KR100451643B1 - Photoresist Norbornene-Copolymer Comprising Acetal Group, Method for Producing the Same and Photoresist Composition Containing the Same - Google Patents
Photoresist Norbornene-Copolymer Comprising Acetal Group, Method for Producing the Same and Photoresist Composition Containing the Same Download PDFInfo
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- KR100451643B1 KR100451643B1 KR10-2001-0085022A KR20010085022A KR100451643B1 KR 100451643 B1 KR100451643 B1 KR 100451643B1 KR 20010085022 A KR20010085022 A KR 20010085022A KR 100451643 B1 KR100451643 B1 KR 100451643B1
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
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- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- 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
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- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- 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
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Abstract
본 발명은 아세탈기를 포함하는 포토레지스트용 노르보넨 공중합체, 그의 제조방법 및 그를 포함하는 포토레지스트 조성물에 관한 것으로, 보다 상세하게는 하기 화학식 1로 표시되는, 아세탈기를 포함하는 포토레지스트용 노르보넨 공중합체, 그의 제조방법 및 그를 포함하는 포토레지스트 조성물에 관한 것이며, 본 발명의 공중합체는 250nm 이하의 자외선 영역에서의 투명성, 해상도, 감도 및 건식 에칭 내성이 우수하고, 기판에 대한 접착력이 뛰어나므로 초고집적 반도체의 엑시머 레이저 미세가공에 유용하다.The present invention relates to a norbornene copolymer for a photoresist comprising an acetal group, a method for producing the same and a photoresist composition comprising the same, and more particularly, to a norbornene air for photoresists including an acetal group represented by the following Chemical Formula 1 The present invention relates to a coalescence, a method for preparing the same, and a photoresist composition including the same, and the copolymer of the present invention is excellent in transparency, resolution, sensitivity, and dry etching resistance in an ultraviolet region of 250 nm or less, and has excellent adhesion to a substrate. It is useful for excimer laser micromachining of highly integrated semiconductors.
[화학식 1][Formula 1]
상기 화학식에서,In the above formula,
R1은 탄소수 1~12개의 선형, 분지형, 또는 환형 알킬기이고;R 1 is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms;
R2, R3, R4, 및 R5는 각각 수소, 불소, 메틸기 또는 트리플루오로메틸기이며;R 2 , R 3 , R 4 , and R 5 are each a hydrogen, fluorine, methyl group or trifluoromethyl group;
R6, 및 R7는 각각 수소원자, 탄소수 1~10개의 선형 또는 분지형 알킬기,─(CH2)t─R8, ─(CH2)t─OR8, ─(CH2)t─C(O)OR8, ─(CH2)t─C(O)R8, ─(CH2)t─OC(O)R8, ─(CH2)t─OC(O)OR8, 또는 ─(CH2)t─C(O)OCH2OR8이며, 이때 R8은 수소, 불소, 또는 탄소수 1~12개의 선형, 분지형, 환형 알킬기, 또는 케톤기를 포함하는 환형알킬기이고, t는 0부터 6까지의 정수이며, 상기 R6및 R7는 서로 연결되어 고리를 형성할 수 있고;R 6 , and R 7 each represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, — (CH 2 ) t ─R 8 , ─ (CH 2 ) t ─OR 8 , ─ (CH 2 ) t ─C (O) OR 8 ,-(CH 2 ) t --C (O) R 8 ,-(CH 2 ) t --OC (O) R 8 ,-(CH 2 ) t --OC (O) OR 8 , or- (CH 2 ) t —C (O) OCH 2 OR 8 , wherein R 8 is hydrogen, fluorine or a cyclic alkyl group containing a linear, branched, cyclic alkyl group, or a ketone group having 1 to 12 carbon atoms, and t is 0 To 6, wherein R 6 and R 7 may be linked to each other to form a ring;
l, m 및 n은 각각 0.1≤l/l+m+n≤0.99, 0≤m/l+m+n≤0.3, 0.01≤n/l+m+n≤0.6를 만족시키는 값이며;l, m and n are values satisfying 0.1 ≦ l / l + m + n ≦ 0.99, 0 ≦ m / l + m + n ≦ 0.3, 0.01 ≦ n / l + m + n ≦ 0.6, respectively;
o, p ,q, r 및 s는 각각 0부터 2까지의 정수이다.o, p, q, r and s are integers from 0 to 2, respectively.
Description
본 발명은 아세탈기를 포함하는 포토레지스트용 노르보넨 공중합체, 그의 제조방법 및 그를 포함하는 포토레지스트 조성물에 관한 것으로, 보다 상세하게는 노르보넨 및 노르보넨 유도체가 주사슬에 도입되어 향상된 물성을 가진 포토레지스트용 노르보넨 공중합체 및 그 공중합체를 보다 용이하게 제조하는 방법에 관한 것이다.The present invention relates to a norbornene copolymer for a photoresist comprising an acetal group, a manufacturing method thereof, and a photoresist composition comprising the same. More specifically, a norbornene and norbornene derivative is introduced into a main chain to provide a photo having improved physical properties. The norbornene copolymer for resists, and a method for producing the copolymer more easily.
현재 미세가공기술(lithography)은 메모리 반도체인 DRAM의 고집적도를 이루는 핵심기술이 되고 있다. 특히, 초고집적 반도체(VLSI) 제조에는 보다 미세한 초미세가공 기술이 필요하므로, 이에 적합한 고성능의 레지스트 재료가 절실히 요구되고 있는 실정이다.At present, lithography has become a key technology for achieving high density of DRAM, a memory semiconductor. In particular, the manufacture of ultra-high density semiconductors (VLSI) requires finer ultra-fine processing techniques, and therefore, there is an urgent need for high-performance resist materials suitable for them.
일반적으로 포토레지스트는 사용되는 광에 대한 투명성, 에칭 내성과 내열성 및 접착성이 요구되며, 특히 엑시머 레이저를 이용한 미세가공 공정에 사용되는 포토레지스트는 2.38중량% TMAH(tetramethylammoniumhydroxide) 수용액으로 현상 가능하여야 하나, 이러한 모든 성질을 만족하는 포토레지스트용 수지를 합성하기는 매우 어렵다. 예를 들어, 아크릴계 고분자는 합성이 쉽고 200nm 이하의 파장영역에서 흡광도가 낮아서 포토레지스트용 매트릭스 수지로 주목받았으나, 이들은 건식 에칭 내성에 문제가 있다.In general, the photoresist requires transparency, etching resistance and heat resistance and adhesion to the light used. In particular, the photoresist used in the micromachining process using an excimer laser should be developed with a 2.38% by weight aqueous solution of tetramethylammoniumhydroxide (TMAH). It is very difficult to synthesize a resin for photoresist that satisfies all these properties. For example, acrylic polymers have been attracting attention as matrix resins for photoresists because they are easy to synthesize and have low absorbance in the wavelength range of 200 nm or less, but these have problems with dry etching resistance.
최근 들어 이러한 아크릴계 고분자의 에칭에 대한 내성을 증가시키기 위하여, 탄소수가 많은 지환족 환형 단위체(alicyclic unit)를 주사슬이나 곁사슬에 도입하는 방법이 사용되고 있다. 아크릴계 고분자의 주사슬에 도입되는 지환족 단량체로는 노르보넨, 노르보넨 유도체, 시클로디엔 및 노르트리시클렌 등이 있으며, 곁사슬에 도입되는 지환족 치환기로는 이소보닐(isobornyl)기, 멘틸(mentyl)기, 트리시클로데카닐(tricyclodecanyl)기, 노르보닐(norbornyl)기, 테트라시클로도데실(tetracyclododecyl)기 및 아다만틸(adamantyl)기 등이 있다. 이때 곁사슬에 지환족 치환기를 함유한 고분자는 주사슬이 아크릴계 고분자로 되어 있어서 지환족의 함량이 전체의 50% 이상이 되지 않기 때문에 알칼리 수용액에서 낮은 용해도를 나타내고, 도입된 지환족 환형 단위체가 Tg(유리전이온도)와 소수성을 증가시켜 기판에 대한 접착력이 떨어지는 단점이 있으며 부서지기 쉬운 상태로만들어 감도가 떨어지는 문제가 있다.In recent years, in order to increase the resistance to the etching of such an acrylic polymer, a method of introducing an alicyclic unit containing a large number of carbon atoms into the main chain or the side chain has been used. The alicyclic monomers introduced into the main chain of the acrylic polymer include norbornene, norbornene derivatives, cyclodiene and nortricyclene, and the alicyclic substituents introduced into the side chain include isobornyl group and mentyl. Groups, tricyclodecanyl groups, norbornyl groups, tetracyclododecyl groups, and adamantyl groups. At this time, the polymer containing the cycloaliphatic substituent in the side chain has a low solubility in an aqueous alkali solution because the main chain is an acrylic polymer so that the alicyclic content is not more than 50% of the total, and the alicyclic cyclic unit introduced is Tg ( Glass transition temperature) and hydrophobicity increase the disadvantage that the adhesion to the substrate is inferior and there is a problem that the sensitivity is reduced by making the brittle state.
