KR20050103584A - Photosensitive polymer and chemically amplified photoresist composition including the same - Google Patents
Photosensitive polymer and chemically amplified photoresist composition including the same Download PDFInfo
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- KR20050103584A KR20050103584A KR1020040028793A KR20040028793A KR20050103584A KR 20050103584 A KR20050103584 A KR 20050103584A KR 1020040028793 A KR1020040028793 A KR 1020040028793A KR 20040028793 A KR20040028793 A KR 20040028793A KR 20050103584 A KR20050103584 A KR 20050103584A
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Abstract
해상도가 우수하여 단파장의 노광원 하에서도 미세한 회로 패턴을 형성할 수 있는 감광성 고분자 수지 및 이를 포함하는 화학증폭형 포토레지스트 조성물이 개시된다. 상기 감광성 고분자 수지는 하기 화학식 1로 표시된다.Disclosed are a photosensitive polymer resin having a high resolution and capable of forming a fine circuit pattern even under a short wavelength exposure source and a chemically amplified photoresist composition comprising the same. The photosensitive polymer resin is represented by the following formula (1).
[화학식 1][Formula 1]
상기 식에서, R은 수소 또는 메틸기, R1은 , 또는 이고, R2는 클로로, 브로모, 하이드록시, 사이아노, t-부톡시, CH2NH2, CONH2, CH=NH, CH(OH)NH2 또는 C(OH)=NH이며, R3는 수소 또는 메틸기이고, 1-x-y, x, y는 상기 감광성 화합물을 구성하는 각 반복단위의 중합도로서, x, y는 각각 0.1∼0.8이고, n은 1 또는 2이다.Wherein R is hydrogen or methyl, R 1 is , or R 2 is chloro, bromo, hydroxy, cyano, t-butoxy, CH 2 NH 2 , CONH 2 , CH = NH, CH (OH) NH 2 or C (OH) = NH, R 3 Is hydrogen or a methyl group, and 1-xy, x, y are degrees of polymerization of each repeating unit constituting the photosensitive compound, x and y are each 0.1 to 0.8, and n is 1 or 2.
Description
본 발명은 감광성 고분자 수지 및 이를 포함하는 화학증폭형 포토레지스트 조성물에 관한 것으로서, 더욱 상세하게는 해상도가 우수하여 단파장(deep UV)의 노광원하에서도 미세 회로 패턴을 형성할 수 있는 감광성 고분자 수지 및 이를 포함하는 화학증폭형 포토레지스트 조성물에 관한 것이다. The present invention relates to a photosensitive polymer resin and a chemically amplified photoresist composition comprising the same, and more particularly, to a photosensitive polymer resin capable of forming a fine circuit pattern even under an exposure source of deep UV due to its excellent resolution and the same. It relates to a chemically amplified photoresist composition comprising.
통상 3년에 4배의 속도로 진행되는 반도체 집적회로소자의 고집적화에 따라, 종래의 256 메가 비트급의 기억용량을 가진 다이나믹 랜덤 액서스 메모리(이하 DRAM이라함)보다 고용량인 기가 비트급 DRAM의 개발이 이루어지고 있으며, 또한 종래의 0.25 ㎛의 선폭보다 미세한 0.20 ㎛이하의 선폭을 가지는 미세 회로 패턴을 형성할 수 있는 감광성 수지 및 포토레지스트 조성물의 개발이 요구되고 있다. As a result of the high integration of semiconductor integrated circuit devices, which are generally performed at four times the speed in three years, the development of gigabit DRAM having a higher capacity than the conventional dynamic random access memory (hereinafter referred to as DRAM) having a memory capacity of 256 mega bits is achieved. The development of the photosensitive resin and photoresist composition which can form the fine-circuit pattern which has a line width of 0.20 micrometer or less finer than the conventional 0.25 micrometer line width is calculated | required.
일반적으로, 반도체의 제조 공정에 있어서 포토리소그래피(photolithography) 공정은 a) 반도체 회로기판의 표면에 감광성 고분자 수지를 포함한 포토레지스트 조성물을 균일하게 도포하는 공정; b) 도포된 포토레지스트 조성물을 가열하여 용제를 증발시킴으로서, 반도체 회로기판의 표면에 레지스트막을 형성하는 소프트베이킹 공정; c) 광원과 상기 레지스트막이 형성된 기판 사이에 반도체 회로 설계도를 새겨 놓은 포토마스크를 놓고, 광원을 켜서 상기 포토마스크의 잠상을 레지스트막에 전사하는 노광 공정; d) 상기 노광 공정으로 노광부와 비노광부의 용해도를 다르게 한 후, 현상액 등을 사용하여 레지스트 조성물을 선택적으로 제거하는 현상 공정; e) 현상된 레지스트막을 가열하여 레지스트막을 기판에 긴밀하게 고착시키는 하드베이킹 공정; f) 하드베이킹된 레지스트막의 패턴을 따라 기판을 에칭하여 전기적인 특성을 부여하는 식각 공정; g) 상기 식각 공정 후 불필요하게 된 레지스트막을 제거하는 박리 공정을 순차적으로 수행하는 공정이다. In general, a photolithography process in a semiconductor manufacturing process includes a) uniformly applying a photoresist composition including a photosensitive polymer resin to a surface of a semiconductor circuit board; b) a soft baking process of heating the coated photoresist composition to evaporate the solvent to form a resist film on the surface of the semiconductor circuit board; c) an exposure step of transferring a latent image of the photomask to a resist film by placing a photomask inscribed with a semiconductor circuit design diagram between a light source and a substrate on which the resist film is formed; d) a developing step of selectively removing the resist composition using a developer or the like after changing the solubility of the exposed portion and the non-exposed portion by the exposure step; e) a hard baking process of heating the developed resist film to closely adhere the resist film to the substrate; f) an etching process of etching the substrate along the pattern of the hard baked resist film to impart electrical characteristics; g) a step of sequentially performing a peeling step of removing the resist film which is unnecessary after the etching step.
