KR20030028987A - Fluorine-containing photosensitive polymer and chemically amplified negative resist composition comprising the same - Google Patents
Fluorine-containing photosensitive polymer and chemically amplified negative resist composition comprising the same Download PDFInfo
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- KR20030028987A KR20030028987A KR1020010061451A KR20010061451A KR20030028987A KR 20030028987 A KR20030028987 A KR 20030028987A KR 1020010061451 A KR1020010061451 A KR 1020010061451A KR 20010061451 A KR20010061451 A KR 20010061451A KR 20030028987 A KR20030028987 A KR 20030028987A
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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
- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F232/08—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 condensed rings
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
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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
- 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
- G03F7/0395—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 a backbone with alicyclic moieties
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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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
- 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
- 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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- G—PHYSICS
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- G—PHYSICS
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- 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
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
Abstract
Description
본 발명은 감광성 폴리머 및 화학증폭형 네가티브형 레지스트 조성물에 관한 것으로, 특히 ArF(193nm) 및 F2(157nm) 엑시머 레이저용으로 사용 가능하며 플루오르를 함유하는 감광성 폴리머 및 이를 포함하는 화학증폭형 네가티브형 레지스트 조성물에 관한 것이다.FIELD OF THE INVENTION The present invention relates to photosensitive polymers and chemically amplified negative resist compositions, in particular for use in ArF (193 nm) and F 2 (157 nm) excimer lasers, including fluorine-containing photosensitive polymers and chemically amplified negative types It relates to a resist composition.
반도체 제조 공정이 복잡해지고 반도체 소자의 집적도가 증가함에 따라 미세한 패턴 형성이 요구된다. 더욱이, 반도체 소자의 용량이 1기가(Giga) 비트급 이상인 소자에 있어서, 디자인 룰이 0.1μm 이하인 패턴 사이즈가 요구되고, 그에 따라 기존의 KrF 엑시머 레이저(248nm)를 이용한 레지스트 재료를 사용하는 데 한계가 있다. 따라서, KrF 엑시머 레이저에 비해 보다 단파장의 에너지원인 ArF 엑시머 레이저(193nm) 또는 F2(157nm) 엑시머 레이저를 이용한 리소그래피 기술이 등장하여 개발되었다. 그 중에서도 F2(157nm) 엑시머 레이저를 이용하는 리소그래피 공정에서는 새로운 구조의 레지스트 재료가 요구된다.As the semiconductor manufacturing process becomes complicated and the degree of integration of semiconductor devices increases, fine pattern formation is required. Furthermore, in devices with a semiconductor device having a capacity of 1 gigabit or more, a pattern size of 0.1 μm or less is required, and thus there is a limit to using a resist material using a conventional KrF excimer laser (248 nm). have. Therefore, a lithography technique using ArF excimer laser (193 nm) or F 2 (157 nm) excimer laser, which is a shorter wavelength energy source than KrF excimer laser, has appeared and was developed. In particular, a lithography process using an F 2 (157 nm) excimer laser requires a resist material having a new structure.
F2(157nm) 엑시머 레이저를 사용하는 리소그래피 기술에서 사용되는 재료들은 다음과 같은 기본적인 특성들을 만족해야 한다. 첫째, 레지스트막은 해당 광원에서 높은 투과도를 가져야 한다. 둘째, 건식 식각 공정시 사용되는 플라즈마에 대하여 식각 내성이 좋아야 한다. 셋째, 패턴이 무너지는 현상을 방지하기 위하여 하부 막질에 대한 접착 특성이 좋아야 한다. 넷째, 통상적으로 사용되고 있는 현상액으로 현상이 가능해야 한다.Materials used in lithography techniques that use F 2 (157 nm) excimer lasers must meet the following basic characteristics: First, the resist film must have high transmittance in the light source. Second, the etching resistance to the plasma used in the dry etching process should be good. Third, in order to prevent the pattern from collapsing, the adhesion property to the underlying film should be good. Fourth, development should be possible with a developer that is commonly used.
상기와 같은 재료적 특성들을 만족하기에는 여러 가지 한계점이 많다. 그 중에서 특히, 고분자 재료의 투과도 측면과 건식 식각에 대한 내성이 가장 큰 문제점으로 지적되어 왔다.There are many limitations to satisfy such material properties. Among them, in particular, the side of permeability of polymer materials and resistance to dry etching have been pointed out as the biggest problems.
