JPH0195115A - Ultraviolet-absorptive polymer material - Google Patents
Ultraviolet-absorptive polymer materialInfo
- Publication number
- JPH0195115A JPH0195115A JP62251635A JP25163587A JPH0195115A JP H0195115 A JPH0195115 A JP H0195115A JP 62251635 A JP62251635 A JP 62251635A JP 25163587 A JP25163587 A JP 25163587A JP H0195115 A JPH0195115 A JP H0195115A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- fluorine atom
- ultraviolet absorbing
- material according
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002861 polymer material Substances 0.000 title claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- FMQPBWHSNCRVQJ-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(F)(F)F)C(F)(F)F FMQPBWHSNCRVQJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 claims description 2
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- MNSWITGNWZSAMC-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl prop-2-enoate Chemical compound FC(F)(F)C(C(F)(F)F)OC(=O)C=C MNSWITGNWZSAMC-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 17
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 15
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 15
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 abstract 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000013532 laser treatment Methods 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 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 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- CCJHDZZUWZIVJF-UHFFFAOYSA-N iodo nitrate Chemical compound [O-][N+](=O)OI CCJHDZZUWZIVJF-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- -1 olefin compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
- G03F7/2043—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means with the production of a chemical active agent from a fluid, e.g. an etching agent; with meterial deposition from the fluid phase, e.g. contamination 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/36—Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はエキシマレーザ加工に適した紫外線吸収高分子
材料に関し、特にレジスト材料作成のために使用したエ
キシマレーザ照射後のエツチング操作に適した紫外線吸
収高分子材料に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an ultraviolet absorbing polymer material suitable for excimer laser processing, and particularly to an ultraviolet absorbing polymer material suitable for etching operation after excimer laser irradiation used to create a resist material. Regarding absorbent polymer materials.
（従来の技術）
ＬＳＩの作成手段としてはガラス板上に主としてポリメ
チルメタアクリレートよりなるフォトレジスト材料を戴
置し、この上にマスキング板を置き上部よりレーザー光
線を照射したのち、マスキング板を取り除き、溶剤によ
り感光部分若しくは不感光部分を溶出するエツチング操
作を経て作成されている。最近、光源として使用するレ
ーザーにエキシマレーザ−が使用されている。エキシマ
レーザ−（ｅｘｃｉｍｅｒ）とは励起原子または分子と
基底原子または分子の二量体のことであり、このレーザ
ーは高出力で短パルスの紫外線を出すことができるので
、従来の水銀ランプやキセノンランプに比して極めて短
時間で反応が行なわれる。エキシマレーザ−で照射後、
感光部分を除去するエツチング操作が行なおれる。今日
、ＬＳＩ技術で最も重要視されているのがこのエツチン
グの技術である。この理由は、基板表面で化学、物理反
応して出来た反応生成物が溶液のエツチング（Ｗｅｔエ
ツチング）で溶解して取り除かれる。この反応生成物の
除去がうまく行われないと、エツチング速度が時間的に
、あるいは局部的に不均一になる。(Prior art) As a means of creating an LSI, a photoresist material mainly made of polymethyl methacrylate is placed on a glass plate, a masking plate is placed on top of the photoresist material, a laser beam is irradiated from above, and the masking plate is removed. It is created through an etching operation in which the photosensitive or non-photosensitive areas are eluted with a solvent. Recently, excimer lasers have been used as lasers as light sources. An excimer laser (excimer) is a dimer of an excited atom or molecule and a base atom or molecule, and this laser can emit high-power, short-pulse ultraviolet light, so it can be The reaction takes place in an extremely short time. After irradiation with excimer laser,
An etching operation is performed to remove the photosensitive areas. Etching technology is the most important technology in LSI technology today. The reason for this is that reaction products produced by chemical and physical reactions on the substrate surface are dissolved and removed by solution etching (wet etching). If this reaction product is not removed successfully, the etching rate will become temporally or locally non-uniform.
