KR20050064462A - Highly polymerized compound capable of using as organic reflection preventive film for krf and arf and manufacturing method thereof - Google Patents
Highly polymerized compound capable of using as organic reflection preventive film for krf and arf and manufacturing method thereof Download PDFInfo
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- KR20050064462A KR20050064462A KR1020030095829A KR20030095829A KR20050064462A KR 20050064462 A KR20050064462 A KR 20050064462A KR 1020030095829 A KR1020030095829 A KR 1020030095829A KR 20030095829 A KR20030095829 A KR 20030095829A KR 20050064462 A KR20050064462 A KR 20050064462A
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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
- G03F7/09—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
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- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0276—Photolithographic processes using an anti-reflective coating
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Abstract
본 발명은 KrF, ArF 포토레지스트용 유기 반사 방지막에 사용할 수 있는 고분자 수지 및 이의 제조 방법에 관한 것이다.The present invention relates to a polymer resin that can be used in an organic antireflection film for KrF and ArF photoresist and a method for producing the same.
이하의 화학식 1로 표시되는 트리페닐-설포니움 이온계 화합물을 주쇄로 포함하고, 중량 평균 분자량이 1000-100000인 것을 특징으로 하는 유기 반사 방지막용 고분자 수지를 제공한다.Provided is a polymer resin for an organic antireflection film comprising a triphenyl-sulfonium ionic compound represented by the following Chemical Formula 1 as a main chain, and having a weight average molecular weight of 1000-100000.
[화학식 1][Formula 1]
여기서, R1은 Cl- 혹은 F-이고, R2는 OH 혹은 탄소수 1-3개의 알코올기이다.Wherein, R1 is Cl - or F - and, R2 is OH or 1 to 3 carbon atoms, the alcohol group.
Description
본 발명은 유기 반사 방지막용 고분자 수지 및 이의 제조방법에 관한 것으로, 특히 KrF, ArF 포토레지스트용 유기 반사 방지막에 사용할 수 있는 고분자 수지 및 이의 제조 방법에 관한 것이다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer resin for an organic antireflection film and a method for producing the same, and more particularly, to a polymer resin for use in an organic antireflection film for KrF and ArF photoresist and a method for producing the same.
기존의 유기 반사 방지막은 별도의 에칭 과정을 통해 패턴을 형성해야만 한다. 종래 알려진 ArF용 포토레지스트는 KrF 포토레지스트에 비해 내에칭성이 약하며, 기존의 유기 반사 방지막용 고분자 물질을 사용할 경우, 반사막 에칭 과정에서 포토레지스트의 손실이 크다는 문제점이 있다.Existing organic antireflection film has to form a pattern through a separate etching process. Conventionally known ArF photoresist has a weak etching resistance compared to KrF photoresist, and when a conventional polymer material for organic antireflection film is used, there is a problem in that the loss of the photoresist is large during the reflective film etching process.
이러한 문제점을 해결하기 위해, 포토레지스트 현상 과정에서 함께 현상되는 유기 반사막 고분자 물질이 알려져 있다. In order to solve this problem, an organic reflective film polymer material that is developed together during the photoresist development process is known.
그러나, 이러한 유기 반사막 고분자 물질은 열공정에 의해 주쇄의 구조가 변화되어 현상액에 대한 용해도가 달라지는 특징이 있어 열공정 조건에 매우 민감한 것이 단점이다.However, the organic reflective film polymer material has a feature that the structure of the main chain is changed by the thermal process, so that the solubility in the developer is changed, which is very sensitive to the thermal process conditions.
이렇게 열공정에 민감한 것이 원인이 되어 패턴의 푸팅(footing) 또는 언더컷(undercut)의 문제를 발생시킨다.This sensitivity to the thermal process causes the problem of patterning footing or undercut.
또한 전체 패턴 밀도에 의한 패턴 프로파일(profile)의 변화로 인해 공정마진이 줄어드는 문제점이 발생한다. In addition, there is a problem that the process margin is reduced due to the change of the pattern profile due to the overall pattern density.
본 발명의 목적은 상기한 바와 같은 종래 기술에서의 문제점을 해결하고자 제안한 것으로, 내에칭성이 약한 포토레지스트가 유기 반사 방지막 에칭단계에서 손실되는 것을 방지하기 위하여 별도의 에칭단계 없이 포토레지스트 현상과정에서 함께 현상되는 고분자 수지를 제공하고자 하는 것이다.An object of the present invention is to solve the problems in the prior art as described above, in order to prevent the loss of photoresist having a weak etching resistance in the organic anti-reflective film etching step in the photoresist development process without a separate etching step It is to provide a polymer resin that is developed together.