현재까지, 차세대 F2엑시머 레이저용 레지스트 재료로서 몇가지 재료들이 알려져 왔는데, 주로 플루오르화된 폴리머 및 실록산 폴리머들이 많이 연구되어져 왔다. 특히, 플루오르화된 폴리머는 157nm에서의 투과도 특성이 우수하여 차세대 레지스트 재료로서 많이 연구되고 있다. 그러나, 이 재료는 모노머 합성이 어려우며 고분자 특성에 있어서도 소수성(hydrophobicity)이 너무 강하여 레지스트 재료로서의 적합한 구조를 찾기가 어려웠다.To date, several materials have been known as resist materials for next generation F 2 excimer lasers, mainly fluorinated polymers and siloxane polymers. In particular, the fluorinated polymer has been excellently studied as a next-generation resist material because of its excellent transmittance at 157 nm. However, this material has difficulty in synthesizing monomers and its hydrophobicity is so strong in polymer properties that it is difficult to find a suitable structure as a resist material.
종래 기술에 따른 초기의 157nm용 레지스트 재료중 하나로서 다음에 표시하는 구조를 가지는 폴리노르보르넨 형태의 코폴리머가 발표되었다.A polynorbornene-type copolymer having a structure shown below as one of the early 157 nm resist materials according to the prior art has been published.
상기 구조는 고분자의 접착 특성 및 건식 식각에 대한 내성 측면에서는 유리한 구조를 가지고 있다. 그러나 고분자 합성에 있어서, 분자량 조절이 어려우며 금속 촉매에 의한 불순물 제거가 어렵다는 단점을 가지고 있다.The structure has an advantageous structure in terms of adhesion properties and dry etching resistance of the polymer. However, in the synthesis of polymers, it is difficult to control the molecular weight and has a disadvantage in that it is difficult to remove impurities by a metal catalyst.
다른 종래 기술에 따른 레지스트 재료로서 다음 구조와 같은 α-트리플루오로메틸아크릴레이트 모노머와 스티렌 유도체와의 코폴리머가 발표되었다.As a resist material according to another prior art, a copolymer of an α-trifluoromethylacrylate monomer and a styrene derivative having the following structure has been disclosed.
상기 구조는 IBM사의 KrF용 레지스트의 개량된 구조로서, 플루오르화된 방향족 화합물이 157nm에서 박막 레지스트로서의 기능을 할 수 있다는 것을 발표하였다. 그러나, 상기 구조의 경우도 여전히 여러 가지 문제점들을 가지고 있으며, 특히 레지스트막의 투과도 및 건식 식각에 대한 내성은 여전히 해결해야 할 과제이다.This structure is an improved structure of IBM's KrF resist, which has revealed that the fluorinated aromatic compound can function as a thin film resist at 157 nm. However, the above structure still has various problems, and in particular, the resist film's permeability and resistance to dry etching are still subjects to be solved.
본 발명의 목적은 상기와 같은 종래의 157nm용 레지스트 재료의 단점을 개선하고자 하는 것으로, 기존의 포지티브형(positive) 레지스트 조성물이 갖는 건식 식각에 대한 내성, 접착 특성 또는 습윤성(wettability)에 따른 문제점을 해결할 수 있는 구조를 가지는 네가티브형 레지스트 조성물을 구성하기 위한 감광성 폴리머를 제공하는 것이다.An object of the present invention is to improve the disadvantages of the conventional resist material for 157nm as described above, to solve the problems caused by the resistance to dry etching, adhesion properties or wettability of the conventional positive resist composition It is to provide a photosensitive polymer for constituting a negative resist composition having a structure that can be solved.
본 발명의 다른 목적은 건식 식각에 대한 내성, 접착 특성 또는 습윤성에 따른 문제점을 해결할 수 있고, 일반적인 현상액을 사용하여 현상을 할 수 있는 네가티브형 레지스트 조성물을 제공하는 것이다.Another object of the present invention is to provide a negative resist composition which can solve problems caused by resistance to dry etching, adhesive properties or wettability, and which can be developed using a general developer.
상기 목적을 달성하기 위하여, 본 발명에 따른 감광성 폴리머는 네가티브형 레지스트 조성물을 구성하는 데 사용되고, 다음 구조의 반복 단위를 포함한다.In order to achieve the above object, the photosensitive polymer according to the present invention is used to construct a negative resist composition, and includes repeating units of the following structure.
식중, R1은 수소 원자, 메틸기 또는 트리플루오로메틸기이고, n은 1 ∼ 7의 정수이다.In formula, R <1> is a hydrogen atom, a methyl group, or a trifluoromethyl group, n is an integer of 1-7.
본 발명에 따른 감광성 폴리머는 다음 구조를 포함할 수 있다.The photosensitive polymer according to the present invention may include the following structure.