그러나, 지환족 환형 단위체가 주사슬에 도입된 중합체는 건식 에칭 내성과 열적 성질이 우수할 뿐 아니라 패턴에 필요한 기능성을 곁사슬에 부여할 수 있다는 장점이 있다. 따라서, 주쇄가 지환족 구조로 이루어진 매트릭스 수지를 제조하려는 연구가 진행되어 오고 있으며 일반적으로 노르보넨 및 노르보넨 유도체를 비롯한 통상의 멀티사이클릭(multicyclic) 단량체의 중합체를 얻기 위해서는 라디칼중합, 양이온중합, 부가중합, 그리고 개환중합 등과 같은 중합기법이 이용되고 있다.However, the polymer in which the cycloaliphatic cyclic unit is introduced into the main chain has the advantage of providing the side chain with excellent dry etching resistance and thermal properties as well as the functionality required for the pattern. Therefore, studies have been conducted to prepare matrix resins having a main chain alicyclic structure, and generally, in order to obtain polymers of conventional multicyclic monomers including norbornene and norbornene derivatives, radical polymerization, cationic polymerization, Polymerization techniques such as addition polymerization and ring-opening polymerization are used.
그러나, 이와 같은 방법들은 전체적으로 중합수율이 낮고 일부 극성을 갖는 단량체에 제한적이며, 중합에 사용되는 대부분의 촉매가 복잡한 구조를 가지므로 중합시에 수분에 민감하여 건조한 탄화수소계 용매 또는 할로겐화 방향족 용매를 사용하여야 하는 단점이 있다.However, these methods are generally limited to monomers having low polymerization yield and some polarity, and since most catalysts used for polymerization have a complicated structure, they are sensitive to moisture during polymerization and use a dry hydrocarbon solvent or a halogenated aromatic solvent. There are disadvantages that must be made.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로, 초고집적 반도체의 엑시머 레이저 미세가공에 적합하도록 투명성, 고감도, 고해상도 및 에칭 내성을 가지는 포토레지스트용 노르보넨 공중합체를 제공함을 목적으로 한다.The present invention is to solve the above problems of the prior art, an object of the present invention is to provide a norbornene copolymer for photoresist having transparency, high sensitivity, high resolution and etching resistance to be suitable for the excimer laser micromachining of ultra-high density semiconductor. .
본 발명의 다른 목적은 상기 포토레지스트용 노르보넨 공중합체를 간단하고 용이하게 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing the norbornene copolymer for photoresist simply and easily.
본 발명의 또다른 목적은 초고집적 반도체의 엑시머 레이저 미세가공에 적합한 포토레지스트용 조성물을 제공하는 것이다.It is another object of the present invention to provide a composition for photoresists suitable for excimer laser micromachining of ultra-high density semiconductors.
즉, 본 발명의 한 측면은 하기 화학식 1로 표시되는, 아세탈기를 포함하는 포토레지스트용 노르보넨 공중합체에 관한 것이다.That is, one aspect of the present invention relates to a norbornene copolymer for photoresists comprising an acetal group represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식에서,In the above formula,
R1은 탄소수 1~12개의 선형, 분지형, 또는 환형 알킬기이고;R 1 is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms;
R2, R3, R4, 및 R5는 각각 수소, 불소, 메틸기 또는 트리플루오로메틸기이며;R 2 , R 3 , R 4 , and R 5 are each a hydrogen, fluorine, methyl group or trifluoromethyl group;
R6, 및 R7는 각각 수소원자, 탄소수 1~10개의 선형 또는 분지형 알킬기, ─(CH2)t─R8, ─(CH2)t─OR8, ─(CH2)t─C(O)OR8, ─(CH2)t─C(O)R8, ─(CH2)t─OC(O)R8, ─(CH2)t─OC(O)OR8, 또는 ─(CH2)t─C(O)OCH2OR8이며, 이때 R8은 수소, 불소, 또는 탄소수 1~12개의 선형, 분지형, 환형 알킬기, 또는 케톤기를 포함하는 환형알킬기이고, t는 0부터 6까지의 정수이며, 상기 R6및 R7는 서로 연결되어 고리를 형성할 수 있고;R 6 and R 7 each represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, ─ (CH 2 ) t ─R 8 , ─ (CH 2 ) t ─OR 8 , ─ (CH 2 ) t ─C (O) OR 8 ,-(CH 2 ) t --C (O) R 8 ,-(CH 2 ) t --OC (O) R 8 ,-(CH 2 ) t --OC (O) OR 8 , or- (CH 2 ) t —C (O) OCH 2 OR 8 , wherein R 8 is hydrogen, fluorine or a cyclic alkyl group containing a linear, branched, cyclic alkyl group, or a ketone group having 1 to 12 carbon atoms, and t is 0 To 6, wherein R 6 and R 7 may be linked to each other to form a ring;
l, m 및 n은 각각 0.1≤l/l+m+n≤0.99, 0≤m/l+m+n≤0.3, 0.01≤n/l+m+n≤0.6를 만족시키는 값이며;l, m and n are values satisfying 0.1 ≦ l / l + m + n ≦ 0.99, 0 ≦ m / l + m + n ≦ 0.3, 0.01 ≦ n / l + m + n ≦ 0.6, respectively;
o, p ,q, r 및 s는 각각 0부터 2까지의 정수이다.o, p, q, r and s are integers from 0 to 2, respectively.
본 발명의 다른 측면은 팔라듐(Ⅱ) 촉매의 존재하에 물 또는 물을 포함한 일반 유기용제 중에서, 하기 화학식 2로 표현되는 단량체와 하기 화학식 3으로 표현되는 단량체를 부가중합한 다음, 화학식 2로 표시되는 단량체에 포함된 산작용기의 일부를 아세탈화하는 단계를 포함하는 상기 포토레지스트용 노르보넨 공중합체의 제조방법에 관한 것이다.According to another aspect of the present invention, in the presence of a palladium (II) catalyst, in a general organic solvent including water or water, the monomer represented by the following formula (2) and the monomer represented by the following formula (3) are added and then polymerized It relates to a method for producing a norbornene copolymer for a photoresist comprising the step of acetalizing a portion of the acid functional groups contained in the monomer.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식에서,In the above formula,
R1은 탄소수 1~12개의 선형, 분지형, 또는 환형 알킬기이고;R 1 is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms;
R2, R3, R4, 및 R5는 각각 수소, 불소, 메틸기 또는 트리플루오로메틸기이며;R 2 , R 3 , R 4 , and R 5 are each a hydrogen, fluorine, methyl group or trifluoromethyl group;
R6, 및 R7는 각각 수소원자, 탄소수 1~10개의 선형 또는 분지형 알킬기, ─(CH2)t─R8, ─(CH2)t─OR8, ─(CH2)t─C(O)OR8, ─(CH2)t─C(O)R8, ─(CH2)t─OC(O)R8, ─(CH2)t─OC(O)OR8, 또는 ─(CH2)t─C(O)OCH2OR8이며, 이때 R8은 수소, 불소, 또는 탄소수 1~12개의 선형, 분지형, 환형 알킬기, 또는 케톤기를 포함하는 환형알킬기이고, t는 0부터 6까지의 정수이며, 상기 R6및 R7는 서로 연결되어 고리를 형성할 수 있고;R 6 and R 7 each represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, ─ (CH 2 ) t ─R 8 , ─ (CH 2 ) t ─OR 8 , ─ (CH 2 ) t ─C (O) OR 8 ,-(CH 2 ) t --C (O) R 8 ,-(CH 2 ) t --OC (O) R 8 ,-(CH 2 ) t --OC (O) OR 8 , or- (CH 2 ) t —C (O) OCH 2 OR 8 , wherein R 8 is hydrogen, fluorine or a cyclic alkyl group containing a linear, branched, cyclic alkyl group, or a ketone group having 1 to 12 carbon atoms, and t is 0 To 6, wherein R 6 and R 7 may be linked to each other to form a ring;
o, p ,q, r 및 s는 각각 0부터 2까지의 정수이다.o, p, q, r and s are integers from 0 to 2, respectively.