この反応生成物だけでなく、エツチングの副反応などに
よって不溶性、不揮発性の反応生成物ができ、これが基
板材料表面を覆ってしまうと、エツチング妨害の原因と
なる。通常シリコーン基板に用いられるエツチング液に
はフッ酸（ＨＦ）と硝酸の混合液（１５：１０：水溶液
３００）が用いられており。In addition to these reaction products, insoluble and non-volatile reaction products are produced by side reactions during etching, and if they cover the surface of the substrate material, they cause etching interference. The etching solution normally used for silicone substrates is a mixed solution of hydrofluoric acid (HF) and nitric acid (15:10:300:aqueous solution).
これは硝酸でＳｉ表面を酸化し、フッ酸（ＨＦ）水溶液
にて取り除くとの考え方に基ずいているのである。とこ
ろがポリメタクリル酸メチルをレジスト材料として使用
し、ベーキング後上記のＨＦと硝酸の混合液からなるエ
ツチング液で処理すると、該ポリマー表面が侵しよくを
受けるという問題が生じるのである。This is based on the concept of oxidizing the Si surface with nitric acid and removing it with a hydrofluoric acid (HF) aqueous solution. However, when polymethyl methacrylate is used as a resist material and treated with the above-mentioned etching solution consisting of a mixture of HF and nitric acid after baking, a problem arises in that the surface of the polymer is easily attacked.
（解決すべき問題点）
そこで本発明者は上記の問題点を解決し、ポリメタクリ
ル酸メチル連鎖を含有するりジグラフイー材料でありな
がら耐エツチング液（ＨＦ：）ＩＮＯ３：Ｈ。(Problems to be Solved) The inventors of the present invention solved the above-mentioned problems and developed an etching-resistant liquid (HF:) INO3:H which is a digraphie material containing polymethyl methacrylate chains.
０）性を有する超高分子量ＰＭＭＡを得るべく種々検討
した結果ＰＭＭＡの連鎖骨格に弗素原子導入することに
よって耐エツチング性が改良できることを見出し本発明
を完成したもので、本発明の目的は上記の特性を有する
紫外線吸収高分子材料を提供するにある。As a result of various studies in order to obtain ultra-high molecular weight PMMA having the properties of The object of the present invention is to provide an ultraviolet absorbing polymer material having the following characteristics.
（問題点を解決するための手段）
すなわち、本発明はメチルメタクリレートの連鎖骨格中
に繰り返し単位当り弗素原子を少なくとも１個含有せし
めたことを特徴とする紫外線吸収高分子材料であって、
得られた紫外線吸収高分子材料としては次の構造式を有
し、分子量は５×１０７〜５ Ｘ １０’好ましくは５
．×１０５〜５ Ｘ １０’である。５Ｘ１０５以下で
は、紫外線吸収高分子材料としての特性を有することが
難しい、ここでいう繰り返し単位当りというのは、下に
示す（ｍ＋ｎ）を１単位とすることを意味する。(Means for Solving the Problems) That is, the present invention is an ultraviolet absorbing polymeric material characterized by containing at least one fluorine atom per repeating unit in the chain skeleton of methyl methacrylate,
The obtained ultraviolet absorbing polymer material has the following structural formula, and the molecular weight is 5 x 107 to 5 x 10', preferably 5
．． x105 to 5 x 10'. If it is less than 5×10 5 , it is difficult to have properties as an ultraviolet absorbing polymer material. Here, per repeating unit means that (m+n) shown below is 1 unit.
ここで、Ｒ１，Ｒ３はＨ又はＣＨ，基、Ｒｚは炭素数１
〜５、好ましくは炭素数１ないし４のアルキル基である
。Here, R1 and R3 are H or CH, groups, and Rz has 1 carbon number.
-5, preferably an alkyl group having 1 to 4 carbon atoms.
Ｒ４は炭素数１〜８．好ましくは炭素数１ないし４のア
ルキル基であって、少なくとも１個の水素原子を弗素原
子で置換したものである。R4 has 1 to 8 carbon atoms. Preferably, it is an alkyl group having 1 to 4 carbon atoms, in which at least one hydrogen atom is replaced with a fluorine atom.
