hexanes were added, and the polymer represented by the following Chemical Formula 8 dropped to precipitate was filtered to obtain a desired sample.
[화학식8][Formula 8]
만들어진 샘플 4.0g에 PGMEA 100g과 에틸락테이트(Ethyl lactate) 100g을 넣어 희석용액을 만들었다. 얻어진 용액을 실리콘웨이퍼에 스핀-코팅법으로 코팅하 여 60초간 240℃에서 구워서 두께 500Å의 필름을 형성시켰다.Into 4.0 g of the prepared sample, 100 g of PGMEA and 100 g of ethyl lactate were added to make a diluted solution. The obtained solution was coated on a silicon wafer by spin-coating and baked at 240 ° C. for 60 seconds to form a film having a thickness of 500 μs.
[실시예1] Example 1
상기 만들어진 희석용액에 피리디늄 p-톨루엔술포네이트(pyridinium p-toluenesulfonate) 0.04g과 1,8-비스(디메틸아미노)나프탈렌(1,8-bis(dimethylamino)naphthalene) 0.04g을 넣어 준 후, 실리콘웨이퍼에 스핀-코팅법으로 코팅하여 60초간 240℃에서 구워서 두께 500Å의 필름을 형성시킨 것을 제외하고는 비교예와 동일하게 하여 실시하였다.Made to the dilute solution of pyridinium p - toluenesulfonate (pyridinium p -toluenesulfonate) it gave after putting 0.04g and 1,8-bis (dimethylamino) naphthalene (1,8-bis (dimethylamino) naphthalene ) 0.04g, silicon The coating was carried out in the same manner as in Comparative Example, except that the wafer was coated with a spin-coating method and baked at 240 ° C. for 60 seconds to form a film having a thickness of 500 mm 3.
[실험예 1]Experimental Example 1
본 실험예는 유기 염기 또는 유기염기의 유도체 사용이 마스크의 광학특성에 열화 현상등 악영향을 미치는지 여부에 대해 확인하기 위한 것이다.This experimental example is to determine whether the use of an organic base or an organic base derivative adversely affects the optical properties of the mask.
비교예와 실시예 1에서 제조된 필름들에 대한 굴절률(refractive index) n과 흡광계수(extinction coefficient) k를 구하였다. 사용기기는 Ellipsometer(J. A. Woollam 사 제품)이고 측정결과는 표 1과 같다.The refractive index n and extinction coefficient k of the films prepared in Comparative Example and Example 1 were obtained. The instrument used was Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 1.
비교예나 실시예1 모두 동일하게 우수한 광학특성을 보였다. 실시예 1에서 유기염기인 1,8-비스(디메틸아미노)나프탈렌(1,8-bis(dimethylamino)naphthalene)를 첨가하여도 열화현상이 발생하지 않고 마스크의 광학적 특성에 악영향을 미치지 않음을 확인할 수 있었다.Both Comparative Examples and Example 1 showed the same excellent optical properties. In Example 1, addition of 1,8-bis (dimethylamino) naphthalene (1,8-bis (dimethylamino) naphthalene) as an organic base did not cause deterioration and did not adversely affect the optical properties of the mask. there was.
[실험예 2]Experimental Example 2
비교예와 실시예 1에서 만들어진 웨이퍼위에 ArF용 포토레지스트를 코팅하고 110℃에서 60초간 굽고 ArF 노광장비인 ASML1250 (FN70 5.0 active, NA 0.82)를 사용해 노광을 한 다음 TMAH(2.38wt% 수용액)으로 현상하였다. 그리고 FE-SEM을 사용하여 80nm의 라인 앤드 스페이스(line and space) 패턴을 고찰한 결과, 하기 표 2와 같은 결과를 얻었다. 노광량의 변화에 따른 EL(expose latitude) 마진(margine), 광원과의 거리변동에 따른 DoF(depth of focus) 마진(margine)과 레지듀(residue)의 두께를 고찰하여 표 2에 기록하였다.The ArF photoresist was coated on the wafer prepared in Comparative Example and Example 1, baked at 110 ° C. for 60 seconds, exposed using an ArF exposure apparatus ASML1250 (FN70 5.0 active, NA 0.82), and then exposed to TMAH (2.38 wt% aqueous solution). Developed. And using a FE-SEM to examine the line and space (line and space) pattern of 80nm, as shown in Table 2 below. The thickness of the exposure latitude (EL) margin according to the change of the exposure amount, the depth of focus (DoF) margin and the residue according to the distance change with the light source was considered and recorded in Table 2.