본 발명의 또 다른 측면은 팔라듐(Ⅱ) 촉매의 존재하에 물 또는 물을 포함한 일반 유기용제 중에서, 하기 화학식 2로 표현되는 단량체 및 화학식 3으로 표현되는 단량체와 더불어 하기 화학식 4로 표현되는 아세탈 치환된 노르보넨 단량체를 함께 부가중합하는 단계를 포함하는 상기 포토레지스트용 노르보넨 공중합체의 제조방법에 관한 것이다.Another aspect of the present invention is acetal substituted in the general organic solvent including water or water in the presence of a palladium (II) catalyst, in addition to the monomer represented by the formula (2) and the monomer represented by the formula (3) It relates to a method for producing the norbornene copolymer for the photoresist comprising the step of addition polymerization of norbornene monomer together.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
상기 화학식에서,In the above formula,
R1은 탄소수 1~12개의 선형, 분지형, 또는 환형 알킬기이고;R 1 is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms;
R2, R3, R4, 및 R5는 각각 수소, 불소, 메틸기 또는 트리플루오로메틸기이며;R 2 , R 3 , R 4 , and R 5 are each a hydrogen, fluorine, methyl group or trifluoromethyl group;
R6, 및 R7는 각각 수소원자, 탄소수 1~10개의 선형 또는 분지형 알킬기, ─(CH2)t─R8, ─(CH2)t─OR8, ─(CH2)t─C(O)OR8, ─(CH2)t─C(O)R8, ─(CH2)t─OC(O)R8, ─(CH2)t─OC(O)OR8, 또는 ─(CH2)t─C(O)OCH2OR8이며, 이때 R8은 수소, 불소, 또는 탄소수 1~12개의 선형, 분지형, 환형 알킬기, 또는 케톤기를 포함하는 환형알킬기이고, t는 0부터 6까지의 정수이며, 상기 R6및 R7는 서로 연결되어 고리를 형성할 수 있고;R 6 and R 7 each represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, ─ (CH 2 ) t ─R 8 , ─ (CH 2 ) t ─OR 8 , ─ (CH 2 ) t ─C (O) OR 8 ,-(CH 2 ) t --C (O) R 8 ,-(CH 2 ) t --OC (O) R 8 ,-(CH 2 ) t --OC (O) OR 8 , or- (CH 2 ) t —C (O) OCH 2 OR 8 , wherein R 8 is hydrogen, fluorine or a cyclic alkyl group containing a linear, branched, cyclic alkyl group, or a ketone group having 1 to 12 carbon atoms, and t is 0 To 6, wherein R 6 and R 7 may be linked to each other to form a ring;
o, p ,q, r 및 s는 각각 0부터 2까지의 정수이다o, p, q, r and s are integers from 0 to 2, respectively
본 발명의 또 다른 측면은 상기 포토레지스트용 노르보넨 공중합체, 광산발생제, 및 유기용매를 포함하는 포토레지스트 조성물에 관한 것이다.Another aspect of the present invention relates to a photoresist composition comprising the norbornene copolymer for photoresist, a photoacid generator, and an organic solvent.
도 1은 본 발명에 따른 패턴 형성 사진이다.1 is a pattern forming picture according to the present invention.
이하 본 발명을 보다 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 아세탈기를 포함하는 포토레지스트 노르보넨 공중합체는 하기 화학식 1로 나타내어지며, 지환족 환형 단위체가 주사슬내에 존재한다.The photoresist norbornene copolymer comprising the acetal group of the present invention is represented by the following formula (1), wherein an alicyclic cyclic unit is present in the main chain.
상기 화학식에서,In the above formula,
R1은 탄소수 1~12개의 선형, 분지형, 또는 환형 알킬기이고;R 1 is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms;
R2, R3, R4, 및 R5는 각각 수소, 불소, 메틸기 또는 트리플루오로메틸기이며;R 2 , R 3 , R 4 , and R 5 are each a hydrogen, fluorine, methyl group or trifluoromethyl group;
R6, 및 R7는 각각 수소원자, 탄소수 1~10개의 선형 또는 분지형 알킬기, ─(CH2)t─R8, ─(CH2)t─OR8, ─(CH2)t─C(O)OR8, ─(CH2)t─C(O)R8, ─(CH2)t─OC(O)R8, ─(CH2)t─OC(O)OR8, 또는 ─(CH2)t─C(O)OCH2OR8이며, 이때 R8은 수소, 불소, 또는 탄소수 1~12개의 선형, 분지형, 환형 알킬기, 또는 케톤기를 포함하는 환형알킬기이고, t는 0부터 6까지의 정수이며, 상기 R6및 R7는 서로 연결되어 고리를 형성할 수 있고;R 6 and R 7 each represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, ─ (CH 2 ) t ─R 8 , ─ (CH 2 ) t ─OR 8 , ─ (CH 2 ) t ─C (O) OR 8 ,-(CH 2 ) t --C (O) R 8 ,-(CH 2 ) t --OC (O) R 8 ,-(CH 2 ) t --OC (O) OR 8 , or- (CH 2 ) t —C (O) OCH 2 OR 8 , wherein R 8 is hydrogen, fluorine or a cyclic alkyl group containing a linear, branched, cyclic alkyl group, or a ketone group having 1 to 12 carbon atoms, and t is 0 To 6, wherein R 6 and R 7 may be linked to each other to form a ring;
l, m 및 n은 각각 0.1≤l/l+m+n≤0.99, 0≤m/l+m+n≤0.3, 0.01≤n/l+m+n≤0.6를 만족시키는 값이며;l, m and n are values satisfying 0.1 ≦ l / l + m + n ≦ 0.99, 0 ≦ m / l + m + n ≦ 0.3, 0.01 ≦ n / l + m + n ≦ 0.6, respectively;
o, p ,q, r 및 s는 각각 0부터 2까지의 정수이다.o, p, q, r and s are integers from 0 to 2, respectively.
본 발명의 노르보넨 공중합체의 제조에 사용되는 노르보넨 단량체로는 하기 화학식 2의 구조를 갖는 노르보넨 유도체, 하기 화학식 3의 구조를 갖는 노르보넨 유도체 및 하기 화학식 4의 구조를 갖는 아세탈 치환된 노르보넨 유도체가 있다.Norbornene monomers used in the preparation of norbornene copolymers of the present invention include norbornene derivatives having the structure of Formula 2, norbornene derivatives having the structure of Formula 3, and acetal substituted nords having the structure of Formula 4 Bonene derivatives.
상기 화학식에서,In the above formula,
R1은 탄소수 1~12개의 선형, 분지형, 또는 환형 알킬기이고;R 1 is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms;
R2, R3, R4, 및 R5는 각각 수소, 불소, 메틸기 또는 트리플루오로메틸기이며;R 2 , R 3 , R 4 , and R 5 are each a hydrogen, fluorine, methyl group or trifluoromethyl group;
R6, 및 R7는 각각 수소원자, 탄소수 1~10개의 선형 또는 분지형 알킬기, ─(CH2)t─R8, ─(CH2)t─OR8, ─(CH2)t─C(O)OR8, ─(CH2)t─C(O)R8, ─(CH2)t─OC(O)R8, ─(CH2)t─OC(O)OR8, 또는 ─(CH2)t─C(O)OCH2OR8이며, 이때 R8은 수소, 불소, 또는 탄소수 1~12개의 선형, 분지형, 환형 알킬기, 또는 케톤기를 포함하는 환형알킬기이고, t는 0부터 6까지의 정수이며, 상기 R6및 R7는 서로 연결되어 고리를 형성할 수 있고;R 6 and R 7 each represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, ─ (CH 2 ) t ─R 8 , ─ (CH 2 ) t ─OR 8 , ─ (CH 2 ) t ─C (O) OR 8 ,-(CH 2 ) t --C (O) R 8 ,-(CH 2 ) t --OC (O) R 8 ,-(CH 2 ) t --OC (O) OR 8 , or- (CH 2 ) t —C (O) OCH 2 OR 8 , wherein R 8 is hydrogen, fluorine or a cyclic alkyl group containing a linear, branched, cyclic alkyl group, or a ketone group having 1 to 12 carbon atoms, and t is 0 To 6, wherein R 6 and R 7 may be linked to each other to form a ring;
o, p ,q, r 및 s는 각각 0부터 2까지의 정수이다.o, p, q, r and s are integers from 0 to 2, respectively.