この−数式においてｎ＋／ｎ（モル比）は０．３−５で
あり、０．３以下では重合反応が進行せず、また５を越
える値では耐エツチング性を示さない。しかして、上記
の弗素原子を含有するポリマーを形成するためにメチル
メタアクリレートと共重合する七ツマ−としてはニー
ヘキサフロロイソプロピルメタクリレートＣ）１２＝Ｃ
Ｃ００ＣＲ（ＣＦ３ ）２
トリフルオロエチルメタクリレート
ＣＨ。In this formula, n+/n (molar ratio) is 0.3-5, and if it is less than 0.3, the polymerization reaction will not proceed, and if it exceeds 5, it will not exhibit etching resistance. Thus, as a hexafluoroisopropyl methacrylate C)12=C C00CR(CF3)2 trifluoroethyl methacrylate CH, which is copolymerized with methyl methacrylate to form the above-mentioned fluorine atom-containing polymer.
■ Ｃ）Ｉ２＝Ｃ ＣＯＯＣＲ，ＣＦ３ トリフロロエチルアクリレート ＣＨ，＝ＣＨ−Ｃ００ＣＩ（、ＣＦ。■ C) I2=C COOCR, CF3 trifluoroethyl acrylate CH,=CH-C00CI(, CF.
ヘキサフロロイソプロピルアクリレートＣＨ２＝ＣＨ−
Ｃ００ＣＨ（ＣＦ、）２などの含弗素ビニル七ツマ−で
ある。或はヘキサフロロブテン ＣＦ、 Ｃ＝ＣＣＦ。Hexafluoroisopropyl acrylate CH2=CH-
It is a fluorine-containing vinyl hexamer such as C00CH(CF, )2. Or hexafluorobutene CF, C=CCF.
ヘキサフロロブタジェン１．３ ＣＦ２＝ＣＦＣＦ＝
ＣＦ。Hexafluorobutadiene 1.3 CF2=CFCF=
C.F.
ヘキサフロロプロパン ＣＦ３ＣＦ＝ＣＦ、等の含弗素
オレフイン化合物等である。These include fluorine-containing olefin compounds such as hexafluoropropane CF3CF=CF.
しかしてメチルメタアクリレートと弗素原子含有モノマ
ーとは先に述べた範囲内の所望の割合で共重合させれば
よい。Therefore, methyl methacrylate and the fluorine atom-containing monomer may be copolymerized in a desired ratio within the above-mentioned range.
メチルメタアクリレートと上記弗素含有化合物（モノマ
ー）との共重合手段としては通常のビニル化合物の共重
合手段の何れもが適用できるが、特にラジカル重合開始
剤存在下にプラズマを照射するプラズマ重合法が最も好
ましい。ラジカル重合開始剤としては一般的ラジカル重
合に使用されるものであれば何れでもよいが例えば過酸
化ベンゾイル、ジクミルパーオキサイド、アゾビスイソ
ブチロニトリルである。ラジカル重合開始剤の七ツマ−
への添加量はモノマーの種類、重合温度、得ようとする
ポリマーの重合等に異なり一部にはいえないが必要以上
のラジカル重合開始剤を添加すると重合開始剤が生成し
たポリマー中に残存し好ましくない。As a method for copolymerizing methyl methacrylate and the above-mentioned fluorine-containing compound (monomer), any of the usual copolymerization methods for vinyl compounds can be applied, but a plasma polymerization method in which plasma is irradiated in the presence of a radical polymerization initiator is particularly suitable. Most preferred. As the radical polymerization initiator, any initiator used in general radical polymerization may be used, such as benzoyl peroxide, dicumyl peroxide, and azobisisobutyronitrile. Radical polymerization initiator
The amount added to the radical polymerization initiator varies depending on the type of monomer, polymerization temperature, polymerization of the polymer to be obtained, etc., but if more radical polymerization initiator is added than necessary, the polymerization initiator may remain in the resulting polymer. Undesirable.