식중, R1및 R2는 각각 수소 원자, 메틸기 또는 트리플루오로메틸기이고, R3는 수소 원자, 2-히드록시에틸기 또는 2-히드록시프로필기이고, R4는 수소 원자, 히드록실기, C3∼ C10의 알킬기 또는 플루오르화된 알킬기이고, n은 1 ∼ 7의 정수이고, p/(p+q+r) = 0.1 ∼ 0.5이고, q/(p+q+r) = 0.0 ∼ 0.5이고, r/(p+q+r) = 0.0 ∼ 0.4이고, q 및 r이 동시에 0은 아니다. 바람직하게는, R4는 2-히드록시헥사플루오로이소프로필기, 2-히드록시-1,1,1-트리플루오로이소프로필기 또는 2-트리플루오로메틸-1,1,1-트리플루오로-2-히드록시프로필기이다.Wherein R 1 and R 2 are each a hydrogen atom, a methyl group or a trifluoromethyl group, R 3 is a hydrogen atom, a 2-hydroxyethyl group or a 2-hydroxypropyl group, R 4 is a hydrogen atom, a hydroxyl group, C and 3 ~ C 10 alkyl group or a fluorinated alkyl group, n is an integer of 1 ~ 7, p / (p + q + r) = 0.1 ~ 0.5 and, q / (p + q + r) = 0.0 ~ 0.5, r / (p + q + r) = 0.0 to 0.4, and q and r are not zero at the same time. Preferably, R 4 is a 2-hydroxyhexafluoroisopropyl group, 2-hydroxy-1,1,1-trifluoroisopropyl group or 2-trifluoromethyl-1,1,1-tri Fluoro-2-hydroxypropyl group.
또한, 본 발명에 따른 감광성 폴리머는 다음 구조를 포함할 수 있다.In addition, the photosensitive polymer according to the present invention may include the following structure.
식중, R1및 R2는 각각 수소 원자, 메틸기 또는 트리플루오로메틸기이고, R3는 수소 원자, 2-히드록시에틸기 또는 2-히드록시프로필기이고, R4는 수소 원자, 히드록실기, C3∼ C10의 알킬기 또는 플루오르화된 알킬기이고, n은 1 ∼ 7의 정수이고, p/(p+q+r) = 0.1 ∼ 0.5이고, q/(p+q+r) = 0.0 ∼ 0.5이고, r/(p+q+r) = 0.0 ∼ 0.4이고, q 및 r이 동시에 0은 아니다.Wherein R 1 and R 2 are each a hydrogen atom, a methyl group or a trifluoromethyl group, R 3 is a hydrogen atom, a 2-hydroxyethyl group or a 2-hydroxypropyl group, R 4 is a hydrogen atom, a hydroxyl group, C and 3 ~ C 10 alkyl group or a fluorinated alkyl group, n is an integer of 1 ~ 7, p / (p + q + r) = 0.1 ~ 0.5 and, q / (p + q + r) = 0.0 ~ 0.5, r / (p + q + r) = 0.0 to 0.4, and q and r are not zero at the same time.
본 발명에 따른 감광성 폴리머는 3,000 ∼ 50,000의 중량 평균 분자량을 가진다.The photosensitive polymer according to the present invention has a weight average molecular weight of 3,000 to 50,000.
상기 다른 목적을 달성하기 위하여, 본 발명에 따른 네가티브형 레지스트 조성물은 (a) 다음 구조의 반복 단위를 포함하는 것을 특징으로 하는 감광성 폴리머와, (b) 가교제(crosslinker)와, (c) PAG(photoacid generator)를 포함한다.In order to achieve the above another object, the negative resist composition according to the present invention comprises (a) a photosensitive polymer comprising a repeating unit having the following structure, (b) a crosslinker, and (c) a PAG ( photoacid generator).
식중, R1은 수소 원자, 메틸기 또는 트리플루오로메틸기이고, n은 1 ∼ 7의 정수이다.In formula, R <1> is a hydrogen atom, a methyl group, or a trifluoromethyl group, n is an integer of 1-7.
상기 가교제는 상기 감광성 폴리머의 중량을 기준으로 5.0 ∼ 20 중량%의 양으로 포함된다. 상기 가교제는 다작용성 우레아 (multifunctional urea) 또는 멜라민 계통의 물질로 이루어진다. 예를 들면, 상기 가교제는 1,3,4,6-테트라키스(메톡시메틸)글리콜우릴 (1,3,4,6-tetrakis(methoxymethyl)glicoluril), 1,3-비스(메톡시메틸)-4,5-비스(메톡시)에틸렌우레아 (1,3-bis(methoxymethyl)-4,5-bis(methoxy)ethylenurea), 1,3-비스(메톡시메틸)우레아 (1,3-bis(methoxymethyl)urea), 또는 헥사메톡시메틸멜라민 (hexamethoxymethylmelamine)으로 이루어질 수 있다.The crosslinking agent is included in an amount of 5.0 to 20% by weight based on the weight of the photosensitive polymer. The crosslinking agent is composed of a multifunctional urea or melamine-based material. For example, the crosslinking agent is 1,3,4,6-tetrakis (methoxymethyl) glycoluril (1,3,4,6-tetrakis (methoxymethyl) glicoluril), 1,3-bis (methoxymethyl) -4,5-bis (methoxy) ethyleneurea (1,3-bis (methoxymethyl) -4,5-bis (methoxy) ethylenurea), 1,3-bis (methoxymethyl) urea (1,3-bis (methoxymethyl) urea), or hexamethoxymethylmelamine.
