KR20030032450A - Novel negative type photoresist polymer and photoresist composition containing the same - Google Patents
Novel negative type photoresist polymer and photoresist composition containing the same Download PDFInfo
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—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
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
Abstract
Description
본 발명은 신규의 네가티브형 포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물에 관한 것으로, 더욱 상세하게는 수산기를 가지는 단량체인 노폴 (nopol)을 포함하는 것을 특징으로 하고 단층 레지스트 공정에 사용하기 적합한 네가티브형 포토레지스트 공중합체 및 이를 함유하는 포토레지스트 조성물에 관한 것이다.The present invention relates to a novel negative type photoresist polymer and a photoresist composition containing the same, and more particularly, to a negative type suitable for use in a single layer resist process, characterized in that it comprises a nopol, a monomer having a hydroxyl group. It relates to a photoresist copolymer and a photoresist composition containing the same.
반도체 제조의 미세회로 형성 공정에서 고감도를 달성하기 위해, 근래에는 화학증폭성인 DUV (Deep Ultra Violet) 포토레지스트가 각광을 받고 있으며, 그 조성은 광산 발생제 (photoacid generator)와 산에 민감하게 반응하는 구조의 매트릭스 고분자를 배합하여 제조한다.In order to achieve high sensitivity in the process of forming microcircuits in semiconductor manufacturing, chemically amplified deep ultra violet (DUV) photoresists have been in the spotlight, and their composition is sensitive to photoacid generators and acids. It is prepared by blending the matrix polymer of the structure.
이러한 포토레지스트의 작용 기전을 네가티브형 포토레지스트를 예로 들어 설명하면, 광산발생제가 광원으로부터 자외선 빛을 받게 되면 산을 발생시키고, 이렇게 발생된 산에 의해 포토레지스트 중합체의 주쇄 또는 측쇄가 가교제와 반응하거나 포토레지스트 중합체 내에 존재하는 작용기들 사이의 가교결합이 생겨서 노광부위는 현상액에 녹아 없어지지 않게 되고, 비노광부위는 현상액에 녹는다. 이렇게 하여 마스크의 상을 기판 위에 음화상으로 남길 수 있게 된다.When the photoresist action mechanism is described using a negative photoresist as an example, when the photoacid generator receives ultraviolet light from a light source, an acid is generated, and the acid or the main chain or side chain of the photoresist polymer reacts with the crosslinking agent. Crosslinking between functional groups present in the photoresist polymer occurs so that the exposed portion is not dissolved in the developer, and the non-exposed portion is dissolved in the developer. In this way, the mask image can be left as a negative image on the substrate.
한편, 0.13㎛ 이하의 초미세 패턴 형성에 있어 기존의 포토레지스트 코팅 두께에서는 아스펙트비 (aspect ratio)가 높아 패턴이 쓰러지는 문제가 발생하고 있으나, 코팅 두께를 낮추면 에칭시 내성이 없어져 후속 공정이 불가능하게 된다. 따라서 최근에는 포토레지스트의 코팅 두께는 낮추고 포토레지스트막의 아래층에 하드 마스크 (hard mask)를 도입하는 씬 레지스트-하드 마스크 (thin resist-hard mask) 공정이 대두되고 있으며, 또 다른 방법으로서 포토레지스트 자체에 실리콘 원소가 함유되어 있는 2층 레지스트 (bilayer resist)를 이용한 공정이 요구되고 있다. 그러나 이들은 추가공정으로 인해 공정이 복잡해지고 공정비용이 상승하는 문제가 있다. 따라서, 본 발명자들은 단층 레지스트 공정에 사용하기에 적합한 포토레지스트를 개발하기 위하여 연구를 계속하던 중, 노폴을 포함하는 포토레지스트 중합체를 도입함으로써 에칭 내성이 크게 향상되어 단층 레지스트로 사용하기에 적합할 뿐만 아니라 중합 수율도 우수해짐을 알아내어 본 발명을 완성하였다.On the other hand, in the formation of ultra fine patterns of 0.13 μm or less, there is a problem in that the pattern collapses due to a high aspect ratio in the conventional photoresist coating thickness. Done. Therefore, in recent years, a thin resist-hard mask process that lowers the coating thickness of the photoresist and introduces a hard mask in the lower layer of the photoresist film has emerged. There is a need for a process using a bilayer resist containing silicon elements. However, they have a problem that the additional process is complicated and the process cost increases. Therefore, the present inventors continue to develop a photoresist suitable for use in a single layer resist process, and by introducing a photoresist polymer containing nopol, the etching resistance is greatly improved, and thus it is suitable for use as a single layer resist. In addition, the polymerization yield was also found to be excellent, and completed the present invention.