又、プラズマ重合法において使用されるプラズマとして
は非平衡プラズマ、特にグロー放電による低温プラズマ
が好ましく、該低温プラズマは減圧下例えば０．１〜１
０ｍｍＨｇの圧力下にある気体に２０〜１００Ｗ好まし
くは３０〜５０ｗの電圧を加えることによって得られる
。使用される電極としては外部または内部平行平板電極
あるいはコイル状電極等があり、好ましくは外部平行平
板電極である。プラズマ発生源の気体は水素、メタン、
窒素、アルゴン、エチレン等の任意の気体あるいはモノ
マーガス自体であってもよい。The plasma used in the plasma polymerization method is preferably non-equilibrium plasma, especially low-temperature plasma generated by glow discharge.
It is obtained by applying a voltage of 20 to 100 W, preferably 30 to 50 W, to a gas under a pressure of 0 mmHg. The electrodes used include external or internal parallel plate electrodes or coiled electrodes, preferably external parallel plate electrodes. The plasma generation source gas is hydrogen, methane,
It may be any gas such as nitrogen, argon, ethylene, or the monomer gas itself.
このようにして得られた紫外線吸収特性は連鎖骨格であ
るポリメチルメタアクリレートの紫外線吸収特性と殆ど
変化はなく、透過率はポリメチルメタアクリレートに比
して極めて大であるばかりでなくエツチング液に対して
は抵抗性を有するのでポジ型レジスト板に適した紫外線
吸収高分子材料である。The ultraviolet absorption properties obtained in this way are almost the same as the ultraviolet absorption properties of polymethyl methacrylate, which is the chain skeleton, and the transmittance is not only extremely high compared to polymethyl methacrylate, but also resistant to etching solutions. It is a UV-absorbing polymer material suitable for positive resist plates because it has resistance to UV rays.
以下、実施例をもって本発明を更に詳細に述べるが本発
明はこれら実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
実験例１
内径１５ｗｎのパイレックスガラス製重合管（容量４２
ｍ１）にメタクリル酸メチル（ＨＭＡ） ５．３４ｍ１
（５，００ｘｌＯ”ｍｏｌ）、ヘキサフロロイソプロピ
ルメタクリレート（ＨＦＩＰＭＡ）１１．８６ｇ（５，
００Ｘ １０ ”ｍｏｌ）および過酸化ベンゾイル（Ｂ
ＰＯ）０．０１７ｇ（４，１３Ｘ１０ ”ｍｏｌ）を入
れ、重合管を真空ラインに接続し、液体窒素で凍結した
。この系を１０ ”Ｔｏｒｒ以下で脱気し系内の酸素を
送り出し再び融解した。この操作を３回繰り返した後、
コックを閉じ重合管中の千ツマ−の一部が溶解しはじめ
た時点で気相中にプラズマを発生させた。 １３．５６
ＭＨｚの高周波発生装置により５０１ｉ１６０秒間プラ
ズマ処理を行った。重合管を封管し２５℃で静置し、５
日間後重合を行った。得られた重合反応物をテトラヒド
ロフラン１００＋ａｌに溶解し、メタノール２．０Ｑで
再沈殿させて精製し、白色ポリマーを得た。得られたポ
リマーの重合は２．３４ｇ（収率は１３．９重量％）で
あった。このポリマーの融解温度は２６３．０〜２７６
．５℃であった。これは、約８，８ Ｘ １０’の分子
量に相当する。Experimental example 1 Pyrex glass polymer tube with inner diameter 15wn (capacity 42
ml) of methyl methacrylate (HMA) 5.34ml
(5,00xlO”mol), hexafluoroisopropyl methacrylate (HFIPMA) 11.86g (5,
00X 10” mol) and benzoyl peroxide (B
PO) 0.017g (4.13 x 10" mol) was added, the polymerization tube was connected to a vacuum line, and frozen with liquid nitrogen. The system was degassed at 10" Torr or less to remove oxygen from the system and melted again. . After repeating this operation three times,
The cock was closed and plasma was generated in the gas phase at the point when a portion of the 1000 yen in the polymerization tube began to dissolve. 13.56
Plasma treatment was performed using a 501i high frequency generator for 160 seconds. Seal the polymerization tube and leave it at 25°C for 5
Polymerization was carried out after 1 day. The obtained polymerization reaction product was dissolved in 100+ al of tetrahydrofuran and purified by reprecipitation with 2.0 Q of methanol to obtain a white polymer. The amount of polymer obtained was 2.34 g (yield: 13.9% by weight). The melting temperature of this polymer is 263.0-276
．． The temperature was 5°C. This corresponds to a molecular weight of approximately 8,8 x 10'.
