KR20060066932A - Photoresist polymer and photoresist composition containing the same - Google Patents

Photoresist polymer and photoresist composition containing the same Download PDF

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KR20060066932A
KR20060066932A KR1020040105478A KR20040105478A KR20060066932A KR 20060066932 A KR20060066932 A KR 20060066932A KR 1020040105478 A KR1020040105478 A KR 1020040105478A KR 20040105478 A KR20040105478 A KR 20040105478A KR 20060066932 A KR20060066932 A KR 20060066932A
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photoresist
formula
polymer
mol
photoresist composition
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이근수
복철규
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주식회사 하이닉스반도체
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • 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
    • C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • 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
    • G03F7/038—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
    • 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
    • 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

Abstract

본 발명은 포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물에 관한 것으로, 하기 화학식 1로 표시되는 반복 단위를 포함하는 포토레지스트 중합체를 함유하는 본 발명의 포토레지스트 조성물을 이용하면 내구성, 에칭내성이 뛰어나고 LER이 개선된 포토레지스트 패턴을 형성할 수 있으며, 1G 이하의 디램(DRAM)은 물론, 4G, 16G 디램 이상의 초미세 패턴 형성에 사용 가능하다. 또한 본 발명의 포토레지스트 중합체는 193nm 및 248nm 파장에서의 광흡수도가 낮아 고집적 반도체 소자의 미세회로를 제조할 때 원자외선 영역의 광원을 이용한 포토리소그래피 공정에 매우 유용하게 사용될 수 있다.The present invention relates to a photoresist polymer and a photoresist composition containing the same, and using the photoresist composition of the present invention containing a photoresist polymer comprising a repeating unit represented by the following formula (1), excellent durability, etching resistance and LER This improved photoresist pattern can be formed, and can be used for forming ultra fine patterns of 4G and 16G DRAMs as well as DRAMs of 1G or less. In addition, the photoresist polymer of the present invention has low light absorption at wavelengths of 193 nm and 248 nm, and thus may be very useful for a photolithography process using a light source in the far ultraviolet region when manufacturing a microcircuit of a highly integrated semiconductor device.

[화학식 1][Formula 1]

Figure 112004058882841-PAT00001
Figure 112004058882841-PAT00001

상기 식에서, R은 H, CH3 또는 CF3이고; m : n의 상대비는 1∼99몰% : 1∼99몰%이며; 분자량은 2000∼20000이다.In which R is H, CH 3 or CF 3 ; the relative ratio of m: n is 1-99 mol%: 1-99 mol%; The molecular weight is 2000-20000.

Description

포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물{Photoresist Polymer and Photoresist Composition Containing the Same}Photoresist polymer and photoresist composition containing the same {Photoresist Polymer and Photoresist Composition Containing the Same}

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.

본 발명은 포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물에 관한 것으로, 더욱 상세하게는 248㎚ 및 193㎚ 파장에서의 광흡수도가 낮아 고집적 반도체 소자의 미세회로를 제조할 때 원자외선 영역의 광원을 이용한 포토리소그래피 공정에 매우 유용하게 사용될 수 있는 포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물에 관한 것이다.The present invention relates to a photoresist polymer and a photoresist composition containing the same. More specifically, the light absorption in the wavelengths of 248 nm and 193 nm is low. It relates to a photoresist polymer and a photoresist composition containing the same which can be very usefully used in the photolithography process.

ArF용 포토레지스트로 이용되기 위해서는 193㎚ 파장에서 광 흡수도가 낮아야 하고, 에칭내성과 기판에 대한 접착성이 우수하여야 하며, 2.38wt% 및 2.6wt% 테트라메틸암모늄하이드록사이드(TMAH) 수용액으로 현상이 가능해야 하는 등의 많은 요건을 충족시켜야 한다.In order to be used as a photoresist for ArF, the light absorption at the wavelength of 193nm should be low, the etching resistance and the adhesion to the substrate should be excellent, and the solution of 2.38wt% and 2.6wt% tetramethylammonium hydroxide (TMAH) Many requirements must be met, such as a phenomenon that must be possible.