비교예나 실시예1 모두 노광량의 변화에 따른 EL(expose latitude) 마진(margine), 광원과의 거리변동에 따른 DoF(depth of focus) 마진(margine)면에서 좋은 photoprofile을 보여 주었다. 유기염기를 첨가한 것이 포토레지스트의 photoprofile에 나쁜 영향을 미치지 않음을 확인할 수 있었다. Both Comparative Examples and Example 1 showed good photoprofiles in terms of the exposure latitude (EL) margin according to the change of the exposure dose and the depth of focus (DoF) margin according to the distance variation with the light source. It was confirmed that the addition of the organic base did not adversely affect the photoprofile of the photoresist.
한편, 비교예의 경우에는 현상후 레지듀 두께가 50Å인데 비해 실시예 1에 의할 경우에는 레지듀 두께가 10Å에 불과하여 본 발명에 의할 경우 현상 후 남는 레지듀의 양을 최소화할 수 있음을 확인할 수 있었다.On the other hand, in the case of the comparative example, the residue thickness after development is 50 kW, whereas in Example 1, the residue thickness is only 10 kW, and according to the present invention, it is possible to minimize the amount of residue remaining after development. I could confirm it.
[실험예 3]Experimental Example 3
상기 표 2의 패턴화된 시편을 CFx 플라즈마를 사용하여 드라이 에칭을 진행하고 이어서 O2 플라즈마를 사용하여 다시 드라이 에칭을 진행한 다음, CFx 플라즈마를 사용하여 드라이 에칭을 다시 진행하였다. 마지막으로 O2가스를 사용하여 남아 있는 유기물을 모두 제거한 다음, FE SEM으로 단면을 고찰하여 표 3에 결과를 수록하였다.The patterned specimens of Table 2 were dry etched using CF x plasma, followed by dry etch again using O 2 plasma, and then dry etched again using CF x plasma. Finally, after removing all remaining organics using O 2 gas, the cross section was examined by FE SEM and the results are listed in Table 3.
비교예나 실시예1 모두 에칭 후 패턴 모양이 수직으로서 좋은 에치특성을 보였다. 본 발명에서 Si-OR을 도입한 것이 마스크의 내에치성, 에치선택성과 에치프로파일(etch profile)에 나쁜 영향을 미치지 않음을 확인할 수 있었다.Both Comparative Examples and Example 1 showed good etch characteristics as the pattern shape was vertical after etching. It was confirmed that the introduction of Si-OR in the present invention does not adversely affect the etch resistance, etch selectivity and etch profile of the mask.
이상에서 설명한 바와 같이 본 발명은 상기 화학식 1에서의 Ph-기가 DUV(Deep UV) 영역(예를 들어 193nm)에서 흡수스펙트럼을 나타내는 점을 활용하여 상기 영역에서의 흡수도가 높은 재료를 제공함과 동시에 Ph-기의 농도비를 조절함으로써 특정 파장영역에서 원하는 흡수도와 굴절률을 갖고, 유기염기 또는 유기염기의 유도체를 첨가하여 노광 후 현상 시에 남는 레지듀의 양을 최소화시킨 레지스트 하층막용 하드마스크 조성물을 제공할 수 있다. As described above, the present invention utilizes a point where the Ph-group in Chemical Formula 1 shows an absorption spectrum in a DUV (Deep UV) region (for example, 193 nm) to provide a material having high absorption in the region. It provides a hard mask composition for a resist underlayer film having a desired absorption and refractive index in a specific wavelength region by controlling the concentration ratio of the Ph-group, and adding an organic base or a derivative of an organic base to minimize the amount of residue remaining during development after exposure. can do.
본 발명에 따르면 우수한 막특성과 저장안정성을 가지며 하드마스크 특성이 우수하여 재료층에 훌륭한 패턴을 전사할 수 있는 레지스트 하층막용 하드마스크 조성물을 제공할 수 있다.According to the present invention, it is possible to provide a hard mask composition for a resist underlayer film capable of transferring excellent patterns to a material layer by having excellent film characteristics and storage stability and excellent hard mask characteristics.
