JPS63258909A - Styrene polymer containing silicon atoms and allyl groups, composition therefrom and its use - Google Patents
Styrene polymer containing silicon atoms and allyl groups, composition therefrom and its useInfo
- Publication number
- JPS63258909A JPS63258909A JP245886A JP245886A JPS63258909A JP S63258909 A JPS63258909 A JP S63258909A JP 245886 A JP245886 A JP 245886A JP 245886 A JP245886 A JP 245886A JP S63258909 A JPS63258909 A JP S63258909A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polymer
- integer
- general formula
- positive integer
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims description 37
- 238000000034 method Methods 0.000 claims description 46
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims 21
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 238000001312 dry etching Methods 0.000 abstract description 12
- 238000010894 electron beam technology Methods 0.000 abstract description 10
- WQDGTJOEMPEHHL-UHFFFAOYSA-N 1-chloro-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(Cl)C=C1 WQDGTJOEMPEHHL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010884 ion-beam technique Methods 0.000 abstract description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 5
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 abstract description 3
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- 239000000178 monomer Substances 0.000 description 40
- 239000010410 layer Substances 0.000 description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000012044 organic layer Substances 0.000 description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 21
- 239000011777 magnesium Substances 0.000 description 21
- 229910052749 magnesium Inorganic materials 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000543 intermediate Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 13
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000011161 development Methods 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 11
- 239000007818 Grignard reagent Substances 0.000 description 10
- 150000004795 grignard reagents Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000000992 sputter etching Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- -1 Polydimethylsiloxane Polymers 0.000 description 6
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000059 patterning Methods 0.000 description 5
- QNMCVACUQGEWJP-UHFFFAOYSA-N 2-[(4-azidophenyl)methylidene]cyclohexan-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=C1C(=O)CCCC1 QNMCVACUQGEWJP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000007261 regionalization Effects 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910018540 Si C Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- LMQNPINUXNVGGV-UHFFFAOYSA-N chloro-tris(prop-2-enyl)silane Chemical compound C=CC[Si](Cl)(CC=C)CC=C LMQNPINUXNVGGV-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 102000001291 MAP Kinase Kinase Kinase Human genes 0.000 description 1
- 108060006687 MAP kinase kinase kinase Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 210000001215 vagina Anatomy 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Compositions Of Macromolecular Compounds (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）
本発明はケイ素原子を含むスチレン系重合体及びレジス
ト組成物および使用方法に［関し、特に半導体条状回路
、ａプ乳バブルメモリ等の鑓則パターン形、ｉ法に通し
たケイ素原子とアリル基とを含むスチレン系重合体及び
レジスト組成物及びパターン形成方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a styrene polymer containing silicon atoms, a resist composition, and a method for using the same, and particularly relates to a styrene polymer containing a silicon atom, a resist composition, and a method for using the same, particularly for semiconductor strip circuits, aperture bubble memories, etc. The present invention relates to a styrenic polymer containing a silicon atom and an allyl group passed through the i-method, a resist composition, and a pattern forming method.
（従来の技術）
集積回路、バブルメモリ素子などの製造に２いて光学的
リソグラフィまた＃ｉ電子ビームリソグラフィーを用い
ては細なパターンを形成する際、光学的リングラフィに
おいては基板からの反射波の彰撞、１子ビームリングラ
フィにおいては電子政乱の影ｊＫよりレジストが厚い場
合は帛像度が低下することが知られている。現像により
得られたレジストパターンを、１度よく基板に転写する
友めに、ドライエッチング：パ用いられるが、高解像度
のレジストパターンを（８もために、薄いレジストノー
を使用すると、ドライエツチングによりレジストもエツ
チングされ基板を加工するための十分な耐性を示さない
という不都合さがある。又１段差部に、臀いては、この
段差を平坦化するために、レジストＪ１！を厚（塗る・
３′模が生じ、かかるレジスト層に微細なパターンを形
成することは著しく困難であるといえる。(Prior art) When optical lithography or #i electron beam lithography is used to form fine patterns in the production of integrated circuits, bubble memory devices, etc., optical lithography involves the generation of reflected waves from a substrate. In single beam phosphorography, it is known that when the resist is thicker, the image quality decreases. Dry etching is used to transfer the resist pattern obtained by development onto the substrate once, but if a thin resist pattern is used to transfer a high-resolution resist pattern (8), dry etching There is an inconvenience that the resist is also etched and does not have sufficient resistance for processing the substrate.Also, in order to flatten this step, a thick layer of resist J1!