본 발명에서 유용한 노르보넨 유도체의 예로서는, 노르보넨, 2,2-디플루오로노르보넨, 2-헥실-5-노르보넨, 5-노르보넨-2-메탄올, 5-노르보넨-2-올, 5-노르보넨-2-헥사플루오로이소프로판올, 5-노르보넨-2-메틸-2-카르복실산, 5-노르보넨-2,3-디메탄올, 또는 5-옥사-트리시클로[5,2,1,0(2,6)]데카-8-엔-3-온 등을 사용할 수 있으며, ─C(CH3)3, 이소보닐(isobornyl)기, 멘틸기, 2-메틸-2-아다만타닐기, 2-에틸-2-아다만타닐기, 테트라시클로데카닐기, 테트라히드로피라닐기, 테트라히드로피라노일기, 3-옥소시클로헥사노일기, 메발로닉 락토닐기, 디시클로프로필메틸기, 메틸시클로프로필메틸기 및 에틸메틸에테르기 등과 같이 산에 의해 해리가가능한 보호기가 노르보넨에 치환된 유도체도 사용할 수 있다.Examples of norbornene derivatives useful in the present invention include norbornene, 2,2-difluoronorbornene, 2-hexyl-5-norbornene, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-hexafluoroisopropanol, 5-norbornene-2-methyl-2-carboxylic acid, 5-norbornene-2,3-dimethanol, or 5-oxa-tricyclo [5,2 , 1,0 (2,6)] deca-8-en-3-one and the like can be used, and -C (CH3) 3, isobornyl group, menthyl group, 2-methyl-2-adamanta Nyl group, 2-ethyl-2-adamantanyl group, tetracyclodecanyl group, tetrahydropyranyl group, tetrahydropyranoyl group, 3-oxocyclohexanoyl group, mechatronic lactonyl group, dicyclopropylmethyl group, methylcyclopropylmethyl group, and Derivatives in which a protecting group that can be dissociated by acid, such as ethyl methyl ether group, are substituted with norbornene can also be used.
본 발명의 노르보넨 공중합체 제조에 사용되는 노르보넨 및 노르보넨 유도체의 단량체는 시클로펜타디엔과 적절히 치환된 친디엔체(dienophile)의 딜스-알더(Diels-Alder) 반응에 의해 합성되며, 그 일반적인 반응식은 하기와 같다.The monomers of norbornene and norbornene derivatives used in the production of norbornene copolymers of the present invention are synthesized by Diels-Alder reaction of a dienophile with an appropriately substituted cyclopentadiene. The reaction scheme is as follows.
또한 상기 화학식 2의 구조를 갖는 노르보넨 유도체 중, 5-노르보넨-2-카르복실산은 하기 반응식 2로 표시되는 딜스-알더(Diels-Alder) 반응에 의해 합성된다.In addition, among norbornene derivatives having the structure of Formula 2, 5-norbornene-2-carboxylic acid is synthesized by Diels-Alder reaction represented by the following Scheme 2.
본 발명의 공중합체 제조에 사용되는 또다른 단량체인 아세탈화된 노르보넨 구조는 상기 5-노르보넨-2-카르복실산을 하기 반응식 3에서와 같이 트리에틸아민(TEA)의 존재하에 클로로메틸에틸에테르와 반응하여 합성할 수 있다.The acetalized norbornene structure, which is another monomer used in the preparation of the copolymer of the present invention, is a 5-norbornene-2-carboxylic acid in the presence of triethylamine (TEA) as shown in Scheme 3 below. It can be synthesized by reaction with ether.
본 발명의 포토레지스트용 노르보넨 공중합체는 노르보넨 및 노르보넨 유도체를 비롯한 통상의 멀티사이클릭 중합체를 얻기 위한 라디칼중합, 양이온중합, 부가중합, 그리고 개환중합 등과 같은 중합기법을 모두 사용할 수 있으나, 바람직하게는 하기 화학식 5로 나타내어지는 팔라듐(Ⅱ) 화합물을 중합촉매로 사용하는 부가중합(addition polymerization)에 의하여 제조할 수 있다.Norbornene copolymers for photoresists of the present invention can be used all polymerization techniques such as radical polymerization, cationic polymerization, addition polymerization, and ring-opening polymerization to obtain conventional multicyclic polymers, including norbornene and norbornene derivatives, Preferably, the palladium (II) compound represented by Chemical Formula 5 may be prepared by addition polymerization using a palladium (II) compound as a polymerization catalyst.
상기 화학식에서,In the above formula,
X는 할로겐 원자 또는 탄소수 1~10의 알킬기이고;X is a halogen atom or an alkyl group having 1 to 10 carbon atoms;
R'은 탄소수 6~12의 알릴 화합물이고;R 'is an allyl compound having 6 to 12 carbon atoms;
R"는 니트릴 화합물 또는 시클로디엔 화합물이며;R ″ is a nitrile compound or a cyclodiene compound;
n은 1 또는 2이다.n is 1 or 2.
상기 중합반응시 중합용매로는 물을 단독으로 사용하거나 알코올 및 일반 유기용제를 물과 혼합하여 사용할 수 있다.As the polymerization solvent in the polymerization reaction, water may be used alone, or an alcohol and a general organic solvent may be mixed with water.
본 발명의 포토레지스트용 아세탈 함유 노르보넨 공중합체의 제조방법은 하기의 반응식 4에서와 같이 크게 두가지 방법으로 제조될 수 있다.The method for preparing the acetal-containing norbornene copolymer for photoresist of the present invention can be prepared by two methods, as shown in Scheme 4 below.
먼저 방법 1에 의하면 화학식 2로 표시되는 단량체와 화학식 3으로 표시되는 단량체를 상기 화학식 5의 팔라듐 촉매의 존재하에 용매 중에서 공중합시킨 후, 산 작용기의 일부를 상기 반응식 3과 동일한 원리로 아세탈화하는 방법이다.According to Method 1, a monomer represented by Formula 2 and a monomer represented by Formula 3 are copolymerized in a solvent in the presence of the palladium catalyst of Formula 5, and then a part of the acid functional groups is acetalized on the same principle as in Scheme 3 above. to be.
방법 2는 화학식 2로 표시되는 단량체 및 화학식 3으로 표시되는 단량체와 더불어 처음부터 화학식 4로 표시되는 아세탈 치환된 노르보넨 단량체를 임의의 비율로 반응기에 투입하여, 상기 화학식 5의 팔라듐 촉매의 존재하에 물을 사용한 용매 중에서 중합하는 방법이다.Method 2, in addition to the monomer represented by the formula (2) and the monomer represented by the formula (3) from the beginning acetal substituted norbornene monomer represented by the formula (4) to the reactor in any ratio, in the presence of the palladium catalyst of formula (5) It is a method of superposing | polymerizing in the solvent using water.
이와 같이 합성한 상기 공중합체의 바람직한 수평균분자량은 1,000~200,000이다. 이때 수평균분자량이 1,000 미만일 경우 공중합체가 무르게 되어 포토레지스트 박막의 형성이 어려우며, 200,000을 초과하는 경우 형성된 포토레지스트 박막이 부서지기 쉬운 상태가 되어 패턴이 불안정하게 된다. 따라서, 상기 제시된 범위내에서 노르보넨 공중합체의 수평균분자량을 조절함으로써 안정된 포토레지스트 박막을 형성할 수 있다.Thus, the preferable number average molecular weight of the said copolymer synthesize | combined is 1,000-200,000. In this case, when the number average molecular weight is less than 1,000, the copolymer becomes soft, which makes it difficult to form the photoresist thin film. When the number average molecular weight exceeds 200,000, the formed photoresist thin film becomes brittle and the pattern becomes unstable. Therefore, it is possible to form a stable photoresist thin film by controlling the number average molecular weight of the norbornene copolymer within the range given above.