노광 기술은 1980년대 초에 고압 수은등을 이용한 G-선(436nm 파장) 노광 장치의 도입으로 1㎛ 해상도를 갖는 회로 패턴을 형성할 수 있게 되었고, 또한 I-선(365nm 파장) 노광 장치의 도입으로 0.5㎛의 해상도를 가지는 회로 패턴을 형성할 수 있게 되었으며, 이 후 248nm 파장인 KrF 엑사이머 레이저 노광기술 등 300nm이하 단파장 노광기술의 발달로 0.5 ㎛ 이하의 해상도를 갖는 반도체 미세회로 패턴을 형성할 수 있게 되어, 현재는 256M DRAM반도체의 대량생산이 이루어지고 있다. 한편, 193nm 파장인 ArF 엑사이머 레이저 노광 기술의 연구와 개발로 인해 향후 1G 메모리 반도체의 생산도 가능할 것으로 전망되고 있으며 X-ray, EUV(Extreme Ultra Violate)를 이용하는 노광 장치의 개발도 진행중이다. The exposure technology was able to form a circuit pattern having a 1 μm resolution with the introduction of a G-ray (436 nm wavelength) exposure apparatus using a high pressure mercury lamp in the early 1980s, and also with the introduction of an I-ray (365 nm wavelength) exposure apparatus. It was possible to form a circuit pattern having a resolution of 0.5 μm, and then to develop a semiconductor microcircuit pattern having a resolution of 0.5 μm or less by the development of short wavelength exposure technology of 300 nm or less, such as KrF excimer laser exposure technology having a wavelength of 248 nm. Now, mass production of 256M DRAM semiconductor is under way. Meanwhile, research and development of ArF excimer laser exposure technology with a wavelength of 193 nm is expected to enable the production of 1G memory semiconductors in the future, and development of exposure apparatus using X-ray and Extreme Ultra Violate (EUV) is also in progress.
상기 포토리소그래피(photolithography) 공정에 사용되는 포토레지스트 조성물은 광학적 성질로서 노광되는 광원에 대하여 우수한 해상도(resolution) 및 감도(sensitivity)를 가져야 하며, 기타 우수한 콘트라스트(contrast), 빠른 현상속도(photospeed), 우수한 열적안정성, 접착성(adhesion) 및 식각 내성(etch resistance)을 가져야 한다. 특히 우수한 감도와 해상도의 성질이 중요하며, 이러한 성질을 향상시키기 위한 기술이 종래부터 개발되어져 왔다.The photoresist composition used in the photolithography process should have excellent resolution and sensitivity with respect to the light source exposed as optical properties, other excellent contrast, fast photospeed, It must have good thermal stability, adhesion and etch resistance. In particular, properties of excellent sensitivity and resolution are important, and techniques for improving such properties have been developed in the past.
감도는 포토레지스트 조성물이 노광된 빛에 반응하는 민감성을 의미하는 것으로, 감도가 크면 단위 노광(시간) 당 노광된 빛에 반응하는 레지스트 조성물의 양이 많아져 생산성을 향상시킬 수 있다. 감도를 크게 하기 위해서 감광성 고분자 수지 및 광산발생제를 포함하는 화학증폭의 개념이 도입된 포토레지스트 조성물이 개발되었는데, 화학증폭작용은 다음과 같은 작용을 말한다. 노광되면 광산발생제에서 산이 발생되어 포토레지스트 조성물에 잠상이 생기게 되고, 발생된 산은 노광 후 가열공정에서 활성화되어 상기 레지스트 조성물에 포함된 a) 감광성 고분자 수지의 가교반응 또는 b) 감광성 고분자 수지의 주쇄 또는 주쇄에 결합된 기능기의 해중합(depolymerization) 혹은 탈보호화반응(deprotection)을 일으키는데, 이러한 산은 상기 가교반응, 해중합반응 또는 탈보호화반응의 부산물로도 발생함으로써 연쇄적 화학반응을 유도하여 포토레지스트 조성물의 감도을 향상시킬 수 있다.The sensitivity means the sensitivity of the photoresist composition to the exposed light. When the sensitivity is large, the amount of the resist composition reacting to the exposed light per unit exposure (time) increases, thereby improving productivity. In order to increase the sensitivity, a photoresist composition incorporating the concept of chemical amplification including a photosensitive polymer resin and a photoacid generator has been developed. The chemical amplification action refers to the following actions. Upon exposure, acid is generated in the photoacid generator to cause a latent image in the photoresist composition, and the generated acid is activated in a heating process after exposure, thereby a) crosslinking reaction of the photosensitive polymer resin or b) main chain of the photosensitive polymer resin. Or depolymerization or deprotection of functional groups bonded to the main chain, and these acids also occur as by-products of the crosslinking, depolymerization or deprotection reactions to induce a chain chemical reaction to induce a photoresist composition. Can improve the sensitivity.
해상도는 포토레지스트가 최적의 공정조건에서 구현할 수 있는 미세 회로 패턴의 최소 크기로 정의되고, 포토레지스트의 우수성을 평가하는 중요한 지표가 되는 것으로, 해상도(R) = κλ/ NA (κ는 공정조건 및 포토레지스트의 고유물성에 의존하는 공정변수, λ는 노광되는 빛의 파장(㎚), NA는 렌즈의 구경수차이다)로 표현된다. 상기 식에서 알 수 있는 바와 같이, 우수한 해상도를 얻기 위해서는 노광공정에서 보다 단파장의 광원을 사용하고, 또한 낮은 공정변수 값(κ)을 가지는 감광성 고분자 수지 및 포토레지스트 조성물을 사용하여야 한다. The resolution is defined as the minimum size of the microcircuit pattern that the photoresist can realize at optimum process conditions, and is an important indicator for evaluating the superiority of the photoresist. The resolution (R) = κλ / NA (κ is the process condition and The process variable depending on the intrinsic properties of the photoresist, λ, is expressed as the wavelength of light to be exposed (nm), NA is the aperture aberration of the lens. As can be seen from the above formula, in order to obtain excellent resolution, a shorter wavelength light source should be used in the exposure process, and a photosensitive polymer resin and a photoresist composition having a lower process parameter value (κ) should be used.