상기 PAG는 상기 감광성 폴리머의 중량을 기준으로 1.0 ∼ 10중량%의 양으로 포함되고, 트리아릴술포늄염 (triarylsulfonium salts), 디아릴이오도늄염 (diaryliodonium salts) 또는 이들의 혼합물로 이루어질 수 있다. 예를 들면, 상기 PAG는 트리페닐술포늄 트리플레이트, 디페닐이오도늄 트리플레이트, 디-t-부틸페닐이오도늄 트리플레이트 또는 이들의 혼합물로 이루어질 수 있다.The PAG is included in an amount of 1.0 to 10% by weight based on the weight of the photosensitive polymer, and may be composed of triarylsulfonium salts, diaryliodonium salts, or mixtures thereof. For example, the PAG may be composed of triphenylsulfonium triflate, diphenyliodonium triflate, di-t-butylphenyliodonium triflate, or a mixture thereof.
본 발명에 따른 네가티브형 레지스트 조성물은 유기 염기를 더 포함할 수 있다. 상기 유기 염기는 상기 감광성 폴리머의 중량을 기준으로 0.01 ∼ 2.0 중량%의 양으로 포함된다.The negative resist composition according to the present invention may further include an organic base. The organic base is included in an amount of 0.01 to 2.0% by weight based on the weight of the photosensitive polymer.
본 발명에 따른 감광성 폴리머는 가교 사이트(crosslinking site)로서 히드록실기를 갖는 플루오르화된 알킬 (메트)아크릴레이트 모노머 유니트를 포함하는 것으로, 종래의 157nm용 레지스트 재료의 단점을 개선하여 건식 식각에 대한 내성, 접착 특성 또는 습윤성(wettability)에 따른 문제점을 해결할 수 있다. 또한, 본 발명에 따른 네가티브형 레지스트 조성물은 건식 식각에 대한 내성, 접착 특성 또는 습윤성에 따른 문제점을 해결할 수 있는 동시에, 일반적인 현상액을 사용하여현상을 할 수 있는 이점이 있다. 따라서, 본 발명에 따른 네가티브형 레지스트 조성물을 사용하여 보다 미세화된 패턴을 형성하는 것이 가능하다.The photosensitive polymer according to the present invention includes a fluorinated alkyl (meth) acrylate monomer unit having a hydroxyl group as a crosslinking site, and improves the disadvantages of the conventional resist material for 157 nm to dry etching. Problems due to resistance, adhesion properties or wettability can be solved. In addition, the negative resist composition according to the present invention can solve the problems caused by resistance to dry etching, adhesive properties or wettability, and at the same time, there is an advantage that development can be carried out using a general developer. Therefore, it is possible to form a more refined pattern using the negative resist composition according to the present invention.
다음에, 본 발명의 바람직한 실시예들에 대하여 상세히 설명한다.Next, preferred embodiments of the present invention will be described in detail.
합성예 1Synthesis Example 1
모노머의 합성Synthesis of Monomers
500mL 3목 플라스크에 α-트리플루오로메틸아크릴산 14g(0.1mol)과, 4-(디메틸아미노)피리딘 (DMAP) 0.6g(5mol%)을 소량의 4-메톡시페놀과 함께 디메틸포름아미드(DMF) 200mL에 녹인 다음, 여기에 글리시딜 2,2,3,3,4,4,5,5-옥타플루오로펜틸 에테르 26g(90mmol)를 적하깔때기(dropping funnel)를 이용하여 상온에서 적하하였다. 그 후, 반응물을 약 110℃의 온도에서 약 3시간 동안 반응시켰다.In a 500 mL three-neck flask, 14 g (0.1 mol) of α-trifluoromethylacrylic acid and 0.6 g (5 mol%) of 4- (dimethylamino) pyridine (DMAP) were added together with a small amount of 4-methoxyphenol to dimethylformamide (DMF). ) Was dissolved in 200 mL, and 26 g (90 mmol) of glycidyl 2,2,3,3,4,4,5,5-octafluoropentyl ether was added dropwise at room temperature using a dropping funnel. . Thereafter, the reaction was reacted for about 3 hours at a temperature of about 110 ℃.