이와 같이 중합된 아세탈 함유 노르보넨 공중합체를 통상의 포토레지스트 조성물 제조와 같은 방법으로 유기용매에 통상의 광산발생제와 함께 용해시킨 다음, 초미세 필터로 여과하여 포토레지스트 조성물을 제조함으로써 레지스트 패턴 형성에 사용할 수 있다.Thus-polymerized acetal-containing norbornene copolymer is dissolved in an organic solvent with a conventional photoacid generator in the same manner as a conventional photoresist composition, and then filtered with an ultrafine filter to form a photoresist composition to form a resist pattern. Can be used for
본 발명의 포토레지스트 조성물 제조에 사용되는 유기용매로서는, 구체적으로 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜프로필에테르아세테이트, 디에틸렌글리콜디메틸에테르, 에틸락테이트, 톨루엔, 크실렌, 자이렌, 메틸에틸케톤, 시클로헥사논, 2-헵타논, 3-헵타논, 및 4-헵타논으로 이루어진 군에서 선택된 1종 이상의 물질을 사용할 수 있다. 또한, 필요에 따라 상기 유기용매 이외에 보조용매로서 N-메틸포름아미드, N,N-디메틸포름아미드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-메틸피롤리돈, 디메틸설폭사이드, 트리페닐이미다졸, 알콜류 등을 병용할 수 있으며, 보조용매를 사용하는 경우 전체 용매중 보조 용매가 차지하는 함량은 10 중량% 이하인 것이 바람직하다.Specific examples of the organic solvent used in the preparation of the photoresist composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol dimethyl ether, ethyl lactate, toluene, xylene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone And at least one substance selected from the group consisting of 4-heptanone. If necessary, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide may be used as co-solvents in addition to the organic solvent. , Triphenylimidazole, alcohols and the like may be used in combination, and when the co-solvent is used, the content of the co-solvent in the total solvent is preferably 10% by weight or less.
상기 포토레지스트 조성물 중 본 발명의 공중합체의 함량은 유기용매, 광산발생제, 및 리소그래피 조건 등에 따라 변할 수 있으나, 대체로 포토레지스트 제조시 사용하는 유기용매 100 중량부 대비 10~30 중량부의 농도로 용해시키는 것이 바람직하다.The content of the copolymer of the present invention in the photoresist composition may vary depending on organic solvents, photoacid generators, and lithography conditions, but is generally dissolved at a concentration of 10 to 30 parts by weight relative to 100 parts by weight of the organic solvent used in preparing the photoresist. It is preferable to make it.
본 발명의 포토레지스트 조성물 제조에 사용되는 광산발생제로서는, 구체적으로 트리페닐설포늄 트리플루오로메탄설포네이트, 트리페닐설포늄 퍼플루오로옥탄설포네이트, 디페닐-p-토릴설포늄 퍼플루오로옥탄설포네이트, 트리스(p-토릴)설포늄 퍼플루오로옥탄설포네이트, 트리스(p-클로로벤젠)설포늄 트리플루오로메탄설포네이트, 트리스(p-토릴)설포늄 트리플루오로메탄설포네이트, 트리메틸설포늄 트리플루오로메탄설포네이트, 디메틸페닐설포늄 트리플루오로메탄설포네이트, 디메틸토릴설포늄 트리플루오로메탄설포네이트, 디메틸토릴설포늄 퍼플루오로옥탄설포네이트, 트리페닐설포늄 p-톨루엔설포네이트, 트리페닐설포늄 메탄설포네이트, 트리페닐설포늄 부탄설포네이트, 트리페닐설포늄 n-옥탄설포네이트, 트리페닐설포늄 1-나프탈렌설포네이트, 트리페닐설포늄 2-나프탈렌설포네이트, 트리페닐설포늄 10-캠퍼설포네이트, 트리페닐설포늄 2,5-디클로로벤젠설포네이트, 디페닐토릴설포늄 1,3,4-트리클로로벤젠설포네이트, 디메틸토릴설포늄 p-톨루엔설포네이트, 디페닐토릴설포늄 2,5-디클로로벤젠설포네이트, 1-시클로헥실설포닐-1-(1,1-디메틸에틸설포닐)디아조메탄, 비스(1,1-디메틸에틸설포닐)디아조메탄, 비스(1-메틸에틸설포닐)메탄, 비스(시클로헥실설포닐)디아조메탄,1-시클로헥실설포닐-1-시클로헥실카르보닐디아조메탄,1-디아조-1-시클로헥실설포닐-3,3'-디메틸부탄-2-논, 1-디아조-1-메틸설포닐-4-페닐부탄-2-논, 1-디아조-1-(1,1-디메틸에틸설포닐)-3,3-디메틸-2-부탄논 및 1-아세틸-1-(1-메틸에틸설포닐)디아조메탄로 이루이전 군에서 선택된 1종 이상의 물질을 사용할 수 있다. 상기 광산발생제의 함량은 상기 공중합체 수지 100중량부 대비 0.1~10 중량부인 것이 바람직하다.Specific examples of photoacid generators used in the preparation of the photoresist composition of the present invention include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, and diphenyl-p-tolylsulfonium perfluoro. Octanesulfonate, tris (p-toryl) sulfonium perfluorooctanesulfonate, tris (p-chlorobenzene) sulfonium trifluoromethanesulfonate, tris (p-tolyl) sulfonium trifluoromethanesulfonate, Trimethylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethyltorylsulfonium trifluoromethanesulfonate, dimethyltorylsulfonium perfluorooctanesulfonate, triphenylsulfonium p-toluene Sulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium butanesulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfonium 1-naphthalenesulfo Acetate, triphenylsulfonium 2-naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2,5-dichlorobenzenesulfonate, diphenyltorylsulfonium 1,3,4-trichlorobenzenesulfo Nitrate, dimethyl torylsulfonium p-toluenesulfonate, diphenyltorylsulfonium 2,5-dichlorobenzenesulfonate, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) methane, bis (cyclohexylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldia Zomethane, 1-diazo-1-cyclohexylsulfonyl-3,3'-dimethylbutan-2-non, 1-diazo-1-methylsulfonyl-4-phenylbutan-2-non, 1-dia 1 selected from the group consisting of crude-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone and 1-acetyl-1- (1-methylethylsulfonyl) diazomethane More than one substance can be used. The content of the photoacid generator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the copolymer resin.
이와 같이 제조된 포토레지스트 조성물을 웨이퍼에 도포하여 포토레지스트 박막을 형성시킨 다음, 후속 공정에서 포토레지스트 패턴을 형성한다.The photoresist composition thus prepared is applied to a wafer to form a photoresist thin film, and then a photoresist pattern is formed in a subsequent process.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안된다.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.
제조예 1: 5-노르보넨-2-에톡시메틸카르복실레이트(이하 ANCA)의 합성 Preparation Example 1 Synthesis of 5-norbornene-2-ethoxymethylcarboxylate (hereinafter ANCA)
반응기에 5-노르보넨-2-카르복실산 1몰을 녹인 THF 용액에 트리에틸아민 1.1몰과 클로로메틸에틸에테르 1.1몰을 넣은 다음 실온에서 약 6시간 동안 반응시켰다. 반응 완료 후 감압 증류하여 5-노르보넨-2-에톡시메틸카르복실레이트를 얻었다. 수율은 89%이었다.1.1 mole of triethylamine and 1.1 mole of chloromethylethyl ether were added to a THF solution in which 1 mole of 5-norbornene-2-carboxylic acid was dissolved in a reactor, and reacted at room temperature for about 6 hours. After completion of the reaction, distillation under reduced pressure to obtain 5-norbornene-2-ethoxymethylcarboxylate. Yield 89%.
제조예 2: 4-옥사-트리시클로[5,2,1,0(2,6)]데카-8-엔-3-온(이하 NL)의 합성 Preparation Example 2 Synthesis of 4-oxa-tricyclo [5,2,1,0 (2,6)] deca-8-en-3-one (hereinafter NL)
반응기에 시클로펜타디엔 1몰과 퓨라논 1.2몰을 넣은 다음 약 60℃에서 약 24시간 반응시켰다. 반응 완료 후 감압 증류하여 엔도(endo)와 엑소(exo) 혼합물의4-옥사-트리시클로[5,2,1,0(2,6)]데카-8-엔-3-온을 얻었다. 수율은 80%이었다.1 mole of cyclopentadiene and 1.2 mole of furanone were added to the reactor and reacted at about 60 ° C. for about 24 hours. After completion of the reaction, distillation under reduced pressure afforded 4-oxa-tricyclo [5,2,1,0 (2,6)] deca-8-en-3-one of a mixture of endo and exo. Yield 80%.