상기 화학증폭형 포토 레지스트 조성물은 네가티브(negative)형과 포지티브(positive)형으로 구분된다. 네가티브형 포토레지스트 조성물은 알카리용액에 가용성인 바인더 수지, 가교제, 광산발생제 및 용매를 포함하는 것으로서 (Jour. Vacuum Science Technology., Vol. B6, 1988), 노광부의 광산발생제에서 발생한 산이 가교제를 활성화하는 촉매로 작용하여 바인더 수지를 불용성으로 변하게 함으로써, 이후 수행되는 현상공정에서 네가티브형의 회로패턴을 형성한다. 그러나 바인더 수지로서 종래의 노블락수지, 멜라민 가교수지 및 광산발생제로 구성된 3 성분계 포토레지스트 조성물은 노광 광원이 248nm 파장인 KrF 엑사이머 레이저 또는 193nm 파장인 ArF 엑시머 레이저인 경우, 바인더 수지 및 가교수지에 의한 흡수 영향이 발생하여 패턴이 역 테이퍼(taper) 형태로 형성되는 문제가 발생한다(Jour. Vacuum Science Technology., Vol. B7, 1989). The chemically amplified photoresist composition is classified into a negative type and a positive type. The negative photoresist composition contains a binder resin, a crosslinking agent, a photoacid generator and a solvent soluble in an alkaline solution (Jour. Vacuum Science Technology., Vol. B6, 1988). By acting as an activating catalyst to make the binder resin insoluble, a negative circuit pattern is formed in a subsequent development step. However, the conventional three-component photoresist composition composed of a novolac resin, a melamine crosslinked resin and a photoacid generator as a binder resin may be used in the binder resin and the crosslinked resin when the exposure light source is a KrF excimer laser having a wavelength of 248 nm or an ArF excimer laser having a wavelength of 193 nm. Due to the absorption effect occurs that the pattern is formed in the form of a reverse taper (Jour. Vacuum Science Technology., Vol. B7, 1989).
이에 대한 대안으로 포지티브 화학증폭형 포토레지스트 조성물이 제안되었다 (Proc. Spie., Vol 1262, p32, 1990). 포지티브형 포토레지스트 조성물은 감광성 고분자수지, 광산발생제 및 용매를 포함하는 것으로서 노광부의 광산발생제에서 발생한 산은 감광성 고분자 수지의 주쇄 또는 주쇄에 결합된 보호기(protection group)의 해분해작용(depolymerization) 또는 탈보호작용(deprotection)의 촉매로 작용하여 이후 수행되는 현상공정에서 포지티브형의 회로패턴을 형성시킨다.As an alternative, a positive chemically amplified photoresist composition has been proposed (Proc. Spie., Vol 1262, p32, 1990). The positive type photoresist composition includes a photosensitive polymer resin, a photoacid generator and a solvent, and the acid generated from the photoacid generator in the exposed portion is depolymerized or deprotected from the main chain or the protection group bonded to the main chain of the photosensitive polymer resin. It acts as a catalyst for deprotection to form a positive circuit pattern in a subsequent development process.
포지티브 화학증폭형 포토레지스트 조성물로는, a) 이토(Ito) 등에 의하여 제안된 t-BOC (tertiary-butoxy carbonyl) 그룹으로 블록된 폴리 하이드록시스티렌(poly(hydroxystyrene)) 및 오늄 염(onium salt)으로 구성된 조성물(American Chemical society, "polymers in electronics", ACS Sym. Series, No. 242)과, b) 우에노(Ueno) 등에 의해 제안된 폴리 파라-스티렌옥시테트라하이드로피라닐(poly(p-styreneoxytetrahydropyranyl)과 광산발생제로 구성된 조성물(제36회 일본 응용물리학회 예고집, 1p-k-7, 1989)과 c) 스케젤(Schlegel) 등에 의해 제안된 노블락 수지, t-BOC 그룹으로 치환된 비스페놀-A, 피로갈롤 메탄설포닉산 에스테르(pyrogallol methanesulfonic ester)로 구성된 3 성분계 포지티브 포토레지스트 조성물 (제37회 일본 응용물리학회 예고집, 28p-ZE-4, 1990)이 알려져 있다. 또한 이러한 제조방법과 관련한 기술들이 일본공고 특허공보 평2-27660호, 일본공개 특허공보 평5-232706호, 일본공개 특허공보 평5-249683호, 미국특허 제4,491,628호, 및 미국특허 제5,310,619호 등에 제시되었다. 그러나, 상기 포토레지스트 조성물은 해상도가 우수한 반면, 노광 후 노출-숙성(post-exposure-bake)까지의 시간지연(PED : post exposure delay)이 발생하면 기판과의 반응에 의하여, 패턴에 푸팅(footing) 현상이 발생하는 문제점이 있었다. Positive chemically amplified photoresist compositions include a) poly (hydroxystyrene) and onium salts blocked with tertiary-butoxy carbonyl (t-BOC) groups proposed by Ito et al. (B) poly para-styreneoxytetrahydropyranyl, proposed by Ueno et al., And a composition consisting of American Chemical society, "polymers in electronics", ACS Sym. ) And a composition consisting of a photoacid generator (Preparation of the 36th Japanese Society for Applied Physics, 1p-k-7, 1989) and c) a bisphenol-substituted with t-BOC group, proposed by Schlegel et al. A, three-component positive photoresist composition composed of pyrogallol methanesulfonic ester (37th Japanese Society for Applied Physics, 28p-ZE-4, 1990) is known. In addition, techniques related to such manufacturing methods are disclosed in Japanese Patent Application Laid-Open No. Hei 2-27660, Japanese Patent Application Laid-Open No. 5-232706, Japanese Patent Application Laid-Open No. 5-249683, US Patent No. 4,491,628, and US Patent No. 5,310,619. And the like. However, while the photoresist composition has excellent resolution, if a post exposure delay (PED) occurs after post-exposure-bake, footing is performed on the pattern by reaction with the substrate. ) There was a problem that occurs.