본 발명의 목적은 단층 네가티브형 포토레지스트로 사용하기에 적합한 포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물을 제공하는 것이다.It is an object of the present invention to provide a photoresist polymer suitable for use as a single layer negative photoresist and a photoresist composition containing the same.
또한 본 발명의 목적은 상기 포토레지스트 조성물을 이용하여 포토레지스트 패턴을 형성하는 방법 및 이러한 방법에 의해 얻어진 반도체 소자를 제공하는 것이다.It is also an object of the present invention to provide a method of forming a photoresist pattern using the photoresist composition and a semiconductor device obtained by the method.
도 1은 본 발명에 따른 실시예 3에 의해 형성된 포토레지스트 패턴 사진.1 is a photoresist pattern photo formed by Example 3 according to the present invention.
도 2는 본 발명에 따른 실시예 4에 의해 형성된 포토레지스트 패턴 사진.Figure 2 is a photoresist pattern photo formed by Example 4 according to the present invention.
상기 목적을 달성하기 위하여 본 발명에서는 노폴을 포함하는 포토레지스트 중합체 및 그의 제조방법; 상기 중합체를 함유하는 포토레지스트 조성물; 상기 조성물을 이용한 포토레지스트 패턴 형성방법; 및 상기 패턴 형성방법에 의해 제조된 반도체 소자를 제공한다.In order to achieve the above object, the present invention provides a photoresist polymer comprising a nopol and a method of manufacturing the same; A photoresist composition containing the polymer; A photoresist pattern forming method using the composition; And a semiconductor device manufactured by the pattern forming method.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 우선, 하기 화학식 2의 노폴을 포함하는 포토레지스트 중합체를 제공한다. 또 선택적으로 하기 화학식 3의 화합물, 화학식 4의 화합물 및 화학식 5의 화합물 중 1 이상의 단량체를 포함하는 포토레지스트 중합체를 제공한다. 바람직하게는 본 발명의 포토레지스트 중합체는 하기 화학식 1의 중합 반복 단위 (repeating unit)를 포함한다.In the present invention, first, a photoresist polymer including a nopol of the following Chemical Formula 2 is provided. Also optionally provided is a photoresist polymer comprising at least one monomer of a compound of Formula 3, a compound of Formula 4, and a compound of Formula 5. Preferably the photoresist polymer of the present invention comprises a polymerizing repeating unit of the formula (1).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 식에서,Where
R은 H 또는 CH3이고;R is H or CH 3 ;
m은 0 또는 1이고;m is 0 or 1;
n은 1 내지 10중에서 선택되는 정수이고;n is an integer selected from 1 to 10;
a : b : c : d는 1∼50몰% : 0∼50몰% : 0∼30몰% : 0∼10몰%이고, 바람직하게는 5∼50몰% : 5∼50몰% : 0∼25몰% : 0∼10몰%이며;a: b: c: d is 1-50 mol%: 0-50 mol%: 0-30 mol%: 0-10 mol%, Preferably 5-50 mol%: 5-50 mol%: 0- 25 mol%: 0-10 mol%;
상기 중합 반복 단위의 중량평균 분자량은 3000 내지 50000이고, 바람직하게는 3000 내지 30000이다.The weight average molecular weight of the said polymerization repeating unit is 3000-50000, Preferably it is 3000-30000.
본 발명에서는 또한 상기 화학식 1의 중합 반복 단위를 포함하는 포토레지스트 중합체를 제조하는 방법을 제공한다.The present invention also provides a method of preparing a photoresist polymer comprising the polymerized repeating unit of Formula 1.
특히, 본 발명의 중합 반복 단위의 제조방법은 하기와 같은 단계를 포함한다.In particular, the method for producing the polymerized repeating unit of the present invention includes the following steps.