현재까지의 주된 연구방향은 248㎚ 및 193㎚에서 높은 투명성이 있으며, 에 칭내성이 노볼락 수지와 같은 수준의 수지를 탐색하는 것이었다. 현재 반도체 소자의 회로가 점점 미세화되고 요구되는 포토레지스트의 두께가 낮아짐에 따라 라인 가장자리 거칠음 (Line Edge Roughness : 이하, 'LER'이라 약칭함)이 큰 문제로 대두되고 있다. 그러나 대부분의 ArF 포토레지스트들은 기존의 KrF나 I-라인 포토레지스트에 비해 LER이 더 심한 경향을 보이는 문제점이 있다.The main research direction to date has been to search for resins having high transparency at 248 nm and 193 nm, and etching resistance at the same level as the novolak resin. As the circuits of semiconductor devices become more miniaturized and the required thickness of the photoresist decreases, line edge roughness (hereinafter, abbreviated as "LER") is a big problem. However, most ArF photoresists have a problem that LER tends to be more severe than conventional KrF or I-line photoresists.

본 발명의 목적은 248㎚ 및 193㎚ 파장에서의 광흡수도가 낮아 고집적 반도체 소자의 미세회로를 제조할 때 원자외선 영역의 광원을 이용한 포토리소그래피 공정에 매우 유용하게 사용될 수 있는 신규의 포토레지스트 중합체 및 이를 함유하는 포토레지스트 조성물을 제공하는 것이다.An object of the present invention is a novel photoresist polymer which can be very useful for photolithography process using a light source in the far ultraviolet region when manufacturing microcircuits of highly integrated semiconductor devices with low light absorption at wavelengths of 248 nm and 193 nm. And to provide a photoresist composition containing the same.

또한 본 발명의 목적은 상기 포토레지스트 조성물을 이용하여 포토레지스트 패턴을 형성하는 방법 및 이러한 방법에 의해 얻어지는 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 such a method.

상기 목적을 달성하기 위하여 본 발명에서는 하기 화학식 1의 반복 단위를 포함하는 신규의 포토레지스트 중합체를 제공한다 : In order to achieve the above object, the present invention provides a novel photoresist polymer comprising a repeating unit represented by Formula 1 below:                     

[화학식 1][Formula 1]

Figure 112004058882841-PAT00002
Figure 112004058882841-PAT00002

상기 식에서, R은 H, CH3 또는 CF3이고; m : n의 상대비는 1∼99몰% : 1∼99몰%이며; 분자량은 2000∼20000이다.In which R is H, CH 3 or CF 3 ; the relative ratio of m: n is 1-99 mol%: 1-99 mol%; The molecular weight is 2000-20000.

상기 화학식 1의 반복 단위를 포함하는 본 발명의 포토레지스트 중합체는 용해억제형 포지티브 중합체이다.The photoresist polymer of the present invention comprising the repeating unit of Formula 1 is a dissolution inhibiting positive polymer.

상기 화학식 1의 반복 단위는 하기 화학식 1a 또는 1b로 표시되는 것이 바람직하다 : The repeating unit of Formula 1 is preferably represented by the following Formula 1a or 1b:                     

[화학식 1a][Formula 1a]

Figure 112004058882841-PAT00003
Figure 112004058882841-PAT00003

[화학식 1b][Formula 1b]

Figure 112004058882841-PAT00004
.
Figure 112004058882841-PAT00004
.

상기 식에서, m : n의 상대비는 1∼99몰% : 1∼99몰%이고; 분자량은 2000∼20000이다.Wherein the relative ratio of m: n is 1-99 mol%: 1-99 mol%; The molecular weight is 2000-20000.

본 발명에 따른 포토레지스트 중합체를 구성하는 상기 화학식 1의 반복 단위를 제조하는 방법은 다음의 단계를 포함한다 :The method for preparing a repeating unit of formula 1 constituting the photoresist polymer according to the present invention includes the following steps:

하기 화학식 2의 4-(1-프로페닐옥시메틸)-1,3-디옥소란-2-온과 하기 화학식 3의 1,2:5,6-디-o-사이클로헥실리덴-α-D-글루코퓨라노스 유도체를 중합 유기용매 에 녹이는 단계; 및4- (1-propenyloxymethyl) -1,3-dioxolan-2-one of Formula 2 and 1,2: 5,6-di-o-cyclohexylidene-α- of Formula 3 Dissolving the D-glucofuranose derivative in a polymerization organic solvent; And

상기 결과물 용액에 중합 개시제를 첨가하여 중합반응 시키는 단계.Adding a polymerization initiator to the resultant solution to perform a polymerization reaction.

