CN1149237C - 共聚物树脂,其制备方法及用其制成的光致抗蚀剂 - Google Patents
共聚物树脂,其制备方法及用其制成的光致抗蚀剂 Download PDFInfo
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- -1 Preparation thereof Polymers 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 229920002120 photoresistant polymer Polymers 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
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- PHSXOZKMZYKHLY-UHFFFAOYSA-N 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCCO)CC1C=C2 PHSXOZKMZYKHLY-UHFFFAOYSA-N 0.000 claims description 5
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 2
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical class C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 claims 7
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- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- DMZTWZZWIPUVMA-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene;furan-2,5-dione Chemical compound C1C2CCC1C=C2.O=C1OC(=O)C=C1 DMZTWZZWIPUVMA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002848 norbornenes Chemical class 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
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- ZQTYQMYDIHMKQB-UHFFFAOYSA-N exo-norborneol Chemical compound C1CC2C(O)CC1C2 ZQTYQMYDIHMKQB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- UOUFRTFWWBCVPV-UHFFFAOYSA-N tert-butyl 4-(2,4-dioxo-1H-thieno[3,2-d]pyrimidin-3-yl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(CC1)n1c(=O)[nH]c2ccsc2c1=O UOUFRTFWWBCVPV-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
Classifications
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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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- 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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