본 발명의 또 다른 목적은 열공정에 의한 고분자 수지의 물성 변화를 방지하기 위해 광반응에 의해 주쇄가 끊어져 저분자 물질을 형성하도록 하여 패턴의 프로파일이 열에 민감하지 않도록 하는 고분자 수지를 제공하는 것이다.Still another object of the present invention is to provide a polymer resin in which a main chain is broken by photoreaction to form a low molecular material in order to prevent physical property change of the polymer resin by a thermal process so that the profile of the pattern is not sensitive to heat.
본 발명의 또 다른 목적은 내에칭성이 약한 포토레지스트가 유기 반사 방지막 에칭단계에서 손실되는 것을 방지하기 위하여 별도의 에칭단계 없이 포토레지스트 현상과정에서 함께 현상되는 고분자 수지 제조 방법을 제공하고자 하는 것이다. It is still another object of the present invention to provide a method for producing a polymer resin, which is developed together in a photoresist development process without a separate etching step in order to prevent a photoresist having weak etching resistance from being lost in an organic anti-reflection film etching step.
상기한 바와 같은 목적을 달성하기 위한 본 발명의 바람직한 일실시예를 실시예를 중심으로 설명한다. One preferred embodiment of the present invention for achieving the above object will be described based on the embodiment.
이하 본 발명에 따른 KrF, ArF 포토레지스트용 유기 반사 방지막으로 사용할 수 있는 고분자 수지 및 이의 제조 방법을 상세히 설명한다.Hereinafter, a polymer resin which can be used as an organic antireflection film for KrF and ArF photoresist according to the present invention, and a method of manufacturing the same will be described in detail.
본 발명의 실시예에 따르면, 이하 화학식 1로 표시되는 트리페닐-설포니움 이온계 화합물을 주쇄로 포함하고, 중량 평균 분자량이 1000-100000인 것을 특징으로 하는 유기 반사 방지막용 고분자 수지를 제공한다. According to an embodiment of the present invention, a triphenyl-sulfonium ionic compound represented by the following formula (1) is provided as a main chain, and a weight average molecular weight of 1000-100000 is provided a polymer resin for an organic antireflection film. .
여기서, R1은 Cl- 혹은 F-이고, R2는 OH 혹은 탄소수 1-3개의 알코올기이다.Wherein, R1 is Cl - or F - and, R2 is OH or 1 to 3 carbon atoms, the alcohol group.
구체적으로, 상기 유기 반사 방지막용 고분자 수지가 하기 화학식 2 또는 화학식 3으로 표시되는 고분자 수지인 것을 특징으로 하는 유기 반사 방지막용 고분자 수지를 제공한다. Specifically, the organic anti-reflection film polymer resin provides a polymer resin for an organic anti-reflection film, characterized in that the polymer resin represented by the following formula (2) or formula (3).
상기, 화학식 1의 화합물은 S+이온에 연결된 3개의 화학결합이 248nm, 193nm의 빛을 흡수하면서 그 결합이 끊어지는 성질을 나타낸 것으로, 이러한 화합물을 포함하는 본 발명의 고분자 수지는 248nm, 193nm의 빛에 노광된 고분자 주쇄가 끊어져 저분자 물질로 된다.The compound of Formula 1 is characterized in that the three chemical bonds connected to the S + ion absorbs the light of 248nm, 193nm, the bond is broken, the polymer resin of the present invention comprising such a compound is 248nm, 193nm light The polymer backbone exposed to the break is broken to form a low molecular weight material.
상기 화학식 2 및 화학식 3의 고분자 구조를 형성하는 화합물 중 이하의 화학식 4로 표시되는 화합물과 화학식 5로 표시되는 화합물은 반사 방지막 고분자 수지의 광흡수율을 높이기 위한 것이다.Among the compounds forming the polymer structures of Chemical Formulas 2 and 3, the compounds represented by the following Chemical Formula 4 and the compounds represented by Chemical Formula 5 are for increasing the light absorption of the antireflection film polymer resin.
상기 화학식 2 및 화학식 3의 고분자 구조를 형성하는 화합물 중 이하의 화학식 6으로 표시되는 화합물은 고분자 수지의 Tg를 조절하기 위한 것이다.Of the compounds forming the polymer structures of Chemical Formulas 2 and 3, the compounds represented by the following Chemical Formula 6 are for controlling the Tg of the polymer resin.
상술한 바와 같이, 상기 유기 반사 방지막용 고분자 수지는 248nm, 193nm의 빛을 흡수하여 저분자화 반응을 일으킨다. 이러한 성질을 이용하여 반도체 소자 형성에 있어 포토레지스트를 이용한 미세패턴을 형성하는 공정에 유용하게 사용할 수 있다.As described above, the organic antireflective polymer resin absorbs light of 248 nm and 193 nm to cause a low molecular weight reaction. By using such a property, it can be usefully used in the process of forming a fine pattern using a photoresist in forming a semiconductor device.
또한, 본 발명은 유기 반사 방지막용 고분자 수지의 제조방법을 제공한다.Moreover, this invention provides the manufacturing method of the polymer resin for organic antireflective films.