(a) (i) 상기 화학식 2의 화합물과, 선택적으로 (ii) 상기 화학식 3의 화합물, 화학식 4의 화합물 및 화학식 5의 화합물 중 1 이상의 단량체를 혼합하는 단계; 및(a) mixing (i) the compound of Formula 2 and optionally (ii) one or more monomers of the compound of Formula 3, the compound of Formula 4 and the compound of Formula 5; And
(b) 상기 결과물 용액에 중합개시제를 첨가하여 중합반응시킴으로써 상기 화학식 1의 중합 반복 단위를 얻는 단계.(b) obtaining a polymerization repeating unit of Chemical Formula 1 by adding a polymerization initiator to the resulting solution and subjecting it to a polymerization reaction.
상기 (b)단계의 중합반응은 질소 또는 아르곤 분위기 하에서 50 내지 120℃, 바람직하게는 50 내지 80℃의 온도에서 4 내지 24시간 동안 수행하는 것이 바람직하다.The polymerization of step (b) is preferably performed at 50 to 120 ° C., preferably at 50 to 80 ° C., for 4 to 24 hours under nitrogen or argon atmosphere.
또한 상기 제조과정에서 라디칼 중합은 벌크 중합 또는 용액 중합으로 수행되는데, 용액 중합의 경우 테트라하이드로퓨란, 디메틸포름아미드, 디메틸술폭사이드, 클로로포름, 에틸아세테이트, 아세톤, 디옥산, 메틸에틸케톤, 벤젠, 톨루엔 및 크실렌로 이루어진 군으로부터 선택된 단독용매 또는 혼합용매를 사용한다.In addition, the radical polymerization in the manufacturing process is carried out by bulk polymerization or solution polymerization, in the case of solution polymerization tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, chloroform, ethyl acetate, acetone, dioxane, methyl ethyl ketone, benzene, toluene And a single solvent or a mixed solvent selected from the group consisting of xylene.
중합개시제로는 2,2'-아조비스이소부티로니트릴 (AIBN), 벤조일퍼옥사이드, 아세틸퍼옥사이드, 라우릴퍼옥사이드, t-부틸퍼아세테이트, 디-t-부틸퍼옥사이드 및 비스아자이드계 화합물로 이루어진 군으로부터 선택된 것을 사용하는 것이 바람직하다.Polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, acetyl peroxide, lauryl peroxide, t-butyl peracetate, di-t-butyl peroxide and bisazide Preference is given to using those selected from the group consisting of compounds.
한편, 생성된 중합 반복 단위는 디에틸에테르, 석유 에테르, n-헥산, 사이클로헥산, 메탄올, 에탄올, 프로판올, 이소프로판올, 물 또는 이들의 혼합용매를 사용하여 결정 정제하는 것이 보다 바람직하다.On the other hand, the resulting polymerization repeating unit is more preferably crystallized using diethyl ether, petroleum ether, n-hexane, cyclohexane, methanol, ethanol, propanol, isopropanol, water or a mixed solvent thereof.
본 발명의 포토레지스트 중합체는 주쇄 내에서 상기 중합 반복 단위를 포함하며, 필요에 따라 기타 공단량체 또는 첨가제 등을 포함한다.The photoresist polymer of the present invention comprises the polymerized repeating unit in the main chain, and other comonomers or additives as necessary.
본 발명에서는 또한 (i) 전술한 본 발명의 포토레지스트 중합체, (ii) 광산발생제 및 (iii) 유기용매를 포함하는 포토레지스트 조성물을 제공한다.The present invention also provides a photoresist composition comprising (i) the photoresist polymer of the invention described above, (ii) a photoacid generator and (iii) an organic solvent.
여기서 포토레지스트 중합체를 구성하는 상기 화학식 5의 화합물은 에폭시기를 가지는 단량체로서 가교기능을 가지며, 만약 상기 화학식 1의 중합 반복 단위가 상기 화학식 5의 화합물을 포함하지 않거나(d = 0몰%), 그 비율이 낮은(d < 1몰%) 경우에는 별도의 가교제를 포토레지스트 조성물에 첨가하는 것이 바람직하다.Wherein the compound of Chemical Formula 5 constituting the photoresist polymer has a crosslinking function as a monomer having an epoxy group, and if the polymerization repeating unit of Chemical Formula 1 does not include the compound of Chemical Formula 5 (d = 0 mol%), When the ratio is low (d <1 mol%), it is preferable to add a separate crosslinking agent to the photoresist composition.