実施例１
実験例１で得られたポリマーの１重量％メチルイソブチ
ルケトン溶液をスピンコーター（ミカサ（株）製ＩＨ−
０２型）を用いてシリコンウェハー上に厚さ３００ｎ＋
ｍポリマーの薄膜のコーティングを行い、そして、ベー
キング（１７０℃、３０分間）を行ったのち、フッ酸に
よる耐エツチング性を調べた。（参考図１−Ａ）耐エツ
チング性は５０％フッ酸水溶液を該ウェハー上に綿棒に
て滴下し、２５℃５分間静置した。水洗後表面を観察し
たが、変性、侵食などはみとめられなかった。また、該
共重合体の紫外吸収スペクトルは、ＰＭＭＡのそれとほ
ぼ同じであり、１９３ｎｍ吸収での透過率は約２０−３
０％の間にある。（第１図の■）これに対し、ＰＭＭＡ
ではほぼ咋である。（第１図の■）比較例１
実験例１の共重合体（ＭＭＡ−ＨＦＩＰＭＡ）の代わり
にポリメタクリル酸メチル（ＰＭＭＡ）超高分子量（Ｍ
ｖ：粘度平均分子量２．７×１０５）を合成し、実施例
１と同様にして耐酸試験を行ったところ、弗酸水（ＨＦ
）溶液によって浸されることが分った。（参考図１−Ｂ
）比較例２
実験例１の共重合体（ＭＭＡ−ＨＦＩＤＭＡ）の代わり
にＭ阿Ａ単位６０モル当り、２・ビニルナフタレン１モ
ルを実施例１と同様に反応させ超高分子量（Ｍｖ：約２
．５×１０６）を合成し、実施１と同様に耐酸試験を行
ったところ、弗酸水Ｈ，Ｆ溶液によって浸される。（参
考図１−Ｃ）。Example 1 A 1% by weight methyl isobutyl ketone solution of the polymer obtained in Experimental Example 1 was coated with a spin coater (IH-
02 type) to a thickness of 300n+ on a silicon wafer.
After coating with a thin film of m polymer and baking (170° C., 30 minutes), the etching resistance with hydrofluoric acid was examined. (Reference Figure 1-A) Etching resistance was determined by dropping a 50% hydrofluoric acid aqueous solution onto the wafer using a cotton swab, and leaving it at 25°C for 5 minutes. After washing with water, the surface was observed, but no degeneration or erosion was observed. Moreover, the ultraviolet absorption spectrum of the copolymer is almost the same as that of PMMA, and the transmittance at 193 nm absorption is about 20-3.
It is between 0%. (■ in Figure 1) On the other hand, PMMA
So it's mostly Kui. (■ in Figure 1) Comparative Example 1 Polymethyl methacrylate (PMMA) was used instead of the copolymer (MMA-HFIPMA) of Experimental Example 1.
v: viscosity average molecular weight 2.7 x 105) was synthesized and an acid resistance test was conducted in the same manner as in Example 1.
) was found to be soaked by the solution. (Reference Figure 1-B
) Comparative Example 2 Instead of the copolymer (MMA-HFIDMA) of Experimental Example 1, 1 mole of 2-vinylnaphthalene was reacted per 60 moles of M-A units in the same manner as in Example 1 to obtain an ultra-high molecular weight (Mv: about 2
．． 5×106) was synthesized and subjected to an acid resistance test in the same manner as in Example 1, and was immersed in hydrofluoric acid H and F solutions. (Reference Figure 1-C).