따라서 본 발명의 목적은 노광 후 노출-숙성까지의 시간지연이 발생하여도 푸팅(footing)현상이 발생하지 않는 감광성 고분자 수지 및 이를 포함하는 화학증폭형 포토레지스트 조성물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a photosensitive polymer resin and a chemically amplified photoresist composition including the same, in which no footing phenomenon occurs even after a time delay from exposure to exposure-maturation occurs.
본 발명의 또 다른 목적은 해상도가 우수하여 단파장인 노광원 하에서도 미세한 회로 패턴을 형성할 수 있는 감광성 고분자 수지 및 이를 포함하는 화학증폭형 포토레지스트 조성물을 제공하는 것이다. Still another object of the present invention is to provide a photosensitive polymer resin and a chemically amplified photoresist composition including the same, which are capable of forming a fine circuit pattern even under an exposure source having a short wavelength with excellent resolution.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 감광성 고분자 수지, 및 상기 감광성 고분자 수지, 광산 발생제 및 유기 용매를 포함하는 화학증폭형 포토레지스트 조성물을 제공한다.In order to achieve the above object, the present invention provides a photosensitive polymer resin represented by the following formula (1), and a chemically amplified photoresist composition comprising the photosensitive polymer resin, a photoacid generator and an organic solvent.
[화학식 1][Formula 1]
상기 식에서, R은 수소 또는 메틸기이고, R1은 , 또는 이고, R2는 클로로, 브로모, 하이드록시, 사이아노, t-부톡시, CH2NH2, CONH2, CH=NH, CH(OH)NH2 또는 C(OH)=NH이며, R3는 수소 또는 메틸기이고, 1-x-y, x, y는 상기 감광성 화합물을 구성하는 각 반복단위의 중합도로서, x, y는 각각 0.1∼0.8이고, n은 1 또는 2이다.Wherein R is hydrogen or a methyl group and R 1 is , or R 2 is chloro, bromo, hydroxy, cyano, t-butoxy, CH 2 NH 2 , CONH 2 , CH = NH, CH (OH) NH 2 or C (OH) = NH, R 3 Is hydrogen or a methyl group, and 1-xy, x, y are degrees of polymerization of each repeating unit constituting the photosensitive compound, x and y are each 0.1 to 0.8, and n is 1 or 2.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 감광성 고분자 수지는 화학증폭형 포토레지스트 조성물을 제조하기 위한 것으로서, 하기 화학식 1로 표시된다.The photosensitive polymer resin according to the present invention is for producing a chemically amplified photoresist composition, represented by the following formula (1).
상기 식에서, R은 수소 또는 메틸기이고, R1 은 , 또는 이고, R2는 클로로, 브로모, 하이드록시, 사이아노, t-부톡시, CH2NH2, CONH2, CH=NH, CH(OH)NH2 또는 C(OH)=NH이며, R3는 수소 또는 메틸기이고, 1-x-y, x, y는 상기 감광성 화합물을 구성하는 각 반복단위의 중합도로서, x, y는 각각 0.1∼0.8이고, n은 1 또는 2이다.Wherein R is hydrogen or a methyl group and R 1 is , or R 2 is chloro, bromo, hydroxy, cyano, t-butoxy, CH 2 NH 2 , CONH 2 , CH = NH, CH (OH) NH 2 or C (OH) = NH, R 3 Is hydrogen or a methyl group, and 1-xy, x, y are degrees of polymerization of each repeating unit constituting the photosensitive compound, x and y are each 0.1 to 0.8, and n is 1 or 2.
상기 감광성 고분자 수지는 아조비스(이소부틸로니트릴) (AIBN)등의 적절한 개시제 및 THF 등의 유기 용매의 존재 하에서, 보호기로 블록된 스틸렌기, 비닐기, 및 아크릴레이트기를 중합, 바람직하게는 에틸렌 중합하여 제조할 수 있으며, 제조된 감광성 고분자 수지의 중량평균분자량은 3,000∼30,000이고, 분산도는 1.01∼3.00인 것이 바람직하다. 여기서 상기 중량평균분자량 및 분산도가 상기 범위를 벗어나면, 포토레지스트막의 물성이 저하되거나, 포토레지스트막의 형성이 곤란하고 패턴의 콘트라스트가 저하될 우려가 있다. The photosensitive polymer resin polymerizes a styrene group, a vinyl group, and an acrylate group blocked with a protecting group in the presence of a suitable initiator such as azobis (isobutylonitrile) (AIBN) and an organic solvent such as THF, preferably ethylene It can be prepared by polymerization, the weight average molecular weight of the produced photosensitive polymer resin is preferably 3,000 to 30,000, the dispersion degree is preferably 1.01 to 3.00. If the weight average molecular weight and the dispersion degree are outside the above ranges, the physical properties of the photoresist film may be lowered, or the formation of the photoresist film may be difficult and the contrast of the pattern may be lowered.
본 발명에 따른 감광성 고분자 수지의 더욱 바람직한 예는 하기 화학식 1a 내지 1c의 구조를 가지는 것이다.A more preferred example of the photosensitive polymer resin according to the present invention is to have a structure of the formula (1a) to (1c).
상기 화학식 1a 내지 1c에서, R, x 및 y는 화학식 1에서 정의한 바와 같다.In Formulas 1a to 1c, R, x, and y are as defined in Formula 1.
상기 화학식 1로 표시되는 감광성 고분자 수지는 벌키한 지방족 고리화 탄화수소를 포함하므로, 포토레지스트의 건식 식각 내성을 향상시키며, 노광공정에서 광산발생제에 의해 발생된 산의 작용으로 탈보호되어 용해도가 증가하는 한편, 비노광부는 충분한 용해 억제 능력을 나타내므로, 포토레지스트 조성물의 콘트라스트, 및 해상도를 증가시켜 단파장의 노광원 하에서도 미세한 회로 패턴을 형성할 수 있다. 아울러 노광 후 노출-숙성(post-exposure-bake)까지의 시간지연(PED : post exposure delay)이 발생하여도 푸팅(footing)현상이 발생하지 않는다. Since the photosensitive polymer resin represented by Chemical Formula 1 includes bulky aliphatic cyclized hydrocarbons, it improves the dry etching resistance of the photoresist, and is deprotected by the action of the acid generated by the photoacid generator in the exposure process to increase the solubility. On the other hand, since the non-exposed part exhibits sufficient dissolution inhibiting ability, the contrast and resolution of the photoresist composition can be increased to form a fine circuit pattern even under a short wavelength exposure source. In addition, footing does not occur even if a post exposure delay (PED) occurs after post-exposure-bake.