제조예 3: 5-노르보넨-2-헥사플루오로이소프로판올(이하 NFO)의 합성 Preparation Example 3 Synthesis of 5-norbornene-2-hexafluoroisopropanol (hereinafter NFO)
알릴브로마이드 1.1몰을 녹인 THF 용액에 헥사플루오로아세톤 1몰을 0℃에서 천천히 적가한 다음, 실온에서 약 4시간 반응시켰다. 반응물을 HCl 처리하고 물과 에테르로 추출한 다음, 유기층을 감압증류하여 중간생성물, 알릴헥사플루오로이소프로판올을 얻는다. 반응기에 시클로펜타디엔 1몰과 중간생성물 1몰을 넣은 다음 약 80℃에서 약 24시간 반응시켰다. 반응 완료 후 감압 증류하여 엔도(endo)와 엑소(exo) 혼합물의 5-노르보넨-2-헥사플루오로이소프로판올을 얻었다. 수율은 60%이었다.1 mol of hexafluoroacetone was slowly added dropwise at 0 ° C to a THF solution in which 1.1 mol of allyl bromide was dissolved, and then reacted at room temperature for about 4 hours. The reaction was treated with HCl, extracted with water and ether, and the organic layer was distilled under reduced pressure to obtain an intermediate product, allylhexafluoroisopropanol. 1 mole of cyclopentadiene and 1 mole of intermediate were placed in a reactor and reacted at about 80 ° C. for about 24 hours. After completion of the reaction, distillation under reduced pressure afforded 5-norbornene-2-hexafluoroisopropanol of an endo and exo mixture. Yield 60%.
제조예 4: 5-노르보넨-2-카르복실산(이하 NCA)과 5-노르보넨-2-메탄올(이하 NM) 공중합체 합성 Preparation Example 4 Synthesis of 5-norbornene-2-carboxylic acid (hereinafter NCA) and 5-norbornene-2-methanol (hereinafter NM) copolymer
1) Poly[NCA/NM]=9/1(w/w)1) Poly [NCA / NM] = 9/1 (w / w)
팔라듐클로라이드 1.0g과 물과 THF의 혼합용액 30g을 반응기에 넣고 공단량체로서 5-노르보넨-2-카르복실산 54g과 5-노르보넨-2-메탄올 6g을 넣은 다음, 약 40℃에서 약 24시간 반응시켰다. 이때, 반응기는 질소 분위기를 유지하였다. 반응 완료 후 중합한 반응액을 적당량의 THF 용매로 희석하여 증류수와 에탄올의 1:1 혼합용액에 침전시킨 다음 여과하고 건조하여 중합체(Mn=2,500)를 얻었다. 수율은 89%였다.1.0 g of palladium chloride and 30 g of a mixture of water and THF were placed in a reactor, and 54 g of 5-norbornene-2-carboxylic acid and 6 g of 5-norbornene-2-methanol were added as comonomers. The reaction was time. At this time, the reactor maintained a nitrogen atmosphere. After completion of the reaction, the polymerized reaction solution was diluted with an appropriate amount of THF solvent, precipitated in a 1: 1 mixed solution of distilled water and ethanol, filtered and dried to obtain a polymer (Mn = 2,500). Yield 89%.
2) Poly[NCA/NM]=7/3(w/w)2) Poly [NCA / NM] = 7/3 (w / w)
5-노르보넨-2-카르복실산 42g과 5-노르보넨-2-메탄올 18g을 넣은 것을 제외하고는 1)에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,600)를 얻었다. 수율은 80%였다.Polymerization (Mn = 2,600) was obtained by polymerization according to the method shown in 1) except that 42 g of 5-norbornene-2-carboxylic acid and 18 g of 5-norbornene-2-methanol were added thereto. Yield 80%.
3) Poly[NCA/NM]=5/5(w/w)3) Poly [NCA / NM] = 5/5 (w / w)
5-노르보넨-2-카르복실산 30g과 5-노르보넨-2-메탄올 30g을 넣은 것을 제외하고는 1)에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,500)를 얻었다. 수율은 64%였다.Polymerization was carried out according to the method shown in 1) except that 30 g of 5-norbornene-2-carboxylic acid and 30 g of 5-norbornene-2-methanol were added to obtain a polymer (Mn = 2,500). Yield 64%.
제조예 5: 5-노르보넨-2-카르복실산과 4-옥사-트리시클로[5,2,1,0(2,6)]데카-8-엔-3-온(이하 NL) 공중합체 합성, Poly[NCA/NL]=7/3(w/w) Preparation Example 5 Synthesis of 5-norbornene-2-carboxylic acid and 4-oxa-tricyclo [5,2,1,0 (2,6)] deca-8-en-3-one (hereinafter NL) copolymer , Poly [NCA / NL] = 7/3 (w / w)
공단량체로서 5-노르보넨-2-카르복실산 42g과 4-옥사-트리시클로[5,2,1,0(2,6)]데카-8-엔-3-온 18g을 사용하는 것을 제외하고는 제조예 4에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,700)를 얻었다. 수율은 60%였다.Except using 42 g of 5-norbornene-2-carboxylic acid and 18 g of 4-oxa-tricyclo [5,2,1,0 (2,6)] deca-8-en-3-one as comonomer Then, polymerization was carried out according to the method shown in Preparation Example 4 to obtain a polymer (Mn = 2,700). Yield 60%.
제조예 6:5-노르보넨-2-카르복실산과 노르보넨(이하 NB) 공중합체 합성, Poly[NCA/NB] =7/3(w/w) Preparation Example 6 Synthesis of 5-norbornene-2-carboxylic acid and norbornene (hereinafter NB) copolymer, Poly [NCA / NB] = 7/3 (w / w)
공단량체로서 5-노르보넨-2-카르복실산 42g과 노르보넨 18g을 사용하는 것을 제외하고는 제조예 4에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,200)를 얻었다. 수율은 52%였다.Polymerization was carried out according to the method shown in Preparation Example 4 except that 42 g of 5-norbornene-2-carboxylic acid and 18 g of norbornene were used as comonomers to obtain a polymer (Mn = 2,200). Yield 52%.
제조예 7: 5-노르보넨-2-카르복실산과 5-노르보넨-2,3-디메탄올(이하 NDM) 공중합체 합성, Poly[NCA/NDM]=7/3(w/w) Preparation Example 7 Synthesis of 5-norbornene-2-carboxylic acid and 5-norbornene-2,3-dimethanol (hereinafter NDM) copolymer, Poly [NCA / NDM] = 7/3 (w / w)
공단량체로서 5-노르보넨-2-카르복실산 42g과 5-노르보넨-2,3-디메탄올 18g을 사용하는 것을 제외하고는 제조예 4에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,800)를 얻었다. 수율은 62%였다.Polymerization was carried out according to the method shown in Preparation Example 4, except that 42 g of 5-norbornene-2-carboxylic acid and 18 g of 5-norbornene-2,3-dimethanol were used as comonomers (Mn = 2,800). ) Yield 62%.
제조예 8: 5-노르보넨-2-카르복실산과 5-노르보넨-2-올(이하 NO) 공중합체 합성, Poly[NCA/NO]=7/3(w/w) Preparation Example 8 Synthesis of 5-norbornene-2-carboxylic acid and 5-norbornene-2-ol (hereinafter NO) copolymer, Poly [NCA / NO] = 7/3 (w / w)
공단량체로서 5-노르보넨-2-카르복실산 42g과 5-노르보넨-2-올 18g을 사용하는 것을 제외하고는 제조예 4에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,300)를 얻었다. 수율은 75%였다.Polymerization was carried out according to the method shown in Preparation Example 4 except that 42 g of 5-norbornene-2-carboxylic acid and 18 g of 5-norbornene-2-ol were used as comonomers to obtain a polymer (Mn = 2,300). . Yield 75%.
제조예 9: 5-노르보넨-2-헥사플루오로이소프로판올(이하 NFO)과 5-노르보넨-2-올(이하 NO) 공중합체 합성, Poly[NFO/NO]=7/3(w/w) Preparation Example 9 Synthesis of 5-norbornene-2-hexafluoroisopropanol (hereinafter referred to as NFO) and 5-norbornene-2-ol (hereinafter referred to as NO) copolymer, Poly [NFO / NO] = 7/3 (w / w )
공단량체로서 5-노르보넨-2-헥사플루오로이소프로판올 42g과 5-노르보넨-2-올 18g을 사용하는 것을 제외하고는 제조예 4에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,700)를 얻었다. 수율은 68%였다.Polymerization (Mn = 2,700) was carried out by polymerization according to the method shown in Preparation Example 4, except that 42 g of 5-norbornene-2-hexafluoroisopropanol and 18 g of 5-norbornene-2-ol were used as comonomers. Got it. Yield 68%.