（効果）
以上、述べたように本発明はポリメチルメタアクリレー
トよりなる連鎖骨格中に弗素原子を導入することによっ
てポリメチルメタアクリレートと同様にエキシマレーサ
ー照射に適した紫外線領域に吸収スペクトルを有すると
共に耐エツチング性に対して極めて優れた抵抗を有する
のレジスト材として適した効果を奏するのである。(Effects) As described above, the present invention has an absorption spectrum in the ultraviolet region suitable for excimer laser irradiation like polymethyl methacrylate by introducing fluorine atoms into the chain skeleton made of polymethyl methacrylate. It has excellent etching resistance and is suitable as a resist material.
第１図は本発明実施例１における共重合体及びＰＭＭＡ
の紫外吸収スペクトルである。
■ 実施例１における共重合体
■ ＰＭＭＡFigure 1 shows the copolymer and PMMA in Example 1 of the present invention.
This is the ultraviolet absorption spectrum of ■ Copolymer in Example 1 ■ PMMA
Claims (1)
位当り弗素原子を少なくとも１個含有せしめた重合体か
らなる紫外線吸収高分子材料。 （２）弗素原子を含有せしめた重合体が次の構造式を有
し、その分子量は５×１０＾５〜５×１０＾７である特
許請求の範囲第１項記載の紫外線吸収高分子材料。 ▲数式、化学式、表等があります▼（１） ここで、Ｒ＿１、Ｒ＿３はＨ又はＣＨ＿３基、Ｒ＿２は
炭素数１〜５のアルキル基である。Ｒ＿４は炭素数１〜
８のアルキル基であって、少なくとも１個の水素原子を
弗素原子で置換したものである。また、ｍ／ｎ＝０・３
〜５である （３）弗素原子を含有せしめた重合体の分子量が５×１
０＾６〜５×１０＾７である特許請求の範囲第１項ない
し第２項のいずれかに記載の紫外線吸収高分子材料。 （４）構造式（１）におけるＲ＿４が炭素数１〜４のア
ルキル基である特許請求の範囲第１項ないし第３項のい
ずれかに記載の紫外線吸収高分子材料。 （５）メチルメタアクリレートと弗素原子を含有せしめ
たモノマーとを共重合させたことから成る特許請求の範
囲第１項ないし第４項のいずれかに記載の紫外線吸収高
分子材料。（６）弗素原子を含有せしめたモノマーがヘ
キサフロロイソプロピルメタクリレート、トリフルオロ
エチルメタクリレート、トリフロロエチルアクリレート
及びヘキサフロロイソプロピルアクリレートからなる群
からえらばれた弗素原子を含有したビニルモノマーであ
る特許請求の範囲第５項記載の紫外線吸収高分子材料。 （７）弗素原子を含有せしめたモノマーがヘキサフロロ
ブテン、ヘキサフロロブタジエン１、３及びヘキサフロ
ロプロパンからなる群からえらばれた少なくとも１個の
弗素原子を含有した弗素含有モノマーである特許請求の
範囲第７項記載の紫外線吸収高分子材料。[Scope of Claims] (1) An ultraviolet absorbing polymeric material comprising a polymer containing at least one fluorine atom per repeating unit in the methyl methacrylate chain skeleton. (2) The ultraviolet absorbing polymeric material according to claim 1, wherein the polymer containing fluorine atoms has the following structural formula and has a molecular weight of 5 x 10^5 to 5 x 10^7. . ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) Here, R_1 and R_3 are H or CH_3 groups, and R_2 is an alkyl group having 1 to 5 carbon atoms. R_4 has 1 or more carbon atoms
8, in which at least one hydrogen atom has been replaced with a fluorine atom. Also, m/n=0.3
~5 (3) The molecular weight of the polymer containing fluorine atoms is 5 × 1
The ultraviolet absorbing polymeric material according to any one of claims 1 to 2, which has a molecular weight of 0^6 to 5x10^7. (4) The ultraviolet absorbing polymeric material according to any one of claims 1 to 3, wherein R_4 in structural formula (1) is an alkyl group having 1 to 4 carbon atoms. (5) The ultraviolet absorbing polymeric material according to any one of claims 1 to 4, which is obtained by copolymerizing methyl methacrylate and a monomer containing a fluorine atom. (6) Claims in which the fluorine atom-containing monomer is a fluorine atom-containing vinyl monomer selected from the group consisting of hexafluoroisopropyl methacrylate, trifluoroethyl methacrylate, trifluoroethyl acrylate, and hexafluoroisopropyl acrylate. The ultraviolet absorbing polymer material according to item 5. (7) Claims in which the monomer containing a fluorine atom is a fluorine-containing monomer containing at least one fluorine atom selected from the group consisting of hexafluorobutene, hexafluorobutadiene 1, 3, and hexafluoropropane. The ultraviolet absorbing polymer material according to item 7.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62251635A JPH0195115A (en) | 1987-10-07 | 1987-10-07 | Ultraviolet-absorptive polymer material |