본 발명에 따른 화학증폭형 포토레지스트 조성물은 a) 상기 화학식 1로 표시되는 감광성 고분자 수지, b) 산을 발생시키는 광산발생제 및 c) 유기 용매를 포함하며, 필요에 따라 각종 첨가제를 더욱 포함할 수 있다.The chemically amplified photoresist composition according to the present invention comprises a) a photosensitive polymer resin represented by Chemical Formula 1, b) a photoacid generator for generating an acid, and c) an organic solvent, and may further include various additives as necessary. Can be.
상기 a) 감광성 고분자 수지의 함량은 전체 포토레지스트 조성물에 대하여 0.1 내지 50 중량%인 것이 바람직하며, 더욱 바람직하게는 1 내지 50 중량% 인 것이다. 만일 상기 감광성 고분자 수지의 함량이 0.1 중량% 미만인 경우에는 코팅 후 남게되는 레지스트 층이 너무 얇아 원하는 두께의 패턴을 형성하기 어렵고, 50중량%를 초과하면 코팅 균일성이 저하될 우려가 있다.The content of the a) photosensitive polymer resin is preferably 0.1 to 50% by weight, more preferably 1 to 50% by weight based on the total photoresist composition. If the content of the photosensitive polymer resin is less than 0.1% by weight, the resist layer remaining after coating is too thin to form a pattern having a desired thickness, and if it exceeds 50% by weight, coating uniformity may be degraded.
상기 b)의 광산발생제는 노광에 의하여 H+ 등 산 성분을 생성하여, 화학증폭작용을 유도하는 것으로서, 당업계에서 통상적으로 알려진 광산발생제를 본 발명에 광범위하게 사용할 수 있다. 상기 광산발생제의 예로는 , , , , , , , , , , , , , , 등의 설포늄염, , , , 등의 아이오도늄 등과 같은 오늄 염(onium salt), , , , 등의 N-이미노설포네이트류, (여기서. R은 -H, -CH3 또는 -C(CH3)3) 등의 다이설폰류, (여기서, R은 -H, -CH3 또는 -C(CH3)3) 등의 비스아릴설포닐다이아조메탄류, (여기서, R은 -H, -CH3 또는 -C(CH3)3) 등의 아릴카보닐아릴설포닐다이아조메탄류 또는 이들의 혼합물을 예시할 수 있으며, 상기 광산발생제의 함량은 전체 포토레지스트 조성물에 대하여 0.1∼30 중량%인 것이 바람직하다. 만일 상기 광산발생제의 함량이 0.1 중량% 미만인 경우에는 노광에 의하여 발생하는 산 성분의 양이 적어 보호기의 탈보호가 곤란할 우려가 있고, 30 중량%를 초과하면 레지스트의 흡광도가 증가하여 패턴의 슬로프(slope)를 유발할 우려가 있다.The photoacid generator of b) generates an acid component such as H + by exposure to induce chemical amplification, and photoacid generators commonly known in the art may be widely used in the present invention. Examples of the photoacid generator include , , , , , , , , , , , , , , Sulfonium salts, , , , Onium salts such as iodonium, and the like, , , , N-iminosulfonates, such as these, Wherein R is -H, -CH 3 or -C (CH 3 ) 3 (Wherein R is -H, -CH 3 or -C (CH 3 ) 3 ) such as bisarylsulfonyldiazomethane, Wherein R is -H, -CH 3 or -C (CH 3 ) 3 , such as arylcarbonylarylsulfonyldiazomethanes or mixtures thereof, and the content of the photoacid generator is It is preferable that it is 0.1-30 weight% with respect to a photoresist composition. If the content of the photoacid generator is less than 0.1% by weight, the amount of acid generated by exposure is small, which may make it difficult to deprotect the protecting group. If the content of the photoacid generator exceeds 30% by weight, the absorbance of the resist may increase to increase the slope of the pattern. It may cause a slope.
본 발명에 따른 포토레지스트 조성물의 나머지 성분을 구성하는 c) 유기 용매로는 포토레지스트 조성물의 제조에 통상적으로 사용되는 다양한 유기 용매를 광범위하게 사용할 수 있다. 이와 같은 유기 용매의 비한정적인 예로는 에틸락테이트, 에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 에틸에테르아세테이트, n-부틸아세테이트, 메틸이소부틸케톤, 3-에톡시-에틸프로피오네이트, 3-메톡시-메틸프로피오네이트, 디글리콜모노에틸에테르, 2-헵타논, 디아세톤알콜, β-메톡시이소부티릭에시드 메틸에스테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸프로피오네이트, 메틸락테이트, 부틸락테이트, 에틸피루베이트, γ-부티롤락톤, 이들의 혼합물 등을 예시할 수 있다.C) As the organic solvent constituting the remaining components of the photoresist composition according to the present invention can be used a wide variety of organic solvents commonly used in the preparation of the photoresist composition. Non-limiting examples of such organic solvents include ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl ether acetate, n-butyl acetate, methyl isobutyl ketone, 3-ethoxy-ethylpropio Nitrate, 3-methoxy-methylpropionate, diglycol monoethyl ether, 2-heptanone, diacetone alcohol, β-methoxyisobutyric acid methyl ester, propylene glycol monomethyl ether, propylene glycol monomethyl propio Nate, methyl lactate, butyl lactate, ethylpyruvate, γ-butyrolactone, mixtures thereof, and the like can be exemplified.