따라서 d가 1몰% 이하인 경우 사용하는 가교제는 에폭시기, 알데히드기 또는 아세탈기를 가지는 화합물로서, 바람직하게는 글리세롤 프로폭실레이트 트리글리시딜 에테르 (Glycerol propoxylate triglycidyl ether), 1,4-디(디메톡시메틸)벤젠 (1,4-di(dimethoxymethyl)benzene) 또는 글루타릭 디알데히드 (glutaric dialdehyde) 등이 사용된다.Therefore, the crosslinking agent used when d is 1 mol% or less is a compound having an epoxy group, an aldehyde group or an acetal group, preferably glycerol propoxylate triglycidyl ether, 1,4-di (dimethoxymethyl) Benzene (1,4-di (dimethoxymethyl) benzene) or glutaric dialdehyde is used.
상기 가교제는 상기 포토레지스트 중합체에 대해 0 내지 10중량% 비율로 사용되는 것이 바람직하다.The crosslinking agent is preferably used in a ratio of 0 to 10% by weight based on the photoresist polymer.
상기 광산 발생제로는 빛에 의해 산을 발생할 수 있는 화합물이면 무엇이든 사용가능하며, US 5,212,043 (1993. 5. 18), WO 97/33198 (1997. 9. 12), WO 96/37526 (1996. 11. 28), EP 0 794 458 (1997. 9. 10), EP 0 789 278 (1997. 8. 13), US 5,750,680 (1998. 5. 12), US 6,051,678 (2000. 4. 18), GB 2,345,286 A (2000. 7. 5), US 6,132,926 (2000. 10. 17), US 6,143,463 (2000. 11. 7), US 6,150,069 (2000. 11. 21), US 6,180,316 BI (2001. 1. 30), US 6,225,020 B1 (2001. 5. 1), US 6,235,448 B1 (2001. 5. 22) 및 US 6,235,447 B1 (2001. 5. 22) 등에 개시된 것을 포함하고, 주로 오니움염계, 황화염계, 할로겐계, 디아조케톤계,술폰계 또는 술폰산계 화합물을 사용한다.As the photo-acid generator, any compound capable of generating an acid by light may be used, for example, US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 (1996. 11.28), EP 0 794 458 (September 10, 1997), EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), US 6,051,678 (April 18, 2000), GB 2,345,286 A (July 5, 2000), US 6,132,926 (October 17, 2000), US 6,143,463 (Nov. 7, 2000), US 6,150,069 (11/21/2000), US 6,180,316 BI (January 30, 2001) , US 6,225,020 B1 (May 1, 2001), US 6,235,448 B1 (May 22, 2001) and US 6,235,447 B1 (May 22, 2001) and the like, mainly onium salts, sulfides, halogens , Diazo ketone type, sulfone type or sulfonic acid type compounds are used.
바람직하게는 디페닐요도염 헥사플루오르포스페이트, 디페닐요도염 헥사플루오르 아르세네이트, 디페닐요도염 헥사플루오르 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 디페닐파라-t-부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오르 포스페이트, 트리페닐설포늄 헥사플루오르 아르세네이트, 트리페닐설포늄 헥사플루오르 안티모네이트, 트리페닐설포늄 트리플레이트 또는 디부틸나프틸설포늄 트리플레이트를 하나 또는 둘 이상 포함하여 사용할 수 있다.Preferably diphenyl iodo hexafluorophosphate, diphenyl iodo hexafluoro arsenate, diphenyl iodo hexafluoro antimonate, diphenyl paramethoxyphenyl triflate, diphenyl paratoluenyl triflate, diphenyl paraiso Butylphenyl triflate, diphenylpara-t-butylphenyl triflate, triphenylsulfonium hexafluoro phosphate, triphenylsulfonium hexafluor arsenate, triphenylsulfonium hexafluor antimonate, triphenylsulfonium triflate Or dibutylnaphthylsulfonium triflate may be used including one or two or more.
상기 광산발생제는 상기 포토레지스트 중합체 대해 0.05 내지 10중량% 비율로 사용되는 것이 바람직하다. 광산발생제가 0.05중량% 이하의 양으로 사용될 때에는 포토레지스트의 광에 대한 민감도가 취약하게 되고 10중량% 이상 사용될 때에는 광산발생제가 원자외선을 많이 흡수하고 산이 다량 발생되어 단면이 좋지 않은 패턴을 얻게 된다.The photoacid generator is preferably used in a proportion of 0.05 to 10% by weight based on the photoresist polymer. When the photoacid generator is used in an amount of 0.05% by weight or less, the photosensitive sensitivity of the photoresist becomes weak. When the photoacid generator is used in an amount of 10% by weight or more, the photoacid generator absorbs a lot of ultraviolet rays and generates a large amount of acid, thereby obtaining a pattern having a bad cross section. .