| EP19880908743 EP0380667A4 (en) | 1987-10-07 | 1988-10-07 | Ultraviolet-absorbing polymer material and photoetching process |
| US07/469,476 US5157091A (en) | 1987-10-07 | 1988-10-07 | Ultraviolet-absorbing polymer material and photoetching process |
| PCT/JP1988/001028 WO1989003402A1 (en) | 1987-10-07 | 1988-10-07 | Ultraviolet-absorbing polymer material and photoetching process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62251635A JPH0195115A (en) | 1987-10-07 | 1987-10-07 | Ultraviolet-absorptive polymer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0195115A true JPH0195115A (en) | 1989-04-13 |
Family
ID=17225754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62251635A Pending JPH0195115A (en) | 1987-10-07 | 1987-10-07 | Ultraviolet-absorptive polymer material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0195115A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3184560A1 (en) * | 2015-12-22 | 2017-06-28 | Solvay SA | Photo-curable copolymer, photo-curable resin composition comprising the same, and anti-fingerprint film made therefrom |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139515A (en) * | 1980-03-31 | 1981-10-31 | Daikin Ind Ltd | Polyfluoroalkyl acrylate copolymer |
| JPS58160951A (en) * | 1982-02-24 | 1983-09-24 | マツクス−プランク−ゲゼルシヤフト・ツ−ル・フエルデルング・デル・ヴイツセンシヤフテン・エ−・フアウ | Positive resist material, manufacture thereof and positive resist for forming surface texture of material made thereof |
| JPS58173104A (en) * | 1982-04-05 | 1983-10-12 | Nippon Telegr & Teleph Corp <Ntt> | Polymer film grafted by electric discharge and its production |
-
1987
- 1987-10-07 JP JP62251635A patent/JPH0195115A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139515A (en) * | 1980-03-31 | 1981-10-31 | Daikin Ind Ltd | Polyfluoroalkyl acrylate copolymer |
| JPS58160951A (en) * | 1982-02-24 | 1983-09-24 | マツクス−プランク−ゲゼルシヤフト・ツ−ル・フエルデルング・デル・ヴイツセンシヤフテン・エ−・フアウ | Positive resist material, manufacture thereof and positive resist for forming surface texture of material made thereof |
| JPS58173104A (en) * | 1982-04-05 | 1983-10-12 | Nippon Telegr & Teleph Corp <Ntt> | Polymer film grafted by electric discharge and its production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3184560A1 (en) * | 2015-12-22 | 2017-06-28 | Solvay SA | Photo-curable copolymer, photo-curable resin composition comprising the same, and anti-fingerprint film made therefrom |
| WO2017108936A1 (en) * | 2015-12-22 | 2017-06-29 | Solvay Sa | Photo-curable copolymer, photo-curable resin composition comprising the same, and anti-fingerprint film made therefrom |
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