반응이 끝난 후, 반응물을 과량의 물에 떨어뜨리고, 적당량의 디에틸 에테르를 이용하여 추출하였다. 그 후, 유기층을 MgSO4를 이용하여 건조시키고, 이어서 로타리 증발기(rotary evaporator)를 이용하여 용매를 날린 다음, 진공 증류(vacuum distillation)를 이용하여 생성물을 분리하였다. (수율: 72%)After the reaction was completed, the reaction mass was dropped into excess water and extracted with an appropriate amount of diethyl ether. The organic layer was then dried using MgSO 4 , followed by blowing off the solvent using a rotary evaporator, and then separating the product using vacuum distillation. (Yield 72%)
합성예 2Synthesis Example 2
모노머의 합성Synthesis of Monomers
아크릴산 7.2g(0.1mmol)과, 글리시딜 2,2,3,3,4,4,5,5,6,6,7,7-도데카플루오로헵틸 에테르 35g(90mmol)을 DMAP 0.6g(5mol%) 촉매 하에 DMF 용액에서 합성예 1에서와 같은 방법으로 합성하여 생성물을 얻었다. (수율: 70%)7.2 g (0.1 mmol) acrylic acid and 35 g (90 mmol) glycidyl 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl ether Synthesis was carried out in the same manner as in Synthesis Example 1 in a DMF solution under a (5 mol%) catalyst to obtain a product. (Yield 70%)
실시예 1Example 1
코폴리머의 합성Synthesis of Copolymer
둥근 플라스크에 합성예 1에서 만든 모노머 8.56g(20mmol)과, 2-히드록시에틸 메타크릴레이트 2.6g(20mmol)을 아조비스이소부티로니트릴 (azobisisobutyronitrile: AIBN) 0.33g(5mol%)과 함께 테트라히드로퓨란 (THF) 30g에 녹인 다음, 질소 가스로 완전히 퍼지시켰다. 그 후, 약 65℃의 온도에서 약 20시간 동안 중합시켰다.8.56 g (20 mmol) of the monomer prepared in Synthesis Example 1 and 2.6 g (20 mmol) of 2-hydroxyethyl methacrylate were added to a round flask with 0.33 g (5 mol%) of azobisisobutyronitrile (AIBN). It was dissolved in 30 g of hydrofuran (THF) and then completely purged with nitrogen gas. Thereafter, the polymerization was carried out at a temperature of about 65 ° C. for about 20 hours.
중합이 끝난 후, 반응물을 과량의 n-헥산 용액에서 천천히 침전시킨 다음, 생성된 침전물을 걸렀다. 그 후, 다시 한번 침전물을 적당량의 THF에 녹여서 n-헥산에서 재침전을 시키고, 침전물을 약 50℃의 진공 오븐에서 약 24시간 동안 말렸다. (수율: 76%)After the end of the polymerization, the reaction was slowly precipitated in excess n-hexane solution, and then the resulting precipitate was filtered off. Thereafter, the precipitate was once again dissolved in an appropriate amount of THF to reprecipitate in n-hexane and the precipitate was dried in a vacuum oven at about 50 ° C. for about 24 hours. (Yield 76%)
이 때, 얻어진 생성물의 중량 평균 분자량(Mw)은 12,500이었고,다분산도(Mw/Mn)는 2.1이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 12,500, and polydispersity (Mw / Mn) was 2.1.
실시예 2Example 2
코폴리머의 합성Synthesis of Copolymer
합성예 2에서 만든 모노머 9.2g(20mmol)과 4-히드록시스티렌 2.4g(20mmol)을 AIBN 0.33g과 함께 THF 30g에 녹인 다음, 실시예 1에서와 같은 방법으로 중합하여 원하는 폴리머를 얻었다. (수율: 80%)9.2 g (20 mmol) of monomers prepared in Synthesis Example 2 and 2.4 g (20 mmol) of 4-hydroxystyrene were dissolved in THF 30 g with 0.33 g of AIBN, and then polymerized in the same manner as in Example 1 to obtain a desired polymer. (Yield 80%)
이 때, 얻어진 생성물의 중량 평균 분자량(Mw)은 11,200이었고, 다분산도(Mw/Mn)는 2.0이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 11,200, and polydispersity (Mw / Mn) was 2.0.
실시예 3Example 3
코폴리머의 합성Synthesis of Copolymer
합성예 1의 방법으로 합성한 아크릴레이트 모노머 10mmol과, 4-(2-히드록시헥사플루오로이소프로필)스티렌 10mmol을 AIBN 5mol%와 함께 THF(모노머 무게비의3배)에 녹인 다음, 실시예 1에서와 같은 방법으로 중합하여 원하는 폴리머를 얻었다. (수율: 75%)10 mmol of the acrylate monomer synthesized by the method of Synthesis Example 1 and 10 mmol of 4- (2-hydroxyhexafluoroisopropyl) styrene were dissolved together with 5 mol% of AIBN in THF (three times the weight of the monomer), followed by Example 1 Polymerization was carried out in the same manner as in to obtain the desired polymer. (Yield 75%)
이 때, 얻어진 생성물의 중량 평균 분자량(Mw)은 13,800이었고, 다분산도(Mw/Mn)는 2.0이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 13,800, and polydispersity (Mw / Mn) was 2.0.