[화학식 2][Formula 2]

Figure 112004058882841-PAT00005
Figure 112004058882841-PAT00005

[화학식 3][Formula 3]

Figure 112004058882841-PAT00006
Figure 112004058882841-PAT00006

상기 식에서, R은 H, CH3 또는 CF3이다.Wherein R is H, CH 3 or CF 3 .

상기 중합 유기용매로는 사이클로헥사논, 테트라하이드로퓨란, 디메틸포름아미드, 디메틸설폭사이드, 디옥산, 메틸에틸케톤, 벤젠, 톨루엔 및 자일렌으로 이루어진 군으로부터 선택된 단독용매 또는 혼합용매를 사용하는 것이 바람직하고, 상기 중합 개시제로는 벤조일퍼옥사이드, 2,2'-아조비스이소부티로니트릴(AIBN), 아세틸퍼옥사이드, 라우릴퍼옥사이드, t-부틸퍼아세테이트, t-부틸하이드로퍼옥사이 드 및 디-t-부틸퍼옥사이드로 이루어진 군으로부터 선택된 것을 사용하는 것이 바람직하다.It is preferable to use a single solvent or a mixed solvent selected from the group consisting of cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, benzene, toluene and xylene as the polymerization organic solvent. As the polymerization initiator, benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butyl peracetate, t-butyl hydroperoxide and di Preference is given to using those selected from the group consisting of -t-butylperoxide.

본 발명에서는 또한 상기 본 발명의 포토레지스트 중합체, 광산발생제 및 유기용매를 포함하는 포토레지스트 조성물을 제공한다.The present invention also provides a photoresist composition comprising the photoresist polymer of the present invention, a photoacid generator and an organic solvent.

상기 광산발생제로는 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 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 황화염계 또는 오니움염계 화합물을 사용한다.As the photoacid 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 6,132,926 (October 17, 2000), US 6,143,463 (7 November 2000), US 6,150,069 (Nov. 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 (2001. 5. 22) and the like, and mainly use sulfide-based or onium salt-based compounds.

바람직하게는 프탈이미도트리플루오로메탄술포네이트, 디니트로벤질토실레이트, n-데실디술폰, 나프틸이미도트리플루오로메탄술포네이트, 디페닐요도염 헥사플루오로포스페이트, 디페닐요도염 헥사플루오로 아르세네이트, 디페닐요도염 헥사플루오로 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오로 아르세네이트, 트리페닐설포늄 헥사플루오로 안티모네이트, 트리페닐설포늄 트리플레이트 또는 디부틸나프틸설포늄 트리플레이트를 하나 또는 둘 이상 포함하여 사용할 수 있으며, 상기 포토레지스트 중합체 대해 0.05 내지 10 중량% 비율로 사용되는 것이 바람직하다. 광산발생제가 0.05 중량% 이하의 양으로 사용될 때에는 포토 레지스트의 광에 대한 민감도가 취약하게 되고 10 중량% 이상 사용될 때에는 광산발생제가 원자외선을 많이 흡수하고 산이 다량 발생되어 단면이 좋지 않은 패턴을 얻게 된다.Preferred phthalimidotrifluoromethanesulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethanesulfonate, diphenylidodoxyl hexafluorophosphate, diphenylurodoxyl hexafluoro arse Acetate, diphenylurodoxyl hexafluoro antimonate, diphenylparamethoxyphenyl triflate, diphenylparatoluenyl triflate, diphenylparaisobutylphenyl triflate, triphenylsulfonium hexafluoro arsenate, Triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate or dibutylnaphthylsulfonium triflate may be used, including one or more, and used in a proportion of 0.05 to 10% by weight relative to the photoresist polymer. It is preferable. When the photoacid generator is used in an amount of 0.05% by weight or less, the sensitivity of the photoresist to light is weak. When the photoacid generator is used at 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 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트, 프로필렌글리콜 메틸에테르아세테이트, 사이클로헥사논, 2-헵타논 또는 에틸락테이트를 사용한다. 상기 유기용매는 포토레지스트 중합체에 대해 500 내지 2000 중량% 비율로 사용되는데, 이는 원하는 두께의 포토레지스트 막을 얻기 위한 것으로 예를 들면, 포토레지스트 중합체에 대해 유기용매가 1000 중량% 사용될 때의 포토레지스트 두께는 약 0.25㎛가 된다.In addition, as the organic solvent, any organic solvent conventionally used in the photoresist composition may be used, and also includes those disclosed in the above literature, preferably methyl 3-methoxypropionate, ethyl 3-ethoxy Propionate, propylene glycol methyl ether acetate, cyclohexanone, 2-heptanone or ethyl lactate are used. The organic solvent is used at a ratio of 500 to 2000% by weight based on the photoresist polymer, which is used to obtain a photoresist film having a desired thickness, for example, the photoresist thickness when the organic solvent is used by 1000% by weight based on the photoresist polymer. Becomes about 0.25 탆.