A 3' pattern occurs, and it can be said that it is extremely difficult to form a fine pattern on such a resist layer.
かかる不都合さを解決するために三層荷造レジストカシ
ェイーエム・モラン（Ｊ−Ｍ＠Ｍｏｒａ口）うによって
ジャーナル・オプ・バキューム・サイエンス・アンド−
テクノロジー（Ｊ−Ｖａｃｔ＋ｕｍＳｃｉｅｎｃｅ ａ
ｎｄ Ｔｅｃｈｎｏｌｏｇｙ）第１６巻１６２０ヘージ
（１９７９年）に提案されている。三Ｍ楢造においては
、第一層（Ｒ下層）に厚い有機層を塗布したのち中間層
としてシリコン酸化膜、シリコン窒化膜、シリコン膜な
どのように０２を使用するドライエツチング（以下ｏ、
二セコ４という）において蝕刻され難い無機物質材料を
形成する。しかる後、中間層の上にレジストをスピン塗
布し、Ｉ’４ 子ビームや光によりレジストをｖ４光、
現１象丁；）。得られたレジストパターンをマスクに中
間ノ・】をドライエツチングし、しかる後この中間１Ｂ
をマスクに第一層の厚い有機層を０２を用いた反応性ス
パッタエツチング法によりエツチングする。この方法に
より薄い高解像度のレジストパターンを厚い４１機層の
パターンに変換することか出来る。しかしながら、この
ような方法においては第一層を形成した後、中間層を蒸
着法、スパッタ法あるいはプラズマＣＶＤ法により形成
し、さらにパターンニング用レジストを塗布するため工
程が複雑で、かつ長くなるという欠点がある。In order to solve this inconvenience, a three-layer packaging resistor was developed by K.M.
Technology (J-Vact+umScience a
nd Technology) Volume 16, 1620 Hage (1979). At SanM Naraso, after coating a thick organic layer on the first layer (R lower layer), dry etching (hereinafter referred to as o,
Forms an inorganic material that is difficult to be etched (referred to as Niseko 4). After that, a resist is spin-coated on the intermediate layer, and the resist is exposed to the I'4 beam or light.
Currently 1 elephant;). Using the obtained resist pattern as a mask, dry-etch the intermediate 1B.
Using this as a mask, the first thick organic layer is etched by reactive sputter etching using 02. This method can convert a thin high-resolution resist pattern into a thick 41-layer pattern. However, in this method, after forming the first layer, the intermediate layer is formed by vapor deposition, sputtering, or plasma CVD, and then a patterning resist is applied, which makes the process complicated and long. There are drawbacks.
バターニング用レジストがドライエツチングに対して強
ければ、パターニング用しジストヲマスクに厚い有機層
をエツチングすることができるので、二層構造とするこ
とができ工程を簡略化することができる。If the resist for patterning is resistant to dry etching, a thick organic layer can be etched onto the resist for patterning, resulting in a two-layer structure and simplifying the process.
かかる三重構造レジストに使用される上記０２几ＩＥに
対する耐性に優れた物質としてはポリジメチルシロキサ
ンが知られており、このポリジメチルシロキサンは０ｚ
ＲＩＢに対して耐性が著しく優れ、エツチングレートは
ほぼ零であることは公知である（ジーエヌテーラー・テ
ィーエムウォルファンドジェーエムモラン、ジャーナル
オブバキュームサイエンスアントテクノロジー、１９（
４）。Polydimethylsiloxane is known as a material with excellent resistance to the above-mentioned 0z IE used in such triple structure resists, and this polydimethylsiloxane is
It is known that the resistance to RIB is extremely high and the etching rate is almost zero (GN Taylor TM Wolffand JM Moran, Journal of Vacuum Science Ant Technology, 19).