특히, 본 발명에 의해 하드마스크를 제조할 경우 노광 후 현상시 발생하는 레지듀(residue)의 양을 최소화시킬 수 있다. In particular, when manufacturing a hard mask according to the present invention it is possible to minimize the amount of resin (residue) generated during development after exposure.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060057559A KR100909384B1 (en) | 2006-06-26 | 2006-06-26 | Hard mask composition for resist underlayer film and manufacturing method of semiconductor integrated circuit device using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060057559A KR100909384B1 (en) | 2006-06-26 | 2006-06-26 | Hard mask composition for resist underlayer film and manufacturing method of semiconductor integrated circuit device using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20070122250A true KR20070122250A (en) | 2007-12-31 |
| KR100909384B1 KR100909384B1 (en) | 2009-07-24 |
Family
ID=39139184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020060057559A KR100909384B1 (en) | 2006-06-26 | 2006-06-26 | Hard mask composition for resist underlayer film and manufacturing method of semiconductor integrated circuit device using same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100909384B1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009088177A3 (en) * | 2008-01-11 | 2009-09-03 | Cheil Industries Inc. | Silicon-based hardmask composition (si-soh; si-based spin-on hardmask) and process of producing semiconductor integrated circuit device using the same |
| WO2010071255A1 (en) * | 2008-12-17 | 2010-06-24 | Cheil Industries Inc. | Hardmask composition with improved storage stability for forming resist underlayer film |
| WO2011081322A2 (en) * | 2009-12-31 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| WO2011081316A2 (en) * | 2009-12-30 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| WO2011081323A2 (en) * | 2009-12-31 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a photoresist, and method using same to manufacture semiconductor device |
| WO2011081321A2 (en) * | 2009-12-31 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| KR101506998B1 (en) * | 2011-12-30 | 2015-03-31 | 제일모직 주식회사 | Resist underlayer composition and process for producing integrated circuit device using same |
| US9291899B2 (en) | 2008-12-30 | 2016-03-22 | Cheil Industries, Inc. | Resist underlayer composition and method of manufacturing semiconductor integrated circuit device using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101556281B1 (en) | 2012-12-28 | 2015-09-30 | 제일모직 주식회사 | Resist underlayer composition and method of manufacturing integrated circuit devices using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100463858B1 (en) * | 1996-08-29 | 2005-02-28 | 마츠시타 덴끼 산교 가부시키가이샤 | Method of forming interlayer insulating film |
| JP3998979B2 (en) * | 1999-12-28 | 2007-10-31 | 触媒化成工業株式会社 | Method for forming low dielectric constant silica-based film and semiconductor substrate with low dielectric constant film |
| KR100373210B1 (en) * | 2000-04-28 | 2003-02-25 | 주식회사 엘지화학 | Method for preparing dielectrics material with low dielectric constant using organic spacer |
| JP2002207296A (en) * | 2000-11-08 | 2002-07-26 | Jsr Corp | Composition for resist lower layer film, method for manufacturing the same and resist lower film and method for manufacturing the same |
-
2006
- 2006-06-26 KR KR1020060057559A patent/KR100909384B1/en active IP Right Grant
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910947B (en) * | 2008-01-11 | 2013-07-03 | 第一毛织株式会社 | Silicon-based hardmask composition (Si-SOH; Si-base spin-coating hardmask) and process of producing semiconductor integrated circuit device using the same |
| KR100930672B1 (en) * | 2008-01-11 | 2009-12-09 | 제일모직주식회사 | Silicon-based hard mask composition and method for manufacturing semiconductor integrated circuit device using same |
| CN101910947A (en) * | 2008-01-11 | 2010-12-08 | 第一毛织株式会社 | Silicon-based hardmask composition (Si-SOH; Si-base spin-coating hardmask) and process of producing semiconductor integrated circuit device using the same |
| WO2009088177A3 (en) * | 2008-01-11 | 2009-09-03 | Cheil Industries Inc. | Silicon-based hardmask composition (si-soh; si-based spin-on hardmask) and process of producing semiconductor integrated circuit device using the same |
| US8524851B2 (en) | 2008-01-11 | 2013-09-03 | Cheil Industries, Inc. | Silicon-based hardmask composition and process of producing semiconductor integrated circuit device using the same |
| WO2010071255A1 (en) * | 2008-12-17 | 2010-06-24 | Cheil Industries Inc. | Hardmask composition with improved storage stability for forming resist underlayer film |
| KR101288572B1 (en) * | 2008-12-17 | 2013-07-22 | 제일모직주식회사 | Hardmask Composition Coated under Photoresist with Improved Storage Stability |
| US9291899B2 (en) | 2008-12-30 | 2016-03-22 | Cheil Industries, Inc. | Resist underlayer composition and method of manufacturing semiconductor integrated circuit device using the same |
| WO2011081316A2 (en) * | 2009-12-30 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| WO2011081316A3 (en) * | 2009-12-30 | 2011-10-27 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| WO2011081323A2 (en) * | 2009-12-31 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a photoresist, and method using same to manufacture semiconductor device |
| WO2011081322A3 (en) * | 2009-12-31 | 2011-11-03 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| CN102695987A (en) * | 2009-12-31 | 2012-09-26 | 第一毛织株式会社 | Composition for the bottom layer of a photoresist, and method using same to manufacture semiconductor device |