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 발명의 포토레지스트 조성물을 피식각층 상부에 코팅하여 포토레지스트 막을 형성하는 단계;(a) coating the photoresist composition of 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 노광 전에 소프트 베이크 공정, 및/또는 (b) 단계의 노광 후에 포스트 베이크 공정을 실시하는 단계를 더 포함할 수 있으며, 이 베 이크 공정은 70 내지 200℃에서 수행되는 것이 바람직하다.The process may further comprise the step of performing a soft bake process before the exposure of step (b), and / or post-bake process after the exposure of step (b), the bake process is carried out at 70 to 200 ℃ It is preferable.

또한, 상기 노광공정은 광원으로서 VUV(vacuum ultraviolet; 157㎚), ArF(193㎚), KrF(248㎚), I-line, E-빔, EUV(extreme ultraviolet) 또는 이온빔을 사용하여, 0.1 내지 100 mJ/cm2의 노광에너지로 수행되는 것이 바람직하다.In addition, the exposure process is performed by using a UV ultraviolet (VUV) (157 nm), ArF (193 nm), KrF (248 nm), I-line, E-beam, EUV (extreme ultraviolet) or ion beam as a light source. It is preferably carried out with an exposure energy of 100 mJ / cm 2 .

한편, 상기에서 현상 단계 (c)는 알칼리 현상액을 이용하여 수행될 수 있으며, 알칼리 현상액은 0.01 내지 5 중량%의 TMAH 수용액인 것이 바람직하다.On the other hand, the developing step (c) in the above may be performed using an alkaline developer, the alkali developer is preferably 0.01 to 5% by weight of TMAH aqueous solution.

전술한 바와 같이, 본 발명의 포토레지스트 중합체는 용해억제형 포지티브 중합체로서, 노광공정시 노광에 의해 포토레지스트 중합체가 빛에 노출되면 화학반응을 거쳐 현상액에 잘 녹는 화합물로 변하기 때문에 빛을 받은 노광영역은 현상액에 녹고, 빛을 받지 않은 비노광영역에는 포토레지스트 중합체가 그대로 존재하기 때문에 현상액에 녹지 않아 패턴으로 남게 된다.As described above, the photoresist polymer of the present invention is a dissolution inhibiting positive polymer, and is exposed to light because the photoresist polymer is exposed to light by exposure during the exposure process, so that the photoresist polymer is converted into a compound that is well soluble in a developing solution through chemical reaction. The silver melts in the developer and remains unpatterned in the developer because the photoresist polymer is present in the non-exposed areas that do not receive light.

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.

실시예 1. 화학식 1a의 화합물의 제조Example 1 Preparation of a Compound of Formula 1a

1,2:5,6-디-o-사이클로헥실리덴-α-D-글루코퓨라노스 메타크릴레이트(0.05M)과 4-(1-프로페닐옥시메틸)-1,3-디옥소란-2-온(0.05M)과 2,2'-아조비스이소부티로니트릴(AIBN) 0.1g을 테트라하이드로퓨란 20mL에 녹인 후 60℃에서 12시간 반응시 킨다. 반응 후 혼합물을 헥산에 떨어뜨려 상기 화학식 1a의 화합물을 54%의 수율로 얻었다.1,2: 5,6-di-o-cyclohexylidene-α-D-glucofuranos methacrylate (0.05M) and 4- (1-propenyloxymethyl) -1,3-dioxolane After dissolving 2-one (0.05 M) and 0.1 g of 2,2'-azobisisobutyronitrile (AIBN) in 20 mL of tetrahydrofuran, the mixture was reacted at 60 ° C. for 12 hours. After the reaction, the mixture was dropped in hexane to obtain the compound of Formula 1a in a yield of 54%.