구체적으로, 화학식 1로 표시되는 트리페닐-설포니움 이온계 화합물과 화학식 6으로 표시되는 다이올을 1-메틸-2-피롤리디논에 혼합 및 교반하는 단계(1 단계), 얻어진 용액에 테레프탈산과 4,4'-이소프로필리덴 디페놀 비스(클로로포르메이트)를 가하여 교반하는 단계(2단계), 얻어진 용액을 농축하는 단계(3단계), 및 얻어진 농축액을 비극성 유기 용매에 떨어뜨려 화학식 2 또는 화학식 3의 고분자 수지를 얻는 단계(단계 4)를 포함하는 것으로 이루어진 고분자 수지의 제조 방법을 제공한다. Specifically, mixing and stirring the triphenyl-sulfonium ionic compound represented by the formula (1) and the diol represented by the formula (6) to 1-methyl-2-pyrrolidinone (step 1), terephthalic acid in the obtained solution And 4,4'-isopropylidene diphenol bis (chloroformate), followed by stirring (Step 2), concentrating the obtained solution (Step 3), and dropping the obtained concentrate into a non-polar organic solvent. Or it provides a method of producing a polymer resin comprising a step (step 4) to obtain a polymer resin of the formula (3).
유기 반사방지막용 고분자 수지의 합성Synthesis of Polymer Resin for Organic Antireflection Film
화학식 1로 표시되는 트리페닐-설포니움 이온계 화합물과 화학식 6으로 표시되는 다이올을 1-메틸-2-피롤리디논에 혼합 및 교반한다(1 단계).The triphenyl-sulfonium ionic compound represented by the formula (1) and the diol represented by the formula (6) are mixed and stirred in 1-methyl-2-pyrrolidinone (step 1).
얻어진 용액에 테레프탈산과 4,4'-이소프로필리덴 디페놀 비스(클로로포르메이트)를 가하여 교반한다(2 단계).Terephthalic acid and 4,4'-isopropylidene diphenol bis (chloroformate) are added to the obtained solution, followed by stirring (step 2).
얻어진 용액을 농축한다(3 단계).The resulting solution is concentrated (3 steps).
얻어진 농축액을 비극성 유기 용매에 떨어뜨려 화학식 2 또는 화학식 3의 고분자 수지를 재결정으로 얻는다.The obtained concentrate is dropped in a nonpolar organic solvent to obtain a polymer resin of formula (2) or formula (3) as recrystallization.
아울러 상기한 본 발명의 바람직한 실시예는 예시의 목적을 위해 개시된 것이며, 당업자라면 본 발명의 사상과 범위 안에서 다양한 수정, 변경, 부가 등이 가능할 것이며, 이러한 수정 변경 등은 이하의 특허청구의 범위에 속하는 것으로 보아야 할 것이다. In addition, preferred embodiments of the present invention described above are disclosed for the purpose of illustration, and those skilled in the art will be able to make various modifications, changes, additions, etc. within the spirit and scope of the present invention, such modifications, modifications and the like are within the scope of the claims It should be seen as belonging.
따라서, 상기한 본 발명에 따른 KrF, ArF 포토레지스트용 유기 반사 방지막으로 사용할 수 있는 고분자 수지 및 이의 제조 방법에 의하면, 본 발명에서 제안하는 고분자 물질을 유기 반사 방지막으로 이용할 경우 기존의 유기 반사 방지막이 포토레지스트를 이용한 패턴형성과정에서 나타냈던 장점을 모두 유지하면서도 그에 더하여, 첫째, 유기 반사 방지막이 패턴 형성을 위해서 에칭하는 공정을 생략할 수 있어서 전체 공정이 단순해지고, 둘째, 내에칭성이 약한 포토레지스트가 유기반사방지막 에칭 단계에서 손실되는 것을 방지할 수 있으며, 셋째, 유기 반사 방지막의 패턴 프로파일이 열공정에 민감하게 변화하는 것을 방지할 수 있는 효과가 있다. Therefore, according to the above-described polymer resin and the manufacturing method thereof can be used as an organic antireflection film for KrF, ArF photoresist according to the present invention, when using the polymer material proposed in the present invention as an organic antireflection film is a conventional organic antireflection film In addition, while maintaining all the advantages shown in the pattern formation process using the photoresist, firstly, the process of etching the organic anti-reflective film to form a pattern can be omitted, and secondly, the overall process is simplified. The resist can be prevented from being lost in the organic anti-reflective coating etch step, and third, there is an effect of preventing the pattern profile of the organic anti-reflective coating from being sensitive to thermal processing.
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| KR1020030095829A KR20050064462A (en) | 2003-12-23 | 2003-12-23 | Highly polymerized compound capable of using as organic reflection preventive film for krf and arf and manufacturing method thereof |
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