| WO2011081323A3 (en) * | 2009-12-31 | 2011-10-27 | 제일모직 주식회사 | Composition for the bottom layer of a photoresist, and method using same to manufacture semiconductor device |
| WO2011081321A2 (en) * | 2009-12-31 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| WO2011081321A3 (en) * | 2009-12-31 | 2011-11-03 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| US8758981B2 (en) | 2009-12-31 | 2014-06-24 | Cheil Industries, Inc. | Photoresist underlayer composition and method of manufacturing semiconductor device by using the same |
| CN102695987B (en) * | 2009-12-31 | 2014-10-01 | 第一毛织株式会社 | Composition for the bottom layer of a photoresist, and method using same to manufacture semiconductor device |
| US8962747B2 (en) | 2009-12-31 | 2015-02-24 | Cheil Industries, Inc. | Resist underlayer composition and process of producing integrated circuit devices using the same |
| US9140986B2 (en) | 2009-12-31 | 2015-09-22 | Cheil Industries, Inc. | Resist underlayer composition and process of producing integrated circuit devices using the same |
| WO2011081322A2 (en) * | 2009-12-31 | 2011-07-07 | 제일모직 주식회사 | Composition for the bottom layer of a resist, and method using same to manufacture a semiconductor integrated circuit device |
| KR101506998B1 (en) * | 2011-12-30 | 2015-03-31 | 제일모직 주식회사 | Resist underlayer composition and process for producing integrated circuit device using same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100909384B1 (en) | 2009-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100796047B1 (en) | Hardmask composition coated under photoresist, process of producing integrated circuit devices using the same and semiconductor device produced by the process | |
| KR100909384B1 (en) | Hard mask composition for resist underlayer film and manufacturing method of semiconductor integrated circuit device using same | |
| US8524851B2 (en) | Silicon-based hardmask composition and process of producing semiconductor integrated circuit device using the same | |
| KR101436336B1 (en) | Silicon-containing resist underlying layer film forming composition for formation of photocrosslinking cured resist underlying layer film | |
| KR100816735B1 (en) | Hardmask composition having antireflective property, process of producing patterned materials by using the same and integrated circuit devices | |
| EP2204399B1 (en) | Resist underlayer composition and method of manufacturing semiconductor integrated circuit device using the same | |
| US20070196773A1 (en) | Top coat for lithography processes | |
| KR100760522B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR20100079020A (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR100792045B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR101344795B1 (en) | Resist underlayer composition and Process of Producing Integrated Circuit Devices Using the Same | |
| KR20070095736A (en) | Hardmask composition coated under photoresist comprising organosilane polymer and process of producing integrated circuit devices using thereof | |
| KR100713231B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR101709596B1 (en) | Gap embedding composition, method of embedding gap and method of producing semiconductor device by using the composition | |
| KR100725793B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR100783064B1 (en) | Organosilane composition, Hardmask Composition Coated under Photoresist and Process of producing integrated circuit devices using thereof | |
| KR20110079202A (en) | Resist underlayer composition and process of producing integrated circuit devices using the same | |
| KR100725794B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR101531611B1 (en) | Process of producing integrated circuit device and an integrated circuit device thereof | |
| KR101506998B1 (en) | Resist underlayer composition and process for producing integrated circuit device using same | |
| KR100725795B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR100713238B1 (en) | Hardmask composition coated under photoresist and process of producing integrated circuit devices using thereof | |
| KR101333702B1 (en) | Polymer for under-layer of resist, under-layer composition of resist, method of patterning device using same | |
| KR100783068B1 (en) | Organosilane composition, Hardmask Composition Coated under Photoresist and Process of producing integrated circuit devices using thereof | |
| KR100783070B1 (en) | Organosilane composition, Hardmask Composition Coated under Photoresist and Process of producing integrated circuit devices using thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application | ||
| J201 | Request for trial against refusal decision | ||
| AMND | Amendment | ||
| B601 | Maintenance of original decision after re-examination before a trial | ||
| E801 | Decision on dismissal of amendment | ||
| S901 | Examination by remand of revocation | ||
| GRNO | Decision to grant (after opposition) | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130607 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20140605 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20150623 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20160617 Year of fee payment: 8 |
|
| FPAY | Annual fee payment |
Payment date: 20170621 Year of fee payment: 9 |
|
| FPAY | Annual fee payment |
Payment date: 20180628 Year of fee payment: 10 |
|
| FPAY | Annual fee payment |
Payment date: 20190626 Year of fee payment: 11 |