또한, 상기 유기용매로는 포토레지스트 조성물에 통상적으로 사용되는 유기용매는 무엇이든 사용가능하며, 역시 상기 문헌에 개시된 것을 포함하고, 바람직하게는 사이클로헥사논, 사이클로펜타논, 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트, 프로필렌글리콜 메틸에테르아세테이트, 2-헵타논 또는 에틸락테이트를 사용하며, 상기 포토레지스트 중합체에 대해 500 내지 2000중량% 비율로 사용되는데, 이는 원하는 두께의 포토레지스트 막을 얻기 위한 것으로 예를 들면, 포토레지스트 중합체에 대해 유기용매가 800중량% 사용될 때의 포토레지스트 두께는약 0.3㎛가 된다.In addition, the organic solvent may be any organic solvent commonly used in the photoresist composition, and also includes those disclosed in the above document, and preferably cyclohexanone, cyclopentanone, methyl 3-methoxyprop Cypionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, 2-heptanone or ethyl lactate are used and are used at a ratio of 500 to 2000% by weight, based on the desired thickness of the photoresist polymer. For obtaining a photoresist film, for example, when the organic solvent is used in an amount of 800% by weight based on the photoresist polymer, the photoresist thickness is about 0.3 mu m.
본 발명에서는 또한 하기와 같은 단계를 포함하는 포토레지스트 패턴 형성방법을 제공한다:The present invention also provides a method of forming a photoresist pattern comprising the following steps:
(a) 상기 본 발명에 따른 포토레지스트 조성물을 피식각층 상부에 코팅하여 포토레지스트 막을 형성하는 단계;(a) coating the photoresist composition according to the present invention on the etched layer to form a photoresist film;
(b) 상기 포토레지스트 막을 노광하는 단계; 및(b) exposing the photoresist film; And
(c) 상기 노광된 포토레지스트 막을 현상하여 포토레지스트 패턴을 얻는 단계.(c) developing the exposed photoresist film to obtain a photoresist pattern.
상기 과정에서 (b)단계의 노광전에 소프트 베이크 공정, 또는 (b)단계의 노광후에 포스트 베이크 공정을 실시하는 단계를 더 포함할 수 있으며, 이 베이크 공정은 70 내지 200℃에서 수행되는 것이 바람직하다.The process may further include a soft bake process before the exposure of step (b), or a post bake process after the exposure of step (b), which is preferably carried out at 70 to 200 ℃. .
또한, 상기 노광공정은 광원으로서 ArF(193nm), KrF(248nm), VUV(157nm), EUV(13nm), E-빔 또는 X-레이 광원을 사용하여, 1 내지 100 mJ/cm2의 노광에너지로 수행되는 것이 바람직하다.In addition, the exposure process using an ArF (193 nm), KrF (248 nm), VUV (157 nm), EUV (13 nm), E-beam or X-ray light source, exposure energy of 1 to 100 mJ / cm 2 Is preferably carried out.
한편, 상기에서 현상 단계 (c)는 알칼리 현상액을 이용하여 수행될 수 있으며, 알칼리 현상액은 0.01 내지 5중량%의 테트라메틸암모늄하이드록사이드(TMAH) 수용액인 것이 바람직하다.On the other hand, the developing step (c) in the above may be carried out using an alkaline developer, the alkaline developer is preferably 0.01 to 5% by weight of tetramethylammonium hydroxide (TMAH) aqueous solution.
이상에서 설명한 조성으로 이루어진 본 발명의 포토레지스트를 이용하여 포토레지스트막을 형성하게 되면 포토레지스트막이 비노광부위에서는 녹고, 노광부위에서는 수산기를 가지는 단량체인 상기 화학식 2의 노폴과 에폭시기를 가지는 단량체인 상기 화학식 5 또는 에폭시기를 가지는 가교제와의 가교가 일어나게 되어 포토레지스트막이 현상액에 녹지 않게 됨으로써 네가티브 패턴이 얻어진다.When the photoresist film is formed using the photoresist of the present invention having the composition described above, the photoresist film is a monomer having a nopol and an epoxy group of the above formula (2), which is a monomer having a hydroxyl group at a non-exposed site and a hydroxyl group at an exposed site. The crosslinking with the crosslinking agent which has 5 or an epoxy group arises, and a photoresist film does not melt | dissolve in a developing solution, and a negative pattern is obtained.