본 발명에 따른 포토레지스트 조성물은 상기 감광성 고분자 수지, 광산발생제, 유기 용매 이외에 용해 억제제를 포함할 수도 있다. 상기 용해 억제제는 비노광부의 현상액에 대한 용해도를 감소시켜 노광부와의 용해도 차이를 크게 함으로서, 콘트라스트를 향상시키기 위한 것으로서, 당업계에서 통상적으로 알려진 광산 발생제를 본 발명에 광범위하게 사용할 수 있다. 상기 용해억제제의 사용량은 감광성 고분자 수지에 대하여 0.1 내지 50 중량% 인 것이 바람직하다. The photoresist composition according to the present invention may include a dissolution inhibitor in addition to the photosensitive polymer resin, a photoacid generator, and an organic solvent. The dissolution inhibitor is to improve the contrast by reducing the solubility in the developer of the non-exposed part to increase the solubility difference with the exposed part, and a photoacid generator commonly known in the art can be widely used in the present invention. The amount of the dissolution inhibitor is preferably 0.1 to 50% by weight based on the photosensitive polymer resin.
본 발명에 따른 화학증폭형 포토레지스트 조성물을 이용하여, 하기와 같은 방법으로 포토레지스트 패턴을 형성할 수 있다.Using the chemically amplified photoresist composition according to the present invention, a photoresist pattern may be formed by the following method.
먼저, 실리콘 웨이퍼, 알루미늄 기판 등의 기판 상부에 본 발명에 따른 화학증폭형 포토레지스트 조성물을 스핀코터 등을 이용하여 도포하여 얇은 박막을 형성시킨다. 이때 형성된 박막은 염기성 수용액으로 처리하여도 감광성 고분자 수지의 용해도가 낮아서 거의 용해되지 않는다. 이와 같이 형성된 박막에 단파장의 광원을 조사하면 포토레지스트 조성물내의 광산발생제가 광원에 감응하여 산을 발생시키고, 열의 부가 작용에 의하여 감광성 고분자수지의 주쇄에 연결된 현상 억제형 보호기가 탈보호되면서 다시 산이 발생된다. 결과적으로 하나의 발생된 산이 여러 개의 산활성 분해 작용을 일으키는 화학 증폭현상을 나타내며, 그 결과 노광부의 현상액에 대한 용해도가 크게 증가하여, 비노광부와 노광부의 용해도 차이가 발생하게 된다. 따라서, 종래의 G-선 및 I-선에서 감응하는 종래의 포지티브형 화학증폭 레지스트 수지를 적용한 조성물보다 우수한 해상도를 얻을 수 있다. First, a chemically amplified photoresist composition according to the present invention is applied to a substrate such as a silicon wafer or an aluminum substrate by using a spin coater to form a thin film. At this time, the formed thin film is hardly dissolved due to low solubility of the photosensitive polymer resin even when treated with a basic aqueous solution. When the light source having a short wavelength is irradiated to the thin film thus formed, the photoacid generator in the photoresist composition reacts with the light source to generate an acid, and the acid is generated again while the development inhibitor type protecting group connected to the main chain of the photosensitive polymer resin is deprotected by the addition of heat. do. As a result, one generated acid exhibits a chemical amplification phenomenon that causes several acid active decomposition activities. As a result, the solubility of the exposed part in the developer is greatly increased, resulting in a difference in the solubility of the non-exposed part and the exposed part. Therefore, a resolution superior to the composition to which the conventional positive chemically amplified resist resin applied in the conventional G-rays and I-rays can be obtained.
이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 하기 실시예에 의하여 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.
[실시예 1] 상기 화학식 1a로 표시되는 Poly(HS-co-MAMA-co-CBCPS) 고분자 수지의 합성 Example 1 Synthesis of Poly (HS-co-MAMA-co-CBCPS) Polymer Resin Represented by Chemical Formula 1a
a) 4-사이아노메틸스타이렌(CyMS)의 합성a) Synthesis of 4-Cyanomethylstyrene (CyMS)
하기 반응식 1a에 나타낸 바와 같이, 먼저 교반봉이 장착된 500 ㎖ 4구 플라스크에서 나트륨사이아나이드(NaCN) 49.01 g을 물 70.07 g과 에탄올 50.96 g에 혼합하고, 온도를 60 ℃로 승온하여 나트륨사이아나이드를 완전히 용해시켰다. 상기 용액에 4-클로로메틸스타이렌 87.50 g을 천천히 투입하고, 반응온도를 60∼70 ℃로 유지하면서 3 시간 동안 교반하면서 반응시켰다. 반응이 완결된 후, 40 ℃로 냉각하고, 다이에틸에테르 100 g을 첨가하여 다이에틸에테르 층을 분리하였다. 분리된 유기층을 물 300 g으로 3회 추출하고, 물 층을 다이에틸에테르 50 g으로 추출하여 유기층에 혼합하였다. 분리 수득된 유기층을 마그네슘설페이트로 1일 동안 건조한 후, 증발기로 유기용제를 제거하여 진한 자주색의 4-사이아노메틸스타이렌을 얻었다(수득률 80%).As shown in Scheme 1a, first, 49.01 g of sodium cyanide (NaCN) was mixed with 70.07 g of water and 50.96 g of ethanol in a 500 ml four-necked flask equipped with a stirring rod, and the temperature was raised to 60 ° C. to give sodium cyanide. Completely dissolved. 87.50 g of 4-chloromethyl styrene was slowly added to the solution, followed by reaction with stirring for 3 hours while maintaining the reaction temperature at 60 to 70 ° C. After the reaction was completed, the mixture was cooled to 40 ° C, and 100 g of diethyl ether was added to separate the diethyl ether layer. The separated organic layer was extracted three times with 300 g of water, and the water layer was extracted with 50 g of diethyl ether and mixed with the organic layer. After separating and drying the obtained organic layer with magnesium sulfate for 1 day, the organic solvent was removed by an evaporator to obtain dark purple 4-cyanomethylstyrene (yield 80%).