실시예 4Example 4
터폴리머의 합성Synthesis of Terpolymer
합성예 1에서 만든 모노머 20mmol과 α-트리플루오로메틸아크릴산 10mmol과, 노르보르넨 20mmol을 AIBN 3mol%와 함께 THF(모노머 무게비의 1.5배)에 녹인 다음, 실시예 1에서와 같은 방법으로 중합하여 원하는 폴리머를 얻었다. (수율: 62%)20 mmol of the monomer prepared in Synthesis Example 1, 10 mmol of α-trifluoromethylacrylic acid, and 20 mmol of norbornene were dissolved in THF (1.5 times the monomer weight ratio) with 3 mol% of AIBN, followed by polymerization in the same manner as in Example 1. The desired polymer was obtained. (Yield 62%)
이 때, 얻어진 생성물의 중량 평균 분자량(Mw)은 8,800이었고, 다분산도(Mw/Mn)는 2.1이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 8,800, and polydispersity (Mw / Mn) was 2.1.
실시예 5Example 5
터폴리머의 합성Synthesis of Terpolymer
합성예 1에서 만든 모노머 20mmol과 α-트리플루오로메틸아크릴산 10mmol과, 스티렌 20mmol을 AIBN 3mol%와 함께 THF(모노머 무게비의 2배)에 녹인 다음, 실시예 1에서와 같은 방법으로 중합하여 원하는 폴리머를 얻었다. (수율: 65%)20 mmol of the monomer prepared in Synthesis Example 1, 10 mmol of α-trifluoromethylacrylic acid, and 20 mmol of styrene were dissolved together with 3 mol% of AIBN in THF (double the weight ratio of the monomer), and then polymerized in the same manner as in Example 1 Got. (Yield 65%)
이 때, 얻어진 생성물의 중량 평균 분자량(Mw)은 7,900이었고, 다분산도(Mw/Mn)는 2.0이었다.At this time, the weight average molecular weight (Mw) of the obtained product was 7,900, and polydispersity (Mw / Mn) was 2.0.
실시예 6Example 6
레지스트 조성물의 제조 및 패턴 형성 공정Preparation of resist composition and pattern forming process
실시예 1 내지 실시예 5에서 합성한 각각의 폴리머 1g을 각각 가교제(crosslinker)인 1,3,4,6-테트라키스(메톡시메틸)글리콜우릴 (TMGU) 0.1g과, PAG(photoacid generator)인 트리페닐술포늄 트리플레이트 0.01g과, 프로필렌 글리콜 메틸 에테르 아세테이트 (PGMEA) 7g에 녹인 다음, 여기에 유기 염기인 트리이소부틸아민 1mg을 넣어서 완전히 녹여 네가티브형 레지스트 조성물을 제조하였다.1 g of each polymer synthesized in Examples 1 to 5 was each 0.1 g of 1,3,4,6-tetrakis (methoxymethyl) glycoluril (TMGU), which is a crosslinker, and a photoacid generator (PAG). It was dissolved in 0.01 g of phosphorus triphenylsulfonium triflate and 7 g of propylene glycol methyl ether acetate (PGMEA), and then 1 mg of triisobutylamine, an organic base, was completely dissolved to prepare a negative resist composition.
얻어진 레지스트 조성물을 HMDS(hexamethyldisilazane) 처리를 한 베어 Si 웨이퍼상에 약 0.33㎛의 두께로 코팅한 다음, 약 120 ~ 140℃의 온도 범위에서 약 60 ~ 90초 동안 프리베이킹(soft bake)을 실시하고, 그 후에, ArF 스테퍼 (0.6NA,σ= 0.75)를 이용하여 노광하였다.The obtained resist composition was coated on a bare Si wafer subjected to HMDS (hexamethyldisilazane) to a thickness of about 0.33 μm, and then prebaked for about 60 to 90 seconds at a temperature range of about 120 to 140 ° C. Then, it exposed using ArF stepper (0.6NA, (sigma) = 0.75).