4).
８７２．１９８１）（Ｇ、Ｎ、Ｔｏｙｌｏｒ、ＴｏＭ、
Ｍｏｒａｎ、Ｊ。872.1981) (G, N, Toylor, ToM,
Moran, J.
Ｖａｃｕｕｍ Ｓｃｉ、ａｎｄ Ｔｅｄ、、１９（４
）、８７２ａ１９８１）が、このポリマーは常温で液状
であるので、はこりが付着しゃ丁い。加えて流動性があ
るため高解像度が得に（いなどの欠点がありレジスト材
料ととしては適さない。Vacuum Sci, and Ted, 19(4
), 872a1981), but since this polymer is liquid at room temperature, it prevents lumps from adhering to it. In addition, its fluidity makes it difficult to achieve high resolution, making it unsuitable as a resist material.
われわれは丁でに上記パターンニング用レジストとして
トリアルキルシリルスチレンの単独重合体および共重合
体を提案した（特願昭５７−１２３８６６号（特開１ｉ
５５９−１５４１９号〕、特願昭５７−１２３８６５号
（特開昭５９−１５２４３号）。We have recently proposed trialkylsilylstyrene homopolymers and copolymers as the above-mentioned patterning resists (Japanese Patent Application No. 123866/1986
No. 559-15419], Japanese Patent Application No. 57-123865 (Japanese Unexamined Patent Publication No. 59-15243).
（発明の解決しようとする問題点）
上記本出願人の提案に係わるパターンニング用レジスト
は、ポリジメチルシロキサンを含むレジストの欠点を解
決するものの、深紫外線またはイオンビーム（Ｄｅｅｐ
ＵＶもしくはＥＢ）露光に対して感度は優れており、Ｄ
ｅｅｐＵＶ もしくはＢＢ露光用レジストとしては適し
ているが、近紫外および可視光の露光に対しては架橋せ
ず、フォト用レジストとして使用出来なかった。(Problems to be Solved by the Invention) Although the patterning resist proposed by the applicant above solves the drawbacks of resists containing polydimethylsiloxane, it
It has excellent sensitivity to UV or EB) exposure, and
Although it is suitable as a resist for eepUV or BB exposure, it does not crosslink when exposed to near-ultraviolet and visible light, and cannot be used as a photoresist.
本発明の目的は、電子線、Ｘ線、深紫外線イオンビーム
あるいはこｎらに加えて近紫外線に対しても非常に高感
度で微細パターンが形成でき、しかもドライエツチング
に対して強い耐性をもつ重合体およびそれを含む組成物
およびその使用方法を提供することにある。The object of the present invention is to be able to form fine patterns with extremely high sensitivity to electron beams, X-rays, deep ultraviolet ion beams, or near ultraviolet rays in addition to these, and to have strong resistance to dry etching. An object of the present invention is to provide a polymer, a composition containing the same, and a method for using the same.
（問題点を解決するための手段）
本発明者らは、このような状況に鑑みて研究を続けた結
果、重合体の単量体ユニット中のシリコン原子およびア
リル基を有すると、０２による反応性スパッタエツチン
グに対して極めて強く、厚い有機膜をエツチングする際
の臂スクになること。(Means for solving the problem) As a result of continuing research in view of the above situation, the present inventors found that when a polymer has a silicon atom and an allyl group in its monomer unit, the reaction by 02 It is extremely resistant to sputter etching and serves as a backbone when etching thick organic films.
また電子線、Ｘ線、深紫外線イオンビームに対して、非
常に高感度であること、さらにビスアジド化合物を添加
すると、近紫外線に対しても非常に高感度であることを
見出し、本発明をな丁に至った。We also discovered that it is extremely sensitive to electron beams, X-rays, and deep ultraviolet ion beams, and that when a bisazide compound is added, it is also extremely sensitive to near ultraviolet rays. It came down to Ding.