b) 4-(3-사이아노-다이-1,5-t-부톡시카보닐-펜틸)스타이렌(CBCPS)의 합성b) Synthesis of 4- (3-cyano-di-1,5-t-butoxycarbonyl-pentyl) styrene (CBCPS)
하기 반응식 1b에 나타낸 바와 같이, 얻어진 4-사이아노메틸스타이렌 57.28 g과 트리톤 비용액 1.4 g을 교반봉이 부착된 500 ㎖ 4구 플라스크에 넣고 다이옥산 40 g으로 용해하였다. 반응기의 온도를 60 ℃로 유지하면서 상기 용액에 t-부틸아크릴레이트 102.54 g을 약 30 분 동안 천천히 투입하고, 24 시간 동안 교반하면서 반응시켰다. 반응이 완결된 후, 반응물을 염산 용액으로 중화하고, 중화된 반응액을 다이에틸에테르 100 g과 물 300 g으로 3 회 추출하고, 물 층을 다이에틸에테르 50 g으로 추출하여 유기층에 혼합하였다. 분리 수득된 유기층을 마그네슘설페이트로 1 일 동안 건조한 후 증발기를 이용하여 유기 용매를 제거하였다. 얻은 결과물을 감압 증류하여 미반응 물질을 제거하고, 메탄올로 재결정하여 연노랑색의 CBCPS를 얻었다(수득률 60 %).As shown in the following Reaction Scheme 1b, 57.28 g of 4-cyanomethylstyrene obtained and 1.4 g of Triton nasal solution were placed in a 500 ml four-necked flask equipped with a stirring rod and dissolved in 40 g of dioxane. While maintaining the temperature of the reactor at 60 ° C, 102.54 g of t-butyl acrylate was slowly added to the solution for about 30 minutes, and reacted with stirring for 24 hours. After the reaction was completed, the reaction was neutralized with a hydrochloric acid solution, the neutralized reaction solution was extracted three times with 100 g of diethyl ether and 300 g of water, and the water layer was extracted with 50 g of diethyl ether, and mixed with the organic layer. Separation The obtained organic layer was dried with magnesium sulfate for 1 day and then the organic solvent was removed using an evaporator. The resulting product was distilled under reduced pressure to remove unreacted material, and recrystallized from methanol to obtain light yellow CBCPS (yield 60%).
c) Poly(HS-co-MAMA-co-CBCPS) 고분자 수지 합성c) Synthesis of Poly (HS-co-MAMA-co-CBCPS) polymer resin
하기 반응식 1c에 나타낸 바와 같이, 온도조절장치 및 질소 투입기가 부착된 500 ㎖ 4구 플라스크에 THF 200 ㎖를 투입하고, 질소를 가하여 30 분간 교반하였다. 반응기의 온도를 25 ℃로 유지하면서 4-아세톡시스틸렌 42.57 g과 상기 실시예 1(b)에서 제조한 CBCPS 13.98 g을 투입한 후, 2-메틸아다멘틸 메타크릴레이트 13.14 g을 투입하고, 2.09 g의 AIBN을 가하였다. 상기 반응기의 온도를 40 ℃로 상승시킨 후 유지하며 질소 분위기 하에서 30 분간 교반하였다. 상기 반응기의 온도를 60∼70 ℃로 상승시켜서 반응액이 환류되도록 유지하면서 24 시간 동안 교반 반응시켰다. 반응이 완결된 후, 온도를 상온(25 ℃)으로 낮추고 반응액을 헥산 2 ℓ에 침적시켜 침전물을 얻었다. 얻은 침전물을 여과하고 2 ℓ의 헥산으로 수 회 세척하고 진공 건조하였다. 건조된 고분자를 플라스크에서 메탄올 200 ㎖로 용해시킨 후, 28 % NH3 수용액 12.75 ㎖를 첨가하여 천천히 교반하고, 고분자가 완전히 용해된 후 30 분간 교반하였다. 상기 교반된 용액을 2 ℓ의 물에 침적시켜서 침전물을 얻었고, 얻어진 침전물을 여과하고 2 ℓ의 순수로 수 회 세척한 후, 2 일 동안 진공 건조하여 poly(HS-co-MAMA-co-CBCPS) 고분자 수지 48 g을 얻었다.As shown in the following Reaction Scheme 1c, 200 ml of THF was added to a 500 ml four-necked flask equipped with a thermostat and a nitrogen injector, and nitrogen was added and stirred for 30 minutes. 42.57 g of 4-acetoxy styrene and 13.98 g of CBCPS prepared in Example 1 (b) were added while maintaining the temperature of the reactor at 25 ° C., followed by 13.14 g of 2-methyladamantyl methacrylate, followed by 2.09. g of AIBN was added. The temperature of the reactor was raised to 40 ° C. and maintained, followed by stirring for 30 minutes under a nitrogen atmosphere. The temperature of the reactor was raised to 60-70 ° C., followed by stirring for 24 hours while maintaining the reaction solution at reflux. After the reaction was completed, the temperature was lowered to room temperature (25 ° C.) and the reaction solution was immersed in 2 L of hexane to obtain a precipitate. The precipitate obtained was filtered off, washed several times with 2 L of hexane and dried in vacuo. The dried polymer was dissolved in 200 ml of methanol in a flask, then 12.75 ml of an aqueous 28% NH 3 solution was added thereto, and stirred slowly. After the polymer was completely dissolved, the mixture was stirred for 30 minutes. The stirred solution was dipped in 2 L of water to obtain a precipitate, which was filtered, washed several times with 2 L of pure water, and then vacuum dried for 2 days to give poly (HS-co-MAMA-co-CBCPS) 48 g of a polymer resin was obtained.
[실시예 2] 상기 화학식 1b로 표시되는 poly(HS-co-EAMA-co-CBCPS) 고분자 수지의 합성 Example 2 Synthesis of poly (HS-co-EAMA-co-CBCPS) polymer resin represented by Chemical Formula 1b
하기 반응식 2에 나타낸 바와 같이, 단량체로서 2-메틸아다멘틸 메타크릴레이트 13.14 g 대신 2-에틸아다멘틸 메타크릴레이트 13.88 g을 사용하고, 개시제로서 AIBN 2.11 g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 poly(HS-co-EAMA-co-CBCPS) 고분자 수지 49 g을 얻었다.As shown in Scheme 2, Example 1, except that 13.88 g of 2-ethyladamantyl methacrylate was used instead of 13.14 g of 2-methyladamantyl methacrylate as the monomer, and 2.11 g of AIBN was used as the initiator. 49 g of a poly (HS-co-EAMA-co-CBCPS) polymer resin was obtained by the same method as described above.