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- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
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Abstract
本发明涉及一种使用于远紫外线(像KrF或ArF)的光致抗蚀剂的共聚物树脂、其制备方法及包含此树脂的光致抗蚀剂。本发明的共聚物因其可将顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元导入用作光致抗蚀剂之降冰片烯-顺丁烯二酸酐共聚物的结构中,因此可以传统自由基聚合反应容易地制备。此树脂在193nm波长时具有高的透明性,蚀刻阻抗性增加,并解决了在共聚物树脂合成过程中产生刺激性气味的问题。再者,因为此树脂组成由于分子结构的原因,所以可轻易的控制,因此,此树脂可以大规模地制造。
Description
本发明涉及一种用于制造电子装置的光致抗蚀剂的共聚物树脂。此光致抗蚀剂可用于紫外线,像KrF或ArF。更具体的说,本发明涉及一种制备该光致抗蚀剂的方法,使用此光致抗蚀剂的方法,以及光致抗蚀剂本身。在一示列性实施方案中,本发明涉及一种光致抗蚀剂树脂,其中顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元已被导入用作光致抗蚀剂的降冰片烯-顺丁烯二酸酐共聚物结构中,此光致抗蚀剂可应用于能用来制造1G或4G DRAM元件及其它元件而使用的KrF(248nm)或ArF(193nm)光源的光刻程序;本发明也涉及制备此共聚物树脂的方法,及包含此树脂的光致抗蚀剂。
各种类型的光致抗蚀剂已被使用或建议使用。这些光致抗蚀剂通常具有各种特征或特性,像蚀刻阻抗性、粘着性,及其它性质。一般而言,蚀刻阻抗性、具有193nm波长低光吸收的粘着性等性质对用于ArF的共聚物树脂是必须的。此共聚物树脂应使用2.38wt%四甲基氢氧化铵水溶液(TMAH)显像。然而,合成一个能够满足一种或数种这些性质的共聚物树脂是非常困难的。许多的研究者致力于研究降冰片基类的树脂以增加在193nm波长的透明性,及增加蚀刻阻抗性。有一个例子为贝尔实验室(Bell Lab)曾尝试将脂环单元导入分子的主干中以提高其蚀刻阻抗性。这类主干具有降冰片基,丙烯酸酯及顺丁烯二酸酐取代基的共聚物树脂的化学式例如下式I所示:[式1]
式I的共聚物树脂,其中用于聚合脂环烯烃基的顺丁烯二酸酐部分(A部分)是唯一和降冰片烯及脂环单元聚合的物质,且没有吸收波长为193nm的ArF光。因此,因为其在2.38%TMAH水溶液中是非常易溶解的,所以一般来说其不能当作ArF树脂。即使没有曝光仍然会溶解,而产生一种“顶部漏失”现象(形成圆形的顶部图像),这是一种在传统光致抗蚀剂产生图像时通常可见的。
因此,为了防止此种现象,具有叔丁基取代基的y部分必须增加。z-部分(可提高敏感性及对基板的粘着性)相对减少会产生一些缺点,如光致抗蚀剂以传统产生图像方法由晶片移去时,不能很有效率的产生图像。另外也有人建议使用其它光致抗蚀剂产物,但这些光致抗蚀剂产物有许多的限制,像不易于制造,有刺激性气味等等。
由上述可看出仍然需要一种具有较佳粘着性及良好分辨度的光致抗蚀剂。
依据本发明,发明人开发了一种顺丁烯二酸酐型式的共聚物树脂,其包括式II所示的作为主要成份的5-降冰片烯-2-羧酸单体,且申请了专利(韩国专利申请第97-26807号,申请日为1997年6月21日),作为解决传统光致抗蚀剂产物限制的一种尝试。[式II]
虽然上述申请案建议使用的顺丁烯二酸酐型式的共聚物树脂具有高粘着性、敏感性及优良分辨度的优点,但其实际制造时仍有问题,这是因为其主要成份之一5-降冰片烯-2-羧酸在合成过程中会产生刺激性极强的气味。因此,本发明人开发出了一具有优良分辨度,且不会引起刺激气味问题的新颖光致抗蚀剂。