실시예 2. 화학식 1b의 화합물의 제조Example 2. Preparation of Compound of Formula 1b

1,2:5,6-디-o-사이클로헥실리덴-α-D-글루코퓨라노스 아크릴레이트(0.05M)과 4-(1-프로페닐옥시메틸)-1,3-디옥소란-2-온(0.05M)과 2,2'-아조비스이소부티로니트릴(AIBN) 0.1g을 테트라하이드로퓨란 20mL에 녹인 후 60℃에서 12시간 반응시킨다. 반응 후 혼합물을 헥산에 떨어뜨려 상기 화학식 1b의 화합물을 56%의 수율로 얻었다.1,2: 5,6-di-o-cyclohexylidene-α-D-glucofuranose acrylate (0.05M) and 4- (1-propenyloxymethyl) -1,3-dioxolane- After dissolving 2-one (0.05M) and 0.1 g of 2,2'-azobisisobutyronitrile (AIBN) in 20 mL of tetrahydrofuran, the mixture was reacted at 60 ° C for 12 hours. After the reaction, the mixture was dropped in hexane to obtain the compound of Formula 1b in 56% yield.

실시예 3. 포토레지스트 조성물의 제조 및 포토레지스트 패턴 형성 (1)Example 3 Preparation of Photoresist Composition and Formation of Photoresist Pattern (1)

상기 실시예 1에서 얻은 포토레지스트 중합체인 화학식 1a이 화합물 2g, 광산발생제인 프탈이미도트리플루오로메탄술포네이트 0.24g 및 트리페닐설포늄 트리플레이트 0.06g을 유기용매인 프로필렌글리콜 메틸에테르아세테이트(PGMEA) 20g에 녹인 후 0.20 ㎛ 필터로 여과하여 포토레지스트 조성물을 얻었다.Formula 1a, a photoresist polymer obtained in Example 1, is a compound of 2g, a photoacid generator, phthalimidotrifluoromethanesulfonate, 0.24g, and 0.06g of triphenylsulfonium triflate, as an organic solvent, propylene glycol methyl ether acetate (PGMEA). It was dissolved in 20g and filtered through a 0.20 ㎛ filter to obtain a photoresist composition.

다음, 상기 포토레지스트 조성물을 실리콘 웨이퍼 위에 스핀 코팅한 후 130 ℃에서 90 초간 베이크 하였다. 베이크 후, ArF 레이저 노광장비를 이용하여 노광 후 130℃에서 90 초간 다시 베이크 하였다. 베이크 완료 후, 2.38 중량% 테트라메틸암모늄하이드록사이드 수용액에 40 초간 현상 후 0.07 ㎛의 라인/스페이스 패턴을 얻었다 (도 1 참조). Next, the photoresist composition was spin coated on a silicon wafer and then baked at 130 ° C. for 90 seconds. After baking, the wafer was baked again at 130 ° C. for 90 seconds using an ArF laser exposure apparatus. After baking was completed, a line / space pattern of 0.07 μm was obtained after developing in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 40 seconds (see FIG. 1).

실시예 4. 포토레지스트 조성물의 제조 및 포토레지스트 패턴 형성 (2)Example 4 Preparation of Photoresist Composition and Forming Photoresist Pattern (2)

상기 실시예 2에서 얻은 포토레지스트 중합체인 화학식 1b의 화합물 2g, 광 산발생제인 프탈이미도트리플루오로메탄술포네이트 0.24g 및 트리페닐설포늄 트리플레이트 0.06g을 유기용매인 프로필렌글리콜 메틸에테르아세테이트(PGMEA) 20g에 녹인 후 0.20 ㎛ 필터로 여과하여 포토레지스트 조성물을 얻었다.2 g of the compound of Formula 1b, a photoresist polymer obtained in Example 2, 0.24 g of phthalimidotrifluoromethanesulfonate as a photoacid generator, and 0.06 g of triphenylsulfonium triflate were used as an organic solvent, propylene glycol methyl ether acetate (PGMEA). ) 20g, and filtered through a 0.20 ㎛ filter to obtain a photoresist composition.

다음, 상기 포토레지스트 조성물을 실리콘 웨이퍼 위에 스핀 코팅한 후 100 ℃에서 90 초간 베이크 하였다. 베이크 후, ArF 레이저 노광장비를 이용하여 노광 후 100℃에서 90 초간 다시 베이크 하였다. 베이크 완료 후, 2.38 중량% 테트라메틸암모늄하이드록사이드 수용액에 40 초간 현상 후 0.07 ㎛의 라인/스페이스 패턴을 얻었다 (도 2 참조). Next, the photoresist composition was spin coated on a silicon wafer and then baked at 100 ° C. for 90 seconds. After baking, the wafer was baked again at 100 ° C. for 90 seconds using an ArF laser exposure apparatus. After baking was completed, a line / space pattern of 0.07 μm was obtained after developing in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 40 seconds (see FIG. 2).