이어서, 약 100 ~ 130℃의 온도 범위에서 약 60 ~ 90초 동안 PEB(post-exposure bake)를 실시한 다음, 2.38wt% TMAH (tetramethylammonium hydroxide) 용액에 약 60초 동안 현상하였다. 그 결과, 노광 도즈량을 약 11 ~ 28mJ/cm2으로 하였을 때 깨끗한 모양의 180nm 라인 앤드 스페이스 패턴(lines and spaces pattern)이 얻어지는 것을 확인할 수 있었다.Then, a post-exposure bake (PEB) was performed for about 60 to 90 seconds at a temperature range of about 100 to 130 ° C., and then developed in a 2.38 wt% TMAH (tetramethylammonium hydroxide) solution for about 60 seconds. As a result, it was confirmed that when the exposure dose was set to about 11 to 28 mJ / cm 2 , a 180 nm line and space pattern having a clean shape was obtained.
본 발명에 따른 네가티브형 레지스트 조성물을 제조하는 데 있어서, 상기 가교제는 베이스 폴리머로 사용되는 감광성 폴리머의 중량을 기준으로 약 5.0 ∼ 20 중량%의 양으로 포함될 수 있으며, 다작용성 우레아 (multifunctional urea) 또는 멜라민 계통의 물질로 이루어질 수 있다. 상기 가교제로서, 예를 들면 1,3,4,6-테트라키스(메톡시메틸)글리콜우릴 (1,3,4,6-tetrakis(methoxymethyl)glicoluril), 1,3-비스(메톡시메틸)-4,5-비스(메톡시)에틸렌우레아 (1,3-bis(methoxymethyl)-4,5-bis(methoxy)ethylenurea), 1,3-비스(메톡시메틸)우레아 (1,3-bis(methoxymethyl)urea), 또는 헥사메톡시메틸멜라민 (hexamethoxymethylmelamine)을 사용할 수 있다.In preparing the negative resist composition according to the present invention, the crosslinking agent may be included in an amount of about 5.0 to 20% by weight based on the weight of the photosensitive polymer used as the base polymer, and may be a multifunctional urea or It can be made of melamine-based material. As the crosslinking agent, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril (1,3,4,6-tetrakis (methoxymethyl) glicoluril), 1,3-bis (methoxymethyl) -4,5-bis (methoxy) ethyleneurea (1,3-bis (methoxymethyl) -4,5-bis (methoxy) ethylenurea), 1,3-bis (methoxymethyl) urea (1,3-bis (methoxymethyl) urea) or hexamethoxymethylmelamine can be used.
상기 PAG는 상기 감광성 폴리머의 중량을 기준으로 1.0 ∼ 10중량%의 양으로 포함되며, 트리아릴술포늄염 (triarylsulfonium salts), 디아릴이오도늄염 (diaryliodonium salts) 또는 이들의 혼합물로 이루어질 수 있다.The PAG may be included in an amount of 1.0 to 10% by weight based on the weight of the photosensitive polymer, and may be composed of triarylsulfonium salts, diaryliodonium salts, or a mixture thereof.
상기한 패턴 형성 단계에 있어서, 웨이퍼상에 레지스트 조성물을 코팅할 때, 그 두께는 용도에 따라 달라질 수 있으며, 약 0.2 ~ 0.7㎛의 두께로 코팅된다. 또한, 프리베이킹 단계에서는 보호기(protecting group)의 종류에 따라 베이킹 온도가 달라지며, 보통 110 ~ 140℃의 온도 범위 내에서 약 60 ~ 90초 동안 행해질 수 있다. 노광 단계에서는 사용되는 심자외선(deep-UV)의 광원에 따라서 도즈량이 달라지며, ArF 또는 F2엑시머 레이저의 경우에 보통 5 ~ 100mJ/cm2의 에너지를 사용할 수 있다. PEB 단계에서는, 보호기의 종류에 따라 베이킹 온도가 달라지며, 보통 100 ~ 130℃의 온도 범위 내에서 약 60 ~ 90초 동안 행해질 수 있다. 현상(development) 단계는 보통 2.38wt% TMAH(0.26N) 용액으로 약 20 ~ 60초 동안 행해진다.In the above pattern forming step, when coating the resist composition on the wafer, the thickness may vary depending on the application, and is coated with a thickness of about 0.2 ~ 0.7㎛. In addition, in the prebaking step, the baking temperature varies according to the type of protecting group, and may be usually performed for about 60 to 90 seconds within a temperature range of 110 to 140 ° C. In the exposure step, the dose amount varies according to the deep-UV light source used, and in the case of an ArF or F 2 excimer laser, energy of 5 to 100 mJ / cm 2 can be used. In the PEB step, the baking temperature varies depending on the type of protecting group, and may be usually performed for about 60 to 90 seconds within a temperature range of 100 to 130 ° C. The development step is usually performed for about 20 to 60 seconds with a 2.38 wt% TMAH (0.26 N) solution.