本願第１発明は、構成単位にケイ素およびアリル基を含
むスチレン重合体であり、その構成単位の一般式として
、
ｎ
（式中、几は水素“または低級アルキル基を表わし、Ｘ
は一〇−または＋ＣＨ２す を表わし、ｌはＯを含む正
の整数、ｎは０，１または２を表わし。The first invention of the present application is a styrene polymer containing silicon and an allyl group as constituent units, and the general formula of the constituent units is n (wherein, 几 represents hydrogen or a lower alkyl group, and
represents 10- or +CH2, l represents a positive integer including O, and n represents 0, 1 or 2.
ｍは１，２または３を表わし、ｎ十ｍは３であり、Ｐと
２とは正の整数を夫わ丁）で示さ７Ｌる一七合体を含む
。m represents 1, 2, or 3, n0m is 3, and P and 2 are positive integers, including 17 combinations.
（１）上記一般式において、炭素Ｃと結合するＲが水素
であり、！がＯであるとき、スチレン糸道；３ ｒ
（ＵＨ２−ＣＨ＝ＣＨ２） ＨＩｎ
（式中Ｘは正の整数を表わす）で示される。(1) In the above general formula, R bonded to carbon C is hydrogen, and! When is O, styrene thread path; 3 r
It is represented by (UH2-CH=CH2) HIn (in the formula, X represents a positive integer).
上記において使用した単量体は次の様な方法で製造され
る。The monomers used above are produced by the following method.
ＣＨ２＝ＣＨ
Ｃ！
（式中、几は低級アルキル基を表わし、ｍは整数で１〜
３を表わし、ｎは整数で１又は２を表わし、ｎ十ｍは３
である。）上式でわかる様に、クロル化スチレン（０２
ｍ又は１位）に乾燥ＴＨＩＩ’中、マグネシウムと反応
させグリニヤール試薬をＨ造Ｌ、ジアルキルアリルクロ
ロシラ／、もしくはアルキルジアリルクロロシラン、も
しくはトリアリルクロロシランと反応きせて本発明で使
用した単量体を製造した。 −
上記（１）で使用した重合体は下記の式に従い製造され
る。CH2=CH C! (In the formula, 几 represents a lower alkyl group, m is an integer from 1 to
3, n is an integer and represents 1 or 2, n0m is 3
It is. ) As can be seen from the above formula, chlorinated styrene (02
The monomer used in the present invention is obtained by reacting the Grignard reagent with magnesium in dry THII', dialkylallylchlorosilane/or alkyldiallylchlorosilane, or triallylchlorosilane. Manufactured. - The polymer used in (1) above is produced according to the following formula.
（式中、几は低級アルキル基を表わし、出は整数で１〜
３を表わし、ｎは整数で１又は２わ表わし、ｎ ＋ｒｏ
は３である。又は正の整数を表わ丁〕上式で示しｆｃ様
に、本発明で使用し７０４１ｍ 献体はＢｕＬ ｉで、
丁なわちアニオン開始剤により、多分散度の小さい、そ
してかつ低分子喧から高分子看の任意の分子量の重合体
をＪＲ造することが出来ろ〇この重合体は一般の有機溶
剤１例えばベンゼン。(In the formula, 几 represents a lower alkyl group, and the number is an integer from 1 to
3, n is an integer and represents 1 or 2, n +ro
is 3. Or a positive integer] As shown in the above formula, fc is used in the present invention, and the donated body is BuLi,
In other words, by using an anionic initiator, it is possible to synthesize a polymer with a low polydispersity and any molecular weight ranging from low molecular weight to high molecular weight. .
トルエン、クロロベンゼン、アセトン、クロロホルム等
に可溶で、ガラス転移点の高いフィルムが容易に得られ
る。メタノール、エタノールなどには不溶である。It is soluble in toluene, chlorobenzene, acetone, chloroform, etc., and a film with a high glass transition point can be easily obtained. Insoluble in methanol, ethanol, etc.