在一具体实施方案中,本发明提供一种限制传统光致抗蚀剂产物所引起的刺激性气味的技艺。具体地讲,本发明提供一种将顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元代替5-降冰片烯-2-羧酸导入降冰片烯-顺丁烯二酸酐共聚物结构中的方法,同时本发明方法解决了刺激性气味逸出的问题。在一优选实施方案中,本发明方法提供了一种光阻敏感性基本上不变劣的光致抗蚀剂。本发明的光致抗蚀剂也具有像优良粘着性及分辨度(0.13μm)的特征。本发明光致抗蚀剂在合成过程中易于控制其组成,所以大量制造是可能的。
相较于传统技艺,本发明具有许多优点或益处。在一具体实施方案中,本发明提供一包含顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元的共聚物树脂;在另一实施方案中,本发明提供一种制备含有顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元的共聚物树脂的方法;又另一实施方案中,本发明提供一种包含上述降冰片烯-顺丁烯二酸酐共聚物树脂、有机溶剂及一光酸产生剂的光致抗蚀剂。再者,本发明提供使用含有上述共聚物树脂的光致抗蚀剂制得的半导体元件。这些及其它优点将由说明书描述,尤其是以下的说明。
本发明涉及一种用作光致抗蚀剂的共聚物树脂,该树脂包含顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元,其由下式III所表示:[式III]
其中,R是叔丁基、四氢吡喃基、四氢呋喃基或乙氧基乙基,且x∶y∶z的比例是(0.1-99%)∶(0.1-99%)∶(0.1-99%);该共聚物树脂的分子量为3000-100000。
依据本发明的实施方案的共聚物树脂优选包括下式IV至VII的降冰片烯-顺丁烯二酸酐共聚物树脂:
[式IV]
[式V]
[式VI]
[式VII]
在这些结构式中,R,x,y及z如上文所定义。
本发明的式III所示的共聚物树脂可在自由基引发剂的存在下,由式VIII的降冰片烯衍生物、式IX的5-降冰片烯-2-羧酸(2-羟乙基)酯、式X的顺丁烯二酸酐及式XI的顺-5-降冰片烯-内-2,3-二羧酸单甲酯聚合制备而得:[式VIII]
[式IX]
[式X]
[式XI]
在上述结构式中,R是叔丁基、四氢吡喃基、四氢呋喃基或乙氧基乙基等基团。
在制备本发明的共聚物树脂时,式VIII的降冰片烯衍生物优选选自5-降冰片烯-2-羧酸叔丁酯、5-降冰片烯-2-羧酸-2-四氢吡喃酯、5-降冰片烯-2-羧酸-2-四氢呋喃酯和5-降冰片烯-2-羧酸(1-乙氧基乙基)酯酯。
本发明的共聚物树脂可由传统聚合方法制备而得,像本体聚合或溶液聚合方法等。溶剂可为环己酮、甲基乙基酮、苯、甲苯、二噁烷及/或二甲基甲酰胺,其可单独使用,或混合使用。用于本发明的聚合反应引发剂包括过氧化苯甲酰、2,2′-偶氮二异丁腈(AIBN)、过氧化乙酰、过氧化月桂酰、过乙酸叔丁酯、二-叔丁基过氧化物等。
在制备本发明共聚物树脂的方法中,可依据反应物的性质来控制一般包括自由基聚合反应的温度和压力在内的聚合化条件,但优选该聚合反应在温度从60至200℃之间进行。
本发明的共聚物树脂能依据传统制备光致抗蚀剂组合物的方法,将本发明的树脂与有机溶剂及传统光酸产生剂混合,制成光致抗蚀剂溶液而用于形成正显微-影像(micro-image)。在形成半导体元件的光致抗蚀剂图像的程序中,本发明共聚物树脂的使用量是依据所使用的有机溶剂或光酸产生剂及光刻的条件而定,但一般传统上采用约10至30%(重量百分比)(依据用于制备此光致抗蚀剂有机溶剂的量而定)。
使用本发明共聚物树脂形成半导体元件光致抗蚀剂图像的程序将在以下作详细的说明:
将本发明的共聚物树脂溶于环己酮中,其浓度为10至30%(重量)。加入光酸产生剂(0.1至10wt%)如三苯基三倍酸锍(triphenylsulfonium triplate)、二丁基萘基三倍酸锍(dibutylnaphthylsulfonium triplate)、2,6-二甲基苯基磺酸酯、双(芳基磺酰基)-二偶氮甲烷、磺酸肟、2,1-二偶氮萘醌-4-磺酸酯至此光致抗蚀剂树脂中。然后用一超微过滤器过滤该混合物。接着将光致抗蚀剂溶液旋转涂覆至一硅晶片上,以形成一薄膜,然后在一烤箱中或在一加热板上以温度80-150℃轻轻地烘烤(soft-baked)1-5分钟,接着使用远紫外线曝光器或激光雷射曝光器曝光,然后以温度100℃至200℃烘烤10秒钟至60分钟。将曝光后的晶片浸渍至2.38%的TMAH水溶液中1至30秒钟,以获得一正光致抗蚀剂图像。