제조예 10: 5-노르보넨-2-카르복실산과 5-노르보넨-2-카르복실산 티부틸레이트(이하 NtB) 공중합체 합성, Poly[NCA/NtB]=7/3(w/w) Preparation Example 10 Synthesis of 5-norbornene-2-carboxylic acid and 5-norbornene-2-carboxylic acid thibutylate (hereinafter referred to as NtB) copolymer, Poly [NCA / NtB] = 7/3 (w / w)
공단량체로서 5-노르보넨-2-카르복실산 42g과 5-노르보넨-2-카르복실산 티부틸레이트 18g을 사용하는 것을 제외하고는 제조예 4에 나타내어진 방법에 따라 중합하여 중합체(Mn=2,600)를 얻었다. 수율은 61%였다.1H-NMR (DMSO-d6) δ 1.4 (-C(CH3)3[t-butyl]), 2~3.0 (-CH2, -CH [bridghead, main chain]), 11.7 (-OH [carboxylic acid]). FTIR (film on NaCl) cm-13200-3400 (OH), 2900-3000 (C-H), 1720 (C=O, ester), 1700 (C=O, carboxylic acid), 1150 (C-O-C, ester).Polymerization was carried out according to the method shown in Preparation Example 4, except that 42 g of 5-norbornene-2-carboxylic acid and 18 g of 5-norbornene-2-carboxylic acid thibutylate were used as comonomers. = 2,600). Yield 61%. 1 H-NMR (DMSO- d 6) δ 1.4 (-C (CH 3 ) 3 [t-butyl]), 2 ~ 3.0 (-CH 2 , -CH [bridghead, main chain]), 11.7 (-OH [ carboxylic acid]). FTIR (film on NaCl) cm -1 3200-3400 (OH), 2900-3000 (CH), 1720 (C = O, ester), 1700 (C = O, carboxylic acid), 1150 (COC, ester).
[제조된 공중합체 중의 금속성분의 제거][Removal of Metal Components in Prepared Copolymers]
상기 제조예 4~9에서 합성한 노르보넨 공중합체를 각각 반응기에 넣고 THF 용매에 10중량% 정도 녹인 다음, 수소 기체를 버블링하면서 약 5시간 동안 교반시켰다. 이때 생성된 검은색 침전물은 여과하여 제거하고, 남은 반응액은 증류수에 침전시킨 다음 여과하고 건조시켰다The norbornene copolymers synthesized in Preparation Examples 4 to 9 were each put in a reactor, dissolved in about 10% by weight of THF solvent, and stirred for about 5 hours while bubbling hydrogen gas. The black precipitate produced at this time was removed by filtration, and the remaining reaction solution was precipitated in distilled water, followed by filtration and drying.
제조예 11: Poly[ANCA/NCA/NM]=4/3/3(w/w/w)의 합성 Preparation Example 11 Synthesis of Poly [ANCA / NCA / NM] = 4/3/3 (w / w / w)
1) 방법 1에 의한 합성1) Synthesis by Method 1
반응기에 제조예 4에서 합성한 공중합체(Poly[NCA/NM]=7/3(w/w)) 30g을 THF 360ml에 녹인 후, 트리에틸아민 8.8g과 클로로메틸에틸에테르 10.6g을 넣은 다음약 3 내지 5시간 반응시켰다. 이때 반응기는 질소 분위기를 유지하였다. 반응 완료 후 중합한 반응액을 증류수에 침전시킨 다음 여과하고 건조하여, 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 질량평균 분자량(Mn)는 2,800, 수율은 96%였다.30 g of the copolymer (Poly [NCA / NM] = 7/3 (w / w)) synthesized in Preparation Example 4 was dissolved in THF 360ml, and then 8.8 g of triethylamine and 10.6 g of chloromethylethyl ether were added thereto. The reaction was performed for about 3 to 5 hours. At this time, the reactor maintained a nitrogen atmosphere. After the reaction was completed, the polymerized reaction solution was precipitated in distilled water, filtered and dried to obtain a norbornene copolymer including an acetal group having the above composition. The mass average molecular weight (Mn) of the polymer was 2,800 and the yield was 96%.
2) 방법 2에 의한 합성2) Synthesis by Method 2
팔라듐클로라이드 0.5g과 물과 THF의 혼합용액 15g을 반응기에 넣은 후, 공단량체로서 제조예 1에서 합성한 5-노르보넨-2-에톡시메틸카르복실레이트 12g과 5-노르보넨-2-카르복실산 9g, 그리고 5-노르보넨-2-메탄올 9g을 넣은 다음 약 40℃에서 약 24시간 반응시켰다. 이때, 반응기는 질소 분위기를 유지하였다. 반응 완료 후 중합한 반응액을 적당량의 THF 용액으로 희석하여 증류수와 에탄올의 1:1 혼합용액에 침전시킨 다음 여과하고 건조하여, 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 2,100, 수율은 51%였다.0.5 g of palladium chloride and 15 g of a mixed solution of water and THF were placed in a reactor, and then 12 g of 5-norbornene-2-ethoxymethylcarboxylate synthesized in Preparation Example 1 as a comonomer and 5-norbornene-2-carr 9 g of acid and 9 g of 5-norbornene-2-methanol were added and then reacted at about 40 ° C. for about 24 hours. At this time, the reactor maintained a nitrogen atmosphere. After completion of the reaction, the polymerized reaction solution was diluted with an appropriate amount of THF solution, precipitated in a 1: 1 mixed solution of distilled water and ethanol, filtered, and dried to obtain a norbornene copolymer including an acetal group having the above composition. The number average molecular weight (Mn) of the polymer was 2,100, and the yield was 51%.
제조예 12: Poly[ANCA/NCA/NL]=4/3/3(w/w/w)의 합성 Preparation Example 12 Synthesis of Poly [ANCA / NCA / NL] = 4/3/3 (w / w / w)
반응기에 제조예 5에서 합성한 공중합체(Poly[NCA/NL]=7/3(w/w))를 사용한 외에는 제조예 10의 방법 1에 의해 반응시켜 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 2,900, 수율은 94%였다.The norbornene air containing the acetal group of the above composition was reacted by the method 1 of Preparation Example 10, except that the copolymer synthesized in Preparation Example 5 (Poly [NCA / NL] = 7/3 (w / w)) was used in the reactor. The coalescence was obtained. The number average molecular weight (Mn) of the polymer was 2,900, and the yield was 94%.
제조예 13: Poly[ANCA/NCA/NB]=4/3/3(w/w/w)의 합성 Preparation Example 13 Synthesis of Poly [ANCA / NCA / NB] = 4/3/3 (w / w / w)
반응기에 제조예 6에서 합성한 공중합체(Poly[NCA/NB]=7/3(w/w))를 사용한 외에는 제조예 10의 방법 1에 의해 반응시켜 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 2,300, 수율은 95%였다.The norbornene air containing the acetal group of the above composition was reacted by the method 1 of Preparation Example 10, except that the copolymer synthesized in Preparation Example 6 (Poly [NCA / NB] = 7/3 (w / w)) was used in the reactor. The coalescence was obtained. The number average molecular weight (Mn) of the polymer was 2,300, and the yield was 95%.
제조예 14: Poly[ANCA/NCA/NDM]=4/3/3(w/w/w)의 합성 Preparation Example 14 Synthesis of Poly [ANCA / NCA / NDM] = 4/3/3 (w / w / w)
반응기에 제조예 7에서 합성한 공중합체(Poly[NCA/NDM]=7/3(w/w))를 사용하는 것을 제외하고는 제조예 10에서 나타내어진 방법 1에 따라 반응시켜 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 2,900, 수율은 90%였다.Acetal of the above composition was reacted according to Method 1 shown in Preparation Example 10, except that the copolymer synthesized in Preparation Example 7 (Poly [NCA / NDM] = 7/3 (w / w)) was used in the reactor. The norbornene copolymer containing group was obtained. The number average molecular weight (Mn) of the polymer was 2,900, and the yield was 90%.
제조예 15: Poly[ANCA/NCA/NO]=4/3/3(w/w/w)의 합성 Preparation Example 15 Synthesis of Poly [ANCA / NCA / NO] = 4/3/3 (w / w / w)
제조예 8에서 합성한 공중합체(Poly[NCA/NO]=7/3(w/w))를 사용하는 것을 제외하고는 제조예 10에서 나타내어진 방법 1에 따라 반응시켜 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 2,500, 수율은 93%였다.Except for using the copolymer synthesized in Preparation Example 8 (Poly [NCA / NO] = 7/3 (w / w)) by reacting according to the method 1 shown in Preparation Example 10 to include the acetal group of the composition The norbornene copolymer was obtained. The number average molecular weight (Mn) of the polymer was 2,500, and the yield was 93%.