이상에서 설명한 바와 같이, 본 발명의 포토레지스트 조성물을 이용하면 내구성, 에칭내성이 뛰어나고 LER이 개선된 포토레지스트 패턴을 형성할 수 있으며 1G 이하의 디램(DRAM)은 물론, 4G, 16G 디램 이상의 초미세 패턴 형성에 사용할 수 있다. 또한, 본 발명의 포토레지스트 중합체는 193nm 및 248nm 파장에서의 광흡수도가 낮아 고집적 반도체 소자의 미세회로를 제조할 때 원자외선 영역의 광원을 이용한 포토리소그래피 공정에 매우 유용하게 사용될 수 있다.As described above, by using the photoresist composition of the present invention, it is possible to form a photoresist pattern with excellent durability and etching resistance and improved LER, and ultra fine 4G and 16G DRAMs as well as DRAMs of 1G or less. Can be used for pattern formation. In addition, the photoresist polymer of the present invention has low light absorption at wavelengths of 193 nm and 248 nm, and thus may be very useful for a photolithography process using a light source in the far ultraviolet region when manufacturing a microcircuit of a highly integrated semiconductor device.

Claims (17)

하기 화학식 1의 반복 단위를 포함하는 것을 특징으로 하는 포토레지스트 중합체 :A photoresist polymer comprising the repeating unit of Formula 1 below: [화학식 1][Formula 1]
Figure 112004058882841-PAT00007
Figure 112004058882841-PAT00007
 상기 식에서, R은 H, CH3 또는 CF3이고; m : n의 상대비는 1∼99몰% : 1∼99몰%이며; 분자량은 2000∼20000이다.In which R is H, CH 3 or CF 3 ; the relative ratio of m: n is 1-99 mol%: 1-99 mol%; The molecular weight is 2000-20000. 제 1 항에 있어서,The method of claim 1, 상기 화학식 1의 반복 단위는 하기 화학식 1a 또는 1b로 표시되는 것을 특징으로 하는 포토레지스트 중합체 :The repeating unit of Formula 1 is a photoresist polymer, characterized in that represented by the formula 1a or 1b: [화학식 1a][Formula 1a]
Figure 112004058882841-PAT00008
Figure 112004058882841-PAT00008
 [화학식 1b][Formula 1b]
Figure 112004058882841-PAT00009
.
Figure 112004058882841-PAT00009
. 상기 식에서, m : n의 상대비는 1∼99몰% : 1∼99몰%이고; 분자량은 2000∼20000이다.Wherein the relative ratio of m: n is 1-99 mol%: 1-99 mol%; The molecular weight is 2000-20000. 하기 화학식 2의 4-(1-프로페닐옥시메틸)-1,3-디옥소란-2-온과 하기 화학식 3의 1,2:5,6-디-o-사이클로헥실리덴-α-D-글루코퓨라노스 유도체를 중합 유기용매에 녹이는 단계와,4- (1-propenyloxymethyl) -1,3-dioxolan-2-one of Formula 2 and 1,2: 5,6-di-o-cyclohexylidene-α- of Formula 3 Dissolving the D-glucofuranose derivative in a polymerization organic solvent, 상기 결과물 용액에 중합개시제를 첨가하여 중합반응 시키는 단계를 포함하는 것을 특징으로 하는 하기 화학식 1의 반복 단위를 포함하는 포토레지스트 중합체의 제조방법 :Method for producing a photoresist polymer comprising a repeating unit of the formula (1) characterized in that it comprises the step of polymerization by adding a polymerization initiator to the resulting solution: [화학식 1][Formula 1]
Figure 112004058882841-PAT00010
Figure 112004058882841-PAT00010
 [화학식 2][Formula 2]
Figure 112004058882841-PAT00011
Figure 112004058882841-PAT00011
 [화학식 3][Formula 3]
Figure 112004058882841-PAT00012
Figure 112004058882841-PAT00012