本发明可通过以说明为目的的下列实施例得到进一步的了解,实施例的目的不是要限制本发明。
制备实施例I
5-降冰片烯-2-羧酸叔丁酯的合成。
[式VIIIa]
在一反应器中,加入环戊二烯(66克)及四氢呋喃溶剂(500克),且搅拌此反应混合物至均匀。于此反应混合物中,加入丙烯酸叔丁酯(128克),且在温度-30℃和60℃之间搅拌所得混合物约10小时,使反应进行。当反应完全时,使用一旋转蒸发器除去溶剂,且在减压下蒸馏该残留物,可得176克(产率:90%)式VIIIa之5-降冰片烯2-羧酸叔丁酯。
制备实施例II
5-降冰片烯-2-羧酸(2-羟基乙基)酯的合成(式IX)
重复制备实施例I的步骤,但使用丙烯酸2-羟基乙基酯(116克)代替丙烯酸叔丁基酯,可得155克(产率:85%)的式IX的5-降冰片烯-2-羧酸(2-羟基乙基)酯。
制备实施例III
5-降冰片烯-2-羧酸-2-四氢吡喃酯的合成
[式VIIIb]
重复制备实施例I的步骤,但使用丙烯酸2-四氢吡喃酯(156克)代替丙烯酸叔丁基酯,可得186克(产率:84%)式VIIIb所示的5-降冰片烯-2-羧酸-2-四氢吡喃酯。
制备实施例IV
5-降冰片烯-2-羧酸-2-四氢呋喃酯的合成[式VIIIc]
重复制备实施例I的步骤,但使用丙烯酸2-四氢呋喃酯(144克)代替丙烯酸叔丁基酯,可得172克(产率:82%)式VIIIc的2-四氢呋喃基-5-降冰片烯-2-羧酸酯。
制备实施例V
5-降冰片烯-2-羧酸(1-乙氧基乙基)酯的合成
[式VIIId]
重复制备实施例I的步骤,但使用丙烯酸乙氧基乙基酯(144克)代替丙烯酸叔丁基酯,可得174克(产率:83%)式VIIId的5-降冰片烯-2-羧酸(1-乙氧基乙基)酯。
制备实施例VI
顺-5-降冰片烯-内-2,3-二羧酸单甲酯(式XI)的合成
在一反应器中,加入环戊二烯(66克),并加入四氢呋喃溶剂(500克)和顺丁烯二酸酐(98克),且均匀搅拌此反应混合物。于此反应混合物中,加入无水乙醇(500克),且在温度50℃于搅拌下使反应进行8小时,当反应完成时,使用一旋转蒸发器除去溶剂,且在减压下蒸馏该残留物,可得156克(产率:87%)式XI的顺-5-降冰片烯-内-2,3-二羧酸单甲酯。
实施例I
聚[5-降冰片烯-2-羧酸叔丁酯/5-降冰片烯-2-羧酸(2-羟基乙基)酯/顺-5-降冰片烯-内-2,3-二羧酸单甲酯/顺丁烯二酸酐]共聚物树脂(式IV)的合成。
将顺丁烯二酸酐(1摩尔)、制备实施例I制备的5-降冰片烯-2-羧酸叔丁酯(0.5-0.9摩尔)、制备实施例II制备的5-降冰片烯-2-羧酸(2-羟基乙基)酯(0.05-0.8摩尔)、制备实施例VI制备的顺-5-降冰片烯-内-2,3-二羧酸单甲酯(0.01-0.5摩尔)溶于四氢呋喃或甲苯中,然后加入作为聚合起始剂的2,2′-偶氮二异丁腈(AIBN)(0.5-10克),且维持温度65℃和70℃之间,在氮气或氩气气氛之下进行反应4-24小时。所得粗产物由乙醚或己烷中沉淀出,且干燥沉淀物后可得标题共聚物树脂(式IV),其分子量3,000-100,000(产率:63%)。所得共聚物树脂对ArF光的透明性高,蚀刻阻抗性增加,且具有优良的粘着性,可由2.38wt%的TMAH水溶液显像。
实施例II
聚[5-降冰片烯-2-羧酸-2-四氢吡喃酯/5-降冰片烯-2-羧酸(2-羟基乙基)酯/顺-5-降冰片烯-内-2,3-二羧酸单甲酯/顺丁烯二酸酐]共聚物树脂(式V)的合成。
重复实施例I的步骤,但使用制备实施III的5-降冰片烯-2-羧酸-2-四氢吡喃酯代替5-降冰片烯-2-羧酸叔丁酯,可得标题共聚物树脂(式V),其分子量:3,000-100,000(产率:68%)。虽然所得共聚物树脂的保护基是由乙酰基所取代的,但树脂的蚀刻阻抗性没有变劣,且具有优良的敏感度(敏感度:11mJ/cm2)。
实施例III
聚[5-降冰片烯-2-羧酸-2-四氢呋喃酯/5-降冰片烯-2-羧酸(2-羟基乙基)酯/顺-5-降冰片烯-内-2,3-二羧酸单甲酯/顺丁烯二酸酐]共聚物树脂(式VI)的合成。
重复实施例I的步骤,但使用制备实施例IV的5-降冰片烯-2-羧酸-2-四氢呋喃酯代替5-降冰片烯-2-羧酸叔丁酯,可得标题共聚物树脂(式VI),其分子量:4,000-100,000(产率:64%)。所得共聚物树脂的性质类似于实施例II的共聚物树脂。