제조예 16: Poly[ANFO/NCA/NO]=4/3/3(w/w/w)의 합성 Preparation Example 16 Synthesis of Poly [ANFO / NCA / NO] = 4/3/3 (w / w / w)
제조예 9에서 합성한 공중합체(Poly[NFO/NO]=7/3(w/w))를 사용하는 것을 제외하고는 제조예 10에서 나타내어진 방법 1에 따라 반응시켜 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 2,900, 수율은 90%였다.Except for using the copolymer synthesized in Preparation Example 9 (Poly [NFO / NO] = 7/3 (w / w)) by reacting according to the method 1 shown in Preparation Example 10 to include the acetal group of the composition The norbornene copolymer was obtained. The number average molecular weight (Mn) of the polymer was 2,900, and the yield was 90%.
제조예 17: Poly[ANCA/NCA/NtB]=4/3/3(w/w/w)의 합성Preparation Example 17 Synthesis of Poly [ANCA / NCA / NtB] = 4/3/3 (w / w / w)
제조예 10에서 합성한 공중합체(Poly[NCA/NtB]=7/3(w/w))를 사용하는 것을 제외하고는 제조예 11에서 나타내어진 방법 1에 따라 반응시켜 상기 조성의 아세탈기를 포함하는 노르보넨 공중합체를 얻었다. 중합체의 수평균 분자량(Mn)는 3,000, 수율은 92%였다.1H-NMR (DMSO-d6) δ 1.1, 3.6 (-CH2CH3[ethyl]), 1.4 (-C(CH3)3[t-butyl]), 2~3.0 (-CH2, -CH [bridghead, main chain]), 5.2 (O-CH2-O [methyl]), 11.7 (-OH [carboxylic acid]). FTIR (film on NaCl) cm-13200-3400 (OH), 2900-3000 (C-H), 1720 (C=O, ester), 1700 (C=O, carboxylic acid), 1150 (C-O-C, ester), 1115 (C-O-C, ether).Except for using the copolymer synthesized in Preparation Example 10 (Poly [NCA / NtB] = 7/3 (w / w)) and reacted according to the method 1 shown in Preparation Example 11 to include the acetal group of the composition The norbornene copolymer was obtained. The number average molecular weight (Mn) of the polymer was 3,000, and the yield was 92%. 1 H-NMR (DMSO- d 6 ) δ 1.1, 3.6 (-CH 2 CH 3 [ethyl]), 1.4 (-C (CH 3) 3 [t-butyl]), 2 ~ 3.0 (-CH 2, - Bridhead, main chain), 5.2 (O-CH 2 -O [methyl]), 11.7 (-OH [carboxylic acid]). FTIR (film on NaCl) cm -1 3200-3400 (OH), 2900-3000 (CH), 1720 (C = O, ester), 1700 (C = O, carboxylic acid), 1150 (COC, ester), 1115 (COC, ether).
[레지스트의 제조 및 패턴 형성][Production of resist and pattern formation]
상기 제조예 11~17에서 합성한 공중합체를 각각 시클로헥사논에 12 중량%의 농도로 용해시키고, 공지의 광산발생제인 트리페닐설포늄 트리플루오로메탄설포네이트를 상기 공중합체 100중량부 대비 3 중량부가 되는 양으로 첨가하여 용해시킨 후, 0.2㎛ 필터로 여과하여 레지스트 용액을 제조하였다. 이와 같이 제조된 레지스트 용액을 실리콘 기판에 회전 도포하여 두께 0.5㎛의 박막을 형성시켰다. 상기 기판을 110℃에서 전열처리하고, ArF 엑시머 레이저(193nm) 장치를 이용하여 노광시키고, 다시 110℃에서 후열처리한 다음 2.38 중량% TMAH(tetramethylammoniumhydroxide) 알칼리 수용액에 60초간 침지현상하여 패턴을 형성시켰다.Each of the copolymers synthesized in Preparation Examples 11 to 17 was dissolved in cyclohexanone at a concentration of 12% by weight, and triphenylsulfonium trifluoromethanesulfonate, a known photoacid generator, was added to 100 parts by weight of the copolymer. After adding and dissolving in an amount to be added in parts by weight, a 0.2 µm filter was used to prepare a resist solution. The resist solution thus prepared was spun onto a silicon substrate to form a thin film having a thickness of 0.5 μm. The substrate was heat-treated at 110 ° C., exposed using an ArF excimer laser (193 nm) device, further heat-treated at 110 ° C., and then immersed in a 2.38 wt% aqueous tetramethylammoniumhydroxide (TMAH) alkali solution for 60 seconds to form a pattern. .
도 1은 제조예 17에 의한 공중합체를 사용하여 형성한 0.15㎛의 포지티브형 패턴의 사진을 나타낸다.1 shows a photograph of a positive pattern of 0.15 탆 formed using the copolymer according to Production Example 17. FIG.
이상에서 설명한 바와 같이, 본 발명의 새로운 중합방법을 사용하여 제조한 아세탈기 함유 노르보넨 공중합체는 200nm 이하 엑시머 레이저 영역에서의 투명성, 해상도, 감도 및 건식 에칭 내성이 우수하고, 알칼리 현상액을 사용할 수 있을 뿐만 아니라, 기판에 대한 접착력이 뛰어나므로, 초고집적 반도체의 엑시머 레이저에 미세가공 뿐만 아니라 전자선이나 원자외선에 의한 미세 가공에도 유용하다.As described above, the acetal group-containing norbornene copolymer prepared using the new polymerization method of the present invention is excellent in transparency, resolution, sensitivity and dry etching resistance in the excimer laser region of 200 nm or less, and can use an alkaline developer. Not only that, but also excellent adhesion to the substrate, it is useful not only for microfabrication in excimer laser of ultra-high density semiconductor but also for microfabrication by electron beam or far ultraviolet ray.
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| TW091104788A TW591329B (en) | 2001-04-21 | 2002-03-13 | Acetal group containing norbornene copolymer for photoresist, method for producing the same and photoresist composition containing the same |
| US10/126,985 US6762268B2 (en) | 2001-04-21 | 2002-04-22 | Acetal group containing norbornene copolymer for photoresist, method for producing the same and photoresist composition containing the same |
| JP2002119638A JP2002348333A (en) | 2001-04-21 | 2002-04-22 | Norbornene copolymer for photoresist, method for producing the same and photoresist composition containing the same |
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| US8449954B2 (en) | 2010-07-07 | 2013-05-28 | Lg Chem, Ltd. | Compound having photoreactive functional group, photoreactive polymer, and alignment film comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980060897A (en) * | 1996-12-31 | 1998-10-07 | 김영환 | ArF photosensitive film resin incorporating amide or imide |
| KR20000009572A (en) * | 1998-07-27 | 2000-02-15 | 김영환 | New polymer and photoresist composition therefrom |
| KR20000056467A (en) * | 1999-02-22 | 2000-09-15 | 김영환 | Novel photoresist crosslinker and photoresist composition using the same |
| KR20010011771A (en) * | 1999-07-30 | 2001-02-15 | 김영환 | Novel photoresist polymer and photoresist composition containing it |
| KR20020057565A (en) * | 2001-01-05 | 2002-07-11 | 윤종용 | Method for preparing norbornene-based resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980060897A (en) * | 1996-12-31 | 1998-10-07 | 김영환 | ArF photosensitive film resin incorporating amide or imide |
| KR20000009572A (en) * | 1998-07-27 | 2000-02-15 | 김영환 | New polymer and photoresist composition therefrom |
| KR20000056467A (en) * | 1999-02-22 | 2000-09-15 | 김영환 | Novel photoresist crosslinker and photoresist composition using the same |
| KR20010011771A (en) * | 1999-07-30 | 2001-02-15 | 김영환 | Novel photoresist polymer and photoresist composition containing it |
| KR20020057565A (en) * | 2001-01-05 | 2002-07-11 | 윤종용 | Method for preparing norbornene-based resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8449954B2 (en) | 2010-07-07 | 2013-05-28 | Lg Chem, Ltd. | Compound having photoreactive functional group, photoreactive polymer, and alignment film comprising the same |
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