본 발명에서는 또한 상기 본 발명의 포토레지스트 조성물을 이용하여 제조된 반도체 소자를 제공한다.The present invention also provides a semiconductor device manufactured using the photoresist composition of the present invention.
이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.
I. 포토레지스트 중합체의 제조I. Preparation of Photoresist Polymer
실시예 1.Example 1.
노폴(0.1mole), 노르보닐렌(0.05mole), 말레익 안하이드라이드(0.15mole), 글리시딜 메타크릴레이트(0.01mole) 및 AIBN(0.4g)을 테트라하이드로퓨란 15ml에 녹인 후, 55℃에서 10시간 반응시켰다. 반응 후 혼합물을 디에틸에테르에 떨어뜨려 폴리머를 침전시키고, 이를 여과 건조시켜 원하는 생성물을 얻었다(수율 : 53%).Nopol (0.1 mole), norbornylene (0.05 mole), maleic anhydride (0.15 mole), glycidyl methacrylate (0.01 mole) and AIBN (0.4 g) were dissolved in 15 ml of tetrahydrofuran, and 55 It was made to react at 10 degreeC. After the reaction, the mixture was dropped in diethyl ether to precipitate a polymer, which was filtered and dried to obtain a desired product (yield: 53%).
실시예 2.Example 2.
노폴(0.1mole), 노르보닐렌(0.1mole), 말레익 안하이드라이드(0.2mole) 및 AIBN(0.4g)을 테트라하이드로퓨란 15ml에 녹인 후, 55℃에서 10시간 반응시켰다. 반응 후 혼합물을 디에틸에테르에 떨어뜨려 폴리머를 침전시키고, 이를 여과 건조시켜 원하는 생성물을 얻었다(수율 : 62%).Nopol (0.1 mole), norbornylene (0.1 mole), maleic anhydride (0.2 mole) and AIBN (0.4 g) were dissolved in 15 ml of tetrahydrofuran and reacted at 55 ° C for 10 hours. After the reaction, the mixture was dropped in diethyl ether to precipitate a polymer, which was filtered and dried to obtain a desired product (yield: 62%).
실시예 3.Example 3.
상기 실시예 1 및 실시예 2로부터 제조된 포토레지스트 중합체를 각각 0.1g씩 취하여 10㎖의 2.38중량% TMAH 수용액에 녹여 본 결과 이들 포토레지스트 중합체가 1분 이내로 깨끗이 녹았다.0.1 g of each of the photoresist polymers prepared in Examples 1 and 2 was taken and dissolved in 10 ml of a 2.38 wt% TMAH aqueous solution, and these photoresist polymers were dissolved in less than 1 minute.
II. 포토레지스트 조성물의 제조 및 패턴 형성II. Preparation and Pattern Formation of Photoresist Composition
실시예 4 : 포토레지스트 조성물의 제조 및 포토레지스트 패턴 형성(1)Example 4 Preparation of Photoresist Composition and Formation of Photoresist Pattern (1)
실시예 1에서 얻은 포토레지스트 중합체 5g, 광산 발생제인 트리페닐설포늄 트리플레이트 0.05g을 유기용매인 프로필렌글라이콜메틸에테르아세테이트(PGMEA) 40g에 녹인 후 0.10㎛ 필터로 여과시켜 포토레지스트 조성물을 얻었다.5 g of the photoresist polymer obtained in Example 1 and 0.05 g of triphenylsulfonium triflate as a photoacid generator were dissolved in 40 g of propylene glycol methyl ether acetate (PGMEA) as an organic solvent, and then filtered through a 0.10 μm filter to obtain a photoresist composition. .