 상기 식에서, R은 H, CH3 또는 CF3이고; m : n의 상대비는 1∼99몰% : 1∼99몰%이며; 분자량은 2000∼20000이다.In which R is H, CH 3 or CF 3 ; the relative ratio of m: n is 1-99 mol%: 1-99 mol%; The molecular weight is 2000-20000. 제 3 항에 있어서,The method of claim 3, wherein 상기 중합 유기용매는 사이클로헥사논, 테트라하이드로퓨란, 디메틸포름아미드, 디메틸설폭사이드, 디옥산, 메틸에틸케톤, 벤젠, 톨루엔 및 자일렌으로 이루어진 군으로부터 선택된 단독용매 또는 혼합용매인 것을 특징으로 하는 포토레지스트 중합체의 제조방법.The polymerized organic solvent may be a single solvent or a mixed solvent selected from the group consisting of cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, benzene, toluene and xylene. Method for producing a resist polymer. 제 3 항에 있어서,The method of claim 3, wherein 상기 중합 개시제는 벤조일퍼옥사이드, 2,2'-아조비스이소부티로니트릴 (AIBN), 아세틸퍼옥사이드, 라우릴퍼옥사이드, t-부틸퍼아세테이트, t-부틸하이드로퍼옥사이드 및 디-t-부틸퍼옥사이드로 이루어진 군으로부터 선택된 것을 특징으로 하는 포토레지스트 중합체의 제조방법.The polymerization initiators are benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), acetyl peroxide, lauryl peroxide, t-butyl peracetate, t-butyl hydroperoxide and di-t-butyl A method for producing a photoresist polymer, characterized in that selected from the group consisting of peroxides. 제 1 항 기재의 포토레지스트 중합체, 광산발생제 및 유기용매를 포함하는 것을 특징으로 포토레지스트 조성물.A photoresist composition comprising the photoresist polymer of claim 1, a photoacid generator and an organic solvent. 제 6 항에 있어서,The method of claim 6, 상기 광산발생제는 프탈이미도트리플루오로메탄술포네이트, 디니트로벤질토실레이트, n-데실디술폰, 나프틸이미도트리플루오로메탄술포네이트, 디페닐요도염 헥사플루오로포스페이트, 디페닐요도염 헥사플루오로 아르세네이트, 디페닐요도염 헥사플루오로 안티모네이트, 디페닐파라메톡시페닐 트리플레이트, 디페닐파라톨루에닐 트리플레이트, 디페닐파라이소부틸페닐 트리플레이트, 트리페닐설포늄 헥사플루오로 아르세네이트, 트리페닐설포늄 헥사플루오로 안티모네이트, 트리페닐설포늄 트리플레이트 및 디부틸나프틸설포늄 트리플레이트로 이루어진 군으로부터 선택된 것을 단독으로 또는 혼합하여 사용하는 것을 특징으로 하는 포토레지스트 조성물.The photoacid generator is phthalimidotrifluoromethanesulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethanesulfonate, diphenyl iodo salt hexafluorophosphate, diphenyl iodo salt hexafluoro Arsenate, Diphenyl iodo hexafluoro antimonate, Diphenyl paramethoxyphenyl triflate, Diphenyl paratoluenyl triflate, Diphenyl paraisobutyl phenyl triflate, Triphenylsulfonium hexafluoro arse A photoresist composition characterized in that it is used singly or in combination with one selected from the group consisting of nitrate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate. 제 6 항에 있어서,The method of claim 6, 상기 광산발생제는 상기 포토레지스트 중합체에 대해 0.05 내지 10중량% 비율로 사용되는 것을 특징으로 하는 포토레지스트 조성물.The photoresist composition is a photoresist composition, characterized in that used in 0.05 to 10% by weight relative to the photoresist polymer. 제 6 항에 있어서,The method of claim 6, 상기 유기용매는 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이 트, 프로필렌글리콜 메틸에테르아세테이트, 사이클로헥사논, 2-헵타논 또는 에틸락테이트로 이루어진 군으로부터 선택된 것을 단독으로 또는 혼합하여 사용하는 것을 특징으로 하는 포토레지스트 조성물.The organic solvent is selected from the group consisting of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, cyclohexanone, 2-heptanone or ethyl lactate alone or mixed. Photoresist composition, characterized in that used. 제 6 항에 있어서,The method of claim 6, 상기 유기용매는 상기 포토레지스트 중합체에 대해 500 내지 2000중량%로 사용되는 것을 특징으로 하는 포토레지스트 조성물.The organic solvent is a photoresist composition, characterized in that used in 500 to 2000% by weight based on the photoresist polymer. (a) 제 6 항에 기재된 포토레지스트 조성물을 피식각층 상부에 코팅하여 포토레지스트 막을 형성하는 단계;(a) coating the photoresist composition of claim 6 on the etched layer to form a photoresist film; (b) 상기 포토레지스트 막을 노광하는 단계; 및(b) exposing the photoresist film; And (c) 상기 결과물을 현상하여 원하는 패턴을 얻는 단계로 이루어지는 것을 특징으로 하는 포토레지스트 패턴 형성방법.(c) developing the resultant to obtain a desired pattern. 