본 발명에 따른 감광성 폴리머는 네가티브형 레지스트 조성물을 제조하는 데 사용하기 위한 것으로, 가교 사이트(crosslinking site)로서 히드록실기를 갖는 플루오르화된 알킬 (메트)아크릴레이트 모노머 유니트를 포함한다. 본 발명에 따른 감광성 폴리머는 상기와 같은 모노머 유니트와 함께 여러가지 구조의 공중합체의 형태로 일반적인 라디칼 중합에 의해 비교적 용이하게 제조될 수 있다. 특히 α-트리플루오로메틸아크릴레이트 모노머 유니트와의 공중합체를 이용해 여러가지 구조를 가지는 터폴리머 이상의 공중합체를 쉽게 얻을 수 있다. 본 발명에 따른 감광성 폴리머를 구성하는 데 필요한 플루오르화된 모노머들은 에폭사이드기를 가지는 플루오르화된 화합물과, (메트)아크릴산과의 반응을 통하여 비교적 쉽게 얻을 수 있다. 이와 같은 방법으로 얻어지는 본 발명에 따른 감광성 폴리머는 종래의 157nm용레지스트 재료의 단점을 개선하여 건식 식각에 대한 내성, 접착 특성 또는 습윤성(wettability)에 따른 문제점을 해결할 수 있다.The photosensitive polymer according to the present invention is for use in preparing a negative resist composition and includes a fluorinated alkyl (meth) acrylate monomer unit having a hydroxyl group as a crosslinking site. The photosensitive polymer according to the present invention can be prepared relatively easily by general radical polymerization in the form of a copolymer of various structures together with the monomer units as described above. In particular, a copolymer of terpolymer or higher having various structures can be easily obtained by using a copolymer with an α-trifluoromethyl acrylate monomer unit. Fluorinated monomers necessary for forming the photosensitive polymer according to the present invention can be obtained relatively easily through the reaction of a fluorinated compound having an epoxide group with (meth) acrylic acid. The photosensitive polymer according to the present invention obtained by such a method can solve the problems caused by resistance to dry etching, adhesive properties or wettability by improving the disadvantages of the conventional 157 nm resist material.
또한, 상기한 바와 같은 감광성 폴리머로부터 얻어지는 본 발명에 따른 네가티브형 레지스트 조성물은 건식 식각에 대한 내성, 접착 특성 또는 습윤성에 따른 문제점을 해결할 수 있는 동시에, 일반적인 현상액을 사용하여 현상을 할 수 있는 이점이 있다. 따라서, 본 발명에 따른 네가티브형 레지스트 조성물을 사용하여 보다 미세화된 패턴을 형성하는 것이 가능하며, F2(157nm) 엑시머 레이저를 이용하는 포토리소그래피 공정에 적용할 때 우수한 리소그래피 퍼포먼스를 나타냄으로써, 향후 차세대 반도체 소자를 제조하는 데 있어서 매우 유용하게 사용될 수 있다.In addition, the negative resist composition according to the present invention obtained from the photosensitive polymer as described above can solve the problems caused by resistance to dry etching, adhesive properties or wettability, and at the same time, it is possible to develop using a common developer have. Therefore, it is possible to form a finer pattern using the negative type resist composition according to the present invention, and exhibits excellent lithography performance when applied to a photolithography process using an F 2 (157 nm) excimer laser, thereby enabling future generation of semiconductors. It can be very useful to manufacture the device.
이상, 본 발명을 바람직한 실시예를 들어 상세하게 설명하였으나, 본 발명은 상기 실시예에 한정되지 않고, 본 발명의 기술적 사상의 범위 내에서 당 분야에서 통상의 지식을 가진 자에 의하여 여러가지 변형이 가능하다.The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. Do.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140064676A (en) * | 2012-11-19 | 2014-05-28 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US9223214B2 (en) | 2012-11-19 | 2015-12-29 | The Texas A&M University System | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US9405189B2 (en) | 2013-09-06 | 2016-08-02 | Rohm And Haas Electronic Materials Llc | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US9447220B2 (en) | 2012-11-19 | 2016-09-20 | Rohm And Haas Electronic Materials Llc | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US10078261B2 (en) | 2013-09-06 | 2018-09-18 | Rohm And Haas Electronic Materials Llc | Self-assembled structures, method of manufacture thereof and articles comprising the same |
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2001
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140064676A (en) * | 2012-11-19 | 2014-05-28 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US9223214B2 (en) | 2012-11-19 | 2015-12-29 | The Texas A&M University System | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US9447220B2 (en) | 2012-11-19 | 2016-09-20 | Rohm And Haas Electronic Materials Llc | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US9405189B2 (en) | 2013-09-06 | 2016-08-02 | Rohm And Haas Electronic Materials Llc | Self-assembled structures, method of manufacture thereof and articles comprising the same |
| US10078261B2 (en) | 2013-09-06 | 2018-09-18 | Rohm And Haas Electronic Materials Llc | Self-assembled structures, method of manufacture thereof and articles comprising the same |
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