（１１）また、上記一般式において、炭素と結合する几
をメチル基とし、ｌを０にすると、スチレン系重合体の
一般式は。(11) Furthermore, in the above general formula, if the group bonding to carbon is a methyl group and l is set to 0, the general formula of the styrene polymer is as follows.
ＣＨ。CH.
番 （式中Ｘは正の整数を表わす）で示される。number (In the formula, X represents a positive integer.)
上記において使用した単量体は次の様な方法で製造され
る。The monomers used above are produced by the following method.
ＣＨ３ Ｃ）（、＝Ｃ ＣＨ。CH3 C)(,=C CH.
ＣＨ，＝Ｃ
（式中、Ｒは低級アルキル基を表わし、ｍは整数で１〜
３を表わし、ｎは整数で１又は２を表わし、ｎ−４−ｒ
ｎは３である）
上式でわかる様に、クロル化スチレン（０＋ ＩＩＩ
ｍ又はｐ位）に乾１ＴＨＦ中、マグネシウムと反応させ
グリニヤール試薬を製造し、ジアルキルアリルクロロシ
ラン、もしくはアルキルジアリルクロロシラン、もしく
はトリアリルクロロシランと反応させて本発明で使用し
た単量体を製造した。CH,=C (wherein R represents a lower alkyl group, m is an integer from 1 to
3, n is an integer and represents 1 or 2, n-4-r
n is 3) As can be seen from the above formula, chlorinated styrene (0+ III
The Grignard reagent was prepared by reacting the m or p position with magnesium in dry 1 THF, and the monomer used in the present invention was prepared by reacting with dialkylallylchlorosilane, alkyldiallylchlorosilane, or triallylchlorosilane.
上記（ｉｔ）で使用した重合体は下記の式に従い製造さ
れる。The polymer used in (it) above is produced according to the following formula.
ＣＨ３
ＣＨ３
（式中、Ｒは低級アルキル基を表わし、ｍは整数で１〜
３を表わし、ｎは整数で１又は２を表わし、ｎ＋ｍは３
である。Ｘは正の整数を表わ丁）上式で示した様に１本
発明で使用した単量体はＢｕＬ ｉで、丁なわちアニオ
ン重合法により、多分散度の小さい、そしてかつ低分子
量から高分子量の任意の分子量の重合体を製造すること
が出来る。CH3 CH3 (in the formula, R represents a lower alkyl group, m is an integer from 1 to
3, n is an integer and represents 1 or 2, n+m is 3
It is. (X represents a positive integer.) As shown in the above formula, the monomer used in the present invention is BuLi, which has a low polydispersity and a low molecular weight by an anionic polymerization method. High molecular weight polymers of any desired molecular weight can be produced.
この重合体は一般の有機溶剤１例えばベンゼン、トルエ
ン、クロロベンゼン、アセトン、クロロホルム等に可溶
で、ガラス転移点の高いフィルムが容易に得られる。メ
タノール、エタノールなどには不溶である。This polymer is soluble in common organic solvents such as benzene, toluene, chlorobenzene, acetone, chloroform, etc., and a film with a high glass transition point can be easily obtained. Insoluble in methanol, ethanol, etc.
（１１〇 一方、上記一般式において、炭素と結合す
る几をメチル基とし、Ｘを−ＣＨ２−にし、ｌを１とし
たとき、スチレン系重合体の構成単位は一般式
Ｃ１（。(110 On the other hand, in the above general formula, when the phosphor bonded to carbon is a methyl group, X is -CH2-, and l is 1, the structural unit of the styrene polymer is the general formula
C1(.
Ｃ■■２ ＣＨ Ｈ２ （式中、Ｘは正の整数を表わ丁）で示される。C■■2 CH H2 (In the formula, X represents a positive integer.)
上記（冊において使用した単１１体は次のような方法で
製造される。The single 11 units used in the above book are manufactured by the following method.