实施例IV
聚[5-降冰片烯-2-羧酸(1-乙氧基乙基)酯/5-降冰片烯-2-羧酸(2-羟乙基)酯/顺-5-降冰片烯-内-2,3-二羧酸单甲酯/顺丁烯二酸酐]共聚物(式VII)的合成。
重复实施例I的步聚,但使用制备实施例V的5-降冰片烯-2-羧酸(1-乙氧基乙基)酯代替5-降冰片烯-2-羧酸叔丁酯,可得标题共聚物树脂(式VII),其分子量:4,000-100,000(产率:59%)。所得共聚物树脂的性质类似于实施例I的共聚物树脂,但相比而言,其性质更佳。
实施例V
实施例I所得的共聚物树脂(式IV)(10克)溶于丙酸3-甲氧基甲基酯(40克,溶剂)中,且加入作为光酸产生剂的三苯基三倍酸锍或二丁基萘基三倍酸锍(约0.2-1克),搅拌后,经由0.10μm过滤器过滤所得混合物,获得一光致抗蚀剂溶液。然后,将光致抗蚀剂溶液旋转涂覆至一晶片表面,制备一厚度为0.4-1.2μm之薄膜,且以70℃-150℃的温度在烘箱中或在热板上轻轻烘烤1-5分钟。以250nm波长的曝光器曝光后,以90-160℃的温度后-烘烤。然后将曝光后的晶片浸渍在浓度为0.01-5%(重量)的TMAH水溶液中1.5分钟,此水溶液为显像剂,可得一超显微光致抗蚀剂图像(分辨度:0.13μm)。
实施例VI
重复实施例V的步骤,但使用实施例II制得的共聚物树脂(式V)作为光致抗蚀剂树脂,来形成一超显微光致抗蚀剂图像。
实施例VII
重复实施例V的步骤,但使用实施例III制备的共聚物树脂(式VI)作为光致抗蚀剂树脂,来形成一超显微光致抗蚀剂图像。
实施例VIII
重复实施例V的步骤,但使用实施例IV制得的共聚物树脂(式VII)作为光致抗蚀剂树脂,来形成一光致抗蚀剂图像。
当使用上述光致抗蚀剂形成图像时,可制得一具有0.13μm超显微图像的半导体元件,所以可有利于制造高度集成的元件。
如上所述,本发明使用KrF(249nm)或ArF(193nm)的光致抗蚀剂的共聚物树脂可以传统自由基聚合反应,将顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元导入聚合物结构中而容易地制备。此树脂在193nm波长具有高度透明性,蚀刻阻抗性增加,且解决了在合成共聚物树脂时产生刺激性气味的问题。再者,因为分子结构的原因,此树脂的组成很容易控制,所以可用于大量制造。因此,本发明的使用KrF或ArF的共聚物树脂能够用于光刻程序。
根据上述教导,各种对本发明的改良及修正皆是可能的,因此,应理解的是在所附权利要求的范围内,除了特别叙述的方式外,本发明可以其它的方法施行。
Claims (18)
1.一种分子量为3,000-100,000的共聚物树脂,包括顺-5-降冰片烯-内-2,3-二羧酸单甲酯单元,该共聚物树脂由下式III所表示:
[式III]
其中,R是叔丁基、四氢吡喃基、四氢呋喃基或乙氧基乙基,且x∶y∶z的比例是(0.1-99%)∶(0.1-99%)∶(0.1-99%)。
4.如权利要求1的共聚物树脂,其是如式VI所示的降冰片烯-顺丁烯二酸酐共聚物树脂:
[式VI]
其中x∶y∶z的比例为(0.1-99%)∶(0.1-99%)∶(0.1-99%)。
7.如权利要求6所述的方法,其中所述的5-降冰片烯衍生物是式VIIIa所示的5-降冰片烯-2-羧酸叔丁酯。
[式VIIIa]
8.如权利要求6所述的方法,其中所述的5-降冰片烯衍生物是式VIIIb所示的5-降冰片烯-2-羧酸-2-四氢吡喃酯。
[式VIIIb]
11.如权利要求6的制备共聚物树脂的方法,其中所述聚合反应引发剂是选自包含下列化合物的族群:过氧化苯甲酰、2,2′-偶氮二异丁腈、过氧化乙酰、过氧化月桂酰、过乙酸叔丁酯及二-叔丁基过氧化物。
12.如权利要求6的制备共聚物树脂的方法,其中所述聚合反应是在溶剂或溶剂混合物的存在下进行反应,所述溶剂选自:环己酮、甲基乙基酮、苯、甲苯、二噁烷及二甲基甲酰胺。
13.如权利要求6的制备共聚物树脂的方法,其中所述聚合反应是在温度60℃和200℃之间,在氩气或氮气气氛下进行。
14.一种光致抗蚀剂组合物,包括如权利要求1所述的降冰片烯-顺丁烯二酸酐共聚物树脂、一种有机溶剂及一种光酸产生剂。