이 포토레지스트 조성물을 실리콘 웨이퍼 위에 스핀 코팅한 후 110℃ 에서 90초간 소프트 베이크 하였다. 베이크 후 ArF 레이저 노광장비를 이용하여 0.1-40mJ/㎠의 범위에서 0.2mJ/㎠의 간격으로 노광량을 늘려가며 노광에너지를 조사한 후, 110℃에서 90초간 다시 포스트 베이크 하였다. 포스트 베이크 완료후 2.38중량% TMAH 수용액에 40초간 현상한 결과, 0.11㎛의 L/S 패턴이 얻어졌다 (도 1 참조).The photoresist composition was spin coated on a silicon wafer and then soft baked at 110 ° C. for 90 seconds. After baking, the exposure energy was increased by increasing the exposure dose at intervals of 0.2 mJ / cm 2 in the range of 0.1-40 mJ / cm 2 using an ArF laser exposure equipment, and then post-baking was again performed at 110 ° C. for 90 seconds. After completion of the post-baking, development was carried out in a 2.38% by weight TMAH aqueous solution for 40 seconds to give a L / S pattern of 0.11 mu m (see FIG. 1).
실시예 5 : 포토레지스트 조성물의 제조 및 포토레지스트 패턴 형성(2)Example 5 Preparation of Photoresist Composition and Formation of Photoresist Pattern (2)
실시예 2에서 얻은 포토레지스트 중합체 5g, 광산 발생제인 트리페닐설포늄 트리플레이트 0.05g, 가교제로서 글리세롤 프로폭실레이트 트리글리시딜 에테르를 유기용매인 프로필렌글라이콜메틸에테르아세테이트(PGMEA) 40g에 녹인 후 0.10㎛ 필터로 여과시켜 포토레지스트 조성물을 얻었다.5 g of the photoresist polymer obtained in Example 2, 0.05 g of triphenylsulfonium triflate as a photoacid generator, and glycerol propoxylate triglycidyl ether as a crosslinking agent were dissolved in 40 g of propylene glycol methyl ether acetate (PGMEA) as an organic solvent. Filtration with a 0.10 μm filter gave a photoresist composition.
이 포토레지스트 조성물을 실리콘 웨이퍼 위에 스핀 코팅한 후 110℃ 에서 90초간 소프트 베이크 하였다. 베이크 후 ArF 레이저 노광장비를 이용하여 0.1-40mJ/㎠의 범위에서 0.2mJ/㎠의 간격으로 노광량을 늘려가며 노광에너지를 조사한 후, 110℃에서 90초간 다시 포스트 베이크 하였다. 포스트 베이크 완료후 2.38중량% TMAH 수용액에 40초간 현상한 결과, 0.11㎛의 L/S 패턴이 얻어졌다 (도 2 참조).The photoresist composition was spin coated on a silicon wafer and then soft baked at 110 ° C. for 90 seconds. After baking, the exposure energy was increased by increasing the exposure dose at intervals of 0.2 mJ / cm 2 in the range of 0.1-40 mJ / cm 2 using an ArF laser exposure equipment, and then post-baking was again performed at 110 ° C. for 90 seconds. After completion of the post-baking, development was carried out in a 2.38% by weight TMAH aqueous solution for 40 seconds to give an L / S pattern of 0.11 mu m (see FIG. 2).
이상에서 살펴본 바와 같이, 본 발명의 포토레지스트 조성물을 이용하면 기존의 사이클로올레핀-말레익안하이드라이드 타입의 포토레지스트에 수산기를 가지는 단량체인 노폴을 도입함으로써, 노광부위는 광산발생제에 의해 에폭시기를 가지는 단량체 또는 가교제와의 가교가 일어나게 되어 포토레지스트가 현상액에 녹지 않고, 비노광부위는 녹게 됨으로써 네가티브 패턴을 얻을 수 있다. 또한 강한 에칭내성과 가교로 인한 부가적인 내성 강화 현상을 부여하며 노광부위와 비노광부위 사이의 대조비를 증가시키기 때문에 단층 레지스트 공정에 사용할 수 있다.As described above, using the photoresist composition of the present invention, by introducing a novol, which is a monomer having a hydroxyl group, in an existing cycloolefin-maleic hydride type photoresist, an exposure site has an epoxy group by a photoacid generator. The crosslinking with the monomer or the crosslinking agent occurs, the photoresist is not dissolved in the developer, and the non-exposed portion is melted to obtain a negative pattern. In addition, it can be used in single layer resist process because it gives strong resistance to etching and strengthens additional resistance due to crosslinking and increases the contrast ratio between exposed and non-exposed areas.
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