[실시예 3] 상기 화학식 1c로 표시되는 poly(HS-co-HMA-co-CBCPS) 고분자 수지의 합성 Example 3 Synthesis of poly (HS-co-HMA-co-CBCPS) polymer resin represented by Chemical Formula 1c
하기 반응식 3에 나타낸 바와 같이, 단량체로서 5-히드록시 2-메틸 아다멘틸 메타크릴레이트 13.98 g 및 개시제로서 AIBN 2.11 g 을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 poly(HS-co-HMA-co-CBCPS) 고분자 수지 49 g을 얻었다.As shown in Scheme 3 below, poly (HS-co-HMA was prepared in the same manner as in Example 1, except that 13.98 g of 5-hydroxy 2-methyl adamantyl methacrylate as the monomer and 2.11 g of AIBN as the initiator were used. 49 g of polymer resin was obtained.
[실시예 4 내지 13] 화학증폭형 포토레지스트 조성물의 제조 및 미세회로패턴의 형성 Examples 4 to 13 Preparation of Chemically Amplified Photoresist Compositions and Formation of Microcircuit Patterns
상기 실시예 1 내지 3에서 얻은 감광성 고분자 수지 및 하기 화학식 2 , 화학식 3, 화학식 4, 및/또는 5로 표시되는 광산발생제를 유기용매인 에틸락테이트(EL)에 표 1에 기재된 중량비로 용해하여 화학증폭형 레지스트 조성물을 얻었다. 얻어진 조성물을 실리콘 웨이퍼 위에 3000 rpm으로 회전 도포하고, 130 ℃ 온도로 90 초 동안 가열하여 박막을 형성하였다. 형성된 박막 위에 미세 패턴 마스크를 장착하고, 248 ㎚의 단파장 빛을 조사한 후, 130 ℃에서 90 초 동안 가열하였다. 가열된 레지스트 조성물을 2.38 % 테트라메틸암모늄하이드록사이드 수용액으로 60초 동안 현상한 후, 순수로 세척하고 건조하여 미세 회로패턴을 얻었다. 얻어진 미세 회로패턴의 상대 감도와 해상도를 측정하여 표 1에 나타내었다.The photosensitive polymer resins obtained in Examples 1 to 3 and the photoacid generator represented by the following Chemical Formulas 2, 3, 4, and / or 5 are dissolved in ethyl lactate (EL) as an organic solvent in a weight ratio shown in Table 1. To obtain a chemically amplified resist composition. The resulting composition was spun onto a silicon wafer at 3000 rpm and heated at 130 ° C. for 90 seconds to form a thin film. A fine pattern mask was mounted on the formed thin film, and was irradiated with short wavelength light of 248 nm, and then heated at 130 ° C. for 90 seconds. The heated resist composition was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, washed with pure water and dried to obtain a fine circuit pattern. Table 1 shows the relative sensitivity and resolution of the obtained fine circuit pattern.
[비교예 1 및 2] 하기 화학식 6 또는 7로 표시되는 감광성 고분자 수지를 포함한 포토레지스트 조성물의 제조 및 회로패턴의 형성 [Comparative Examples 1 and 2] Preparation of a photoresist composition including a photosensitive polymer resin represented by the following Chemical Formula 6 or 7 and formation of a circuit pattern
하기 화학식 6 또는 7로 표시되는 감광성 고분자 수지 및 상기 화학식 2 또는 3으로 표시되는 광산발생제를 유기용매인 에틸락테이트(EL)에 표 1에 기재된 조성비로 용해하여 포토레지스트 조성물을 얻었고, 얻어진 조성물을 사용하여 실시예 4와 동일한 방법으로 반도체회로패턴을 얻었다. 얻어진 회로패턴의 상대 감도와 해상도를 측정하여 표 1에 나타내었다. A photoresist composition was obtained by dissolving the photosensitive polymer resin represented by the following Chemical Formula 6 or 7 and the photoacid generator represented by the above Chemical Formula 2 or 3 in the ethyl lactate (EL) as an organic solvent in the composition ratios shown in Table 1. Using the same method as in Example 4, a semiconductor circuit pattern was obtained. Table 1 shows the relative sensitivity and resolution of the obtained circuit pattern.
상기 표 1에서 상대 감도는 optimal energy(Eop)를 뜻하며, 상기 표에 나타난 바와 같이 본 발명의 실시예에 따른 화학증폭형 포토레지스트 조성물은 비교예에 따른 종래의 레지스트 조성물보다 해상도가 우수하여 248nm의 단파장의 노광원하에서도 미세한 회로패턴을 형성시킬 수 있음을 알 수 있다. In Table 1, the relative sensitivity means optimal energy (Eop), and as shown in the above table, the chemically amplified photoresist composition according to the embodiment of the present invention has a higher resolution than the conventional resist composition according to the comparative example of 248 nm. It can be seen that even a short wavelength exposure source can form a fine circuit pattern.
본 발명에 따른 감광성 고분자 수지 및 화학증폭형 포토레지스트 조성물은 포토리소그래피 공정에서 노광 후 노출-숙성(post-exposure-bake)까지의 시간지연(PED : post exposure delay)이 발생하여도 푸팅(footing)현상이 발생하지 않는 장점이 있다. 또한, 본 발명에 따른 감광성 고분자 수지 및 화학증폭형 포토레지스트 조성물은 포토리소그래피 공정에서 단파장의 노광원하에서도 우수한 해상도를 가져 미세한 회로 패턴을 형성시킬 수 있는 장점이 있다.The photosensitive polymer resin and the chemically amplified photoresist composition according to the present invention have a footing even after a post exposure delay (PED) occurs in a photolithography process to post-exposure-bake. There is an advantage that the phenomenon does not occur. In addition, the photosensitive polymer resin and the chemically amplified photoresist composition according to the present invention have an advantage of forming a fine circuit pattern with excellent resolution even under a short wavelength exposure source in a photolithography process.
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