15.如权利要求14所述的光致抗蚀剂组合物,其中所述光酸产生剂是三苯基三倍酸锍或二丁基萘基三倍酸锍。
16.如权利要求14所述的光致抗蚀剂组合物,其中以溶剂的量为基准,所述共聚物树脂的含量在10wt%到30wt%之间。
17.如权利要求14所述的光致抗蚀剂组合物,其中以共聚物树脂的量为基准,所述光酸产生剂的量在0.01wt%到10wt%之间。
18.一种使用如权利要求14所述的光致抗蚀剂组合物制成的半导体器件。
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-
1997
- 1997-12-29 KR KR1019970077412A patent/KR100321080B1/ko active IP Right Grant
-
1998
- 1998-12-08 TW TW087120308A patent/TW515930B/zh not_active IP Right Cessation
- 1998-12-09 GB GB9827043A patent/GB2332679B/en not_active Expired - Fee Related
- 1998-12-22 JP JP36522798A patent/JP3847991B2/ja not_active Expired - Fee Related
- 1998-12-23 IT IT1998TO001083A patent/IT1312366B1/it active
- 1998-12-28 FR FR9816498A patent/FR2773160B1/fr not_active Expired - Fee Related
- 1998-12-29 DE DE19860654A patent/DE19860654A1/de not_active Withdrawn
- 1998-12-29 NL NL1010914A patent/NL1010914C2/nl not_active IP Right Cessation
- 1998-12-29 CN CNB98126607XA patent/CN1149237C/zh not_active Expired - Lifetime
- 1998-12-29 US US09/222,053 patent/US6369181B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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US6608158B2 (en) | 2003-08-19 |
IT1312366B1 (it) | 2002-04-15 |
GB2332679A (en) | 1999-06-30 |
KR100321080B1 (ko) | 2002-11-22 |
GB2332679B (en) | 2002-07-24 |
DE19860654A1 (de) | 1999-07-08 |
US20020068803A1 (en) | 2002-06-06 |
US6369181B1 (en) | 2002-04-09 |
CN1226565A (zh) | 1999-08-25 |
JP3847991B2 (ja) | 2006-11-22 |
TW515930B (en) | 2003-01-01 |
ITTO981083A1 (it) | 2000-06-23 |
KR19990057361A (ko) | 1999-07-15 |
NL1010914C2 (nl) | 1999-08-26 |
ITTO981083A0 (it) | 1998-12-23 |
NL1010914A1 (nl) | 1999-06-30 |
GB9827043D0 (en) | 1999-02-03 |
FR2773160B1 (fr) | 2001-01-12 |
JPH11255840A (ja) | 1999-09-21 |
FR2773160A1 (fr) | 1999-07-02 |
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