제 11 항에 있어서, The method of claim 11, 상기 (b) 단계의 노광 전에 소프트 베이크 공정, (b) 단계의 노광 후에 포스트 베이크 공정, 또는 (b) 단계의 노광전 및 노광후 각각에 대해 베이크 공정을 실시하는 단계를 더 포함하는 것을 특징으로 하는 포토레지스트 패턴 형성방법.And performing a bake process for each of the soft bake process before exposure of step (b), the post bake process after exposure of step (b), or the pre-exposure and post-exposure of step (b). A photoresist pattern forming method. 제 12 항에 있어서, The method of claim 12, 상기 베이크 공정은 70 내지 200℃에서 수행되는 것을 특징으로 하는 포토레지스트 패턴 형성방법.The baking process is a photoresist pattern forming method, characterized in that performed at 70 to 200 ℃. 제 11 항에 있어서, The method of claim 11, 상기 노광공정은 광원으로서 VUV(vacuum ultraviolet; 157㎚), ArF(193㎚), KrF(248㎚), I-line, E-빔, EUV(extreme ultraviolet) 및 이온빔으로 이루어진 군으로부터 선택된 것을 이용하여 수행되는 것을 특징으로 하는 포토레지스트 패턴 형성방법.The exposure process uses a light source selected from the group consisting of VUV (vacuum ultraviolet (157 nm)), ArF (193 nm), KrF (248 nm), I-line, E-beam, EUV (extreme ultraviolet) and ion beam. A method of forming a photoresist pattern, characterized in that carried out. 제 11 항에 있어서, The method of claim 11, 상기 노광공정은 0.1 내지 100mJ/cm2의 노광에너지로 수행되는 것을 특징으로 하는 포토레지스트 패턴 형성방법.The exposure process is a photoresist pattern forming method, characterized in that performed with an exposure energy of 0.1 to 100mJ / cm 2 . 제 11 항에 있어서,The method of claim 11, 상기 현상 단계 (c)는 알칼리 현상액을 이용하여 수행되는 것을 특징으로 하는 포토레지스트 패턴 형성방법.The developing step (c) is a photoresist pattern forming method, characterized in that carried out using an alkaline developer. 제 11 항 기재의 방법을 이용하여 제조된 반도체 소자.A semiconductor device manufactured using the method of claim 11.
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EP2428843A1 (en) * 2010-09-10 2012-03-14 Rohm and Haas Electronic Materials LLC Photoresist compositions and methods of forming photolithographic patterns
US8614050B2 (en) 2010-12-31 2013-12-24 Rohm And Haas Electronic Materials Llc Polymers, photoresist compositions and methods of forming photolithographic patterns
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Publication number Priority date Publication date Assignee Title
EP2428843A1 (en) * 2010-09-10 2012-03-14 Rohm and Haas Electronic Materials LLC Photoresist compositions and methods of forming photolithographic patterns
US20120064456A1 (en) * 2010-09-10 2012-03-15 Dow Global Technologies Llc Photoresist compositions and methods of forming photolithographic patterns
CN102445848A (en) * 2010-09-10 2012-05-09 罗门哈斯电子材料有限公司 Photoresist compositions and methods of forming photolithographic patterns
JP2012103679A (en) * 2010-09-10 2012-05-31 Rohm & Haas Electronic Materials Llc Photoresist composition and method for forming photolithographic pattern
EP2527919A1 (en) * 2010-09-10 2012-11-28 Rohm and Haas Electronic Materials LLC Photoresist compositions and methods of forming photolithographic patterns
CN102445848B (en) * 2010-09-10 2015-08-05 罗门哈斯电子材料有限公司 The method of photoetching compositions and formation photoengraving pattern
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