ＣＨ。CH.
Ｃ１−Ｉ□Ｃ１
Ｈｓ
ＣＨ２＝Ｃ
■
Ｃ）１３−８ｉ −ＣＨ３
鴬
ＣＨ２
ＣＨ３−８ｔ−ＣＨ３
ＣＨ２
ＣＨ
ＣＨ２
上式でわかる様に、４−クロル−α−メチルスチレンに
乾燥ＴＨＦ中、マグネシウムと反応させグリニヤール試
薬を製造し未反応のマグネシウムをろ過でのぞき、クロ
ルメチルジメチルクロルシランと反応させてクロルメチ
ルジメチルシリル−α−メチルスチレンを合成した。さ
らに、乾燥ＴＨＦ中、マグネシウムと反応させグリニヤ
ール試薬を製造し、アリルジメチルクロルシランと反応
させて本発明で使用した単量体を製造した。C1-I□C1 Hs CH2=C ■ C)13-8i -CH3 Tsumugi CH2 CH3-8t-CH3 CH2 CH CH2 As shown in the above formula, 4-chloro-α-methylstyrene reacts with magnesium in dry THF. A Grignard reagent was prepared, unreacted magnesium was removed by filtration, and it was reacted with chloromethyldimethylchlorosilane to synthesize chloromethyldimethylsilyl-α-methylstyrene. Furthermore, a Grignard reagent was produced by reacting with magnesium in dry THF, and a monomer used in the present invention was produced by reacting with allyldimethylchlorosilane.
上記（１１Ｄで使用した重合体は下記の式に基づいて製
造した。The polymer used in (11D) above was manufactured based on the following formula.
（式中、Ｘは正の整数を表わ丁）
上式で示した様に、上記（ｆｉｌ）で製造した単量体は
ＢｕＬｉで、すなわちアニオン重合法により、多分散度
の小さい、そしてかつ低分子量から高分子量の任意の分
子量の重合体を製造することか出来る。(In the formula, X represents a positive integer.) As shown in the above formula, the monomer produced in the above (fil) is BuLi, which has a low polydispersity and Polymers of any molecular weight, from low molecular weight to high molecular weight, can be produced.
この重合体は一般の有機溶剤、例えばベンゼン、トルエ
ン、キシレン、クロロベンゼン、アセトン、クロロホル
ム等に可溶で、メタノール、エタノールなどには不溶で
ある。This polymer is soluble in common organic solvents such as benzene, toluene, xylene, chlorobenzene, acetone, chloroform, etc., and insoluble in methanol, ethanol, etc.
（■公 上記一般式において、炭素と結合する几をメ
チル基とし、Ｘを−ＣＨ２−とし、ｌを２にすると、重
合体の構成単位の一般式は、
ＣＨ３
ＣＨ３−８１０Ｈ３
ＣＨ２
■
ＣＨ２
ＣＨ３−８ｉ−ＣＨ８
ＣＨ２
ＣＨ
ＣＨ２
（式中Ｘは正の整数を表わ丁）で示される。(■ Public) In the above general formula, if the phosphor bonded to carbon is a methyl group, X is -CH2-, and l is 2, the general formula of the constituent units of the polymer is: CH3 CH3-810H3 CH2 ■ CH2 CH3- It is represented by 8i-CH8 CH2 CH CH2 (in the formula, X represents a positive integer).
本発明において使用した中間体、ｊＡｆ体、重合体は次
の俤な方法で製造した。The intermediate, jAf body, and polymer used in the present invention were produced by the following extensive methods.
Ｍｇ 、ＴＨＦ −７８℃ ＣＨｌ ＣＨ，−８ｉ−ＣＨ。Mg, THF -78℃ CHl CH, -8i-CH.
■ ＣＨ２ ＣＨ２ 「 ＣＨ，−８ｉ−ＣＨ。■ CH2 CH2 " CH, -8i-CH.
■
ＣＨ２
ＣＨ
ＣＨ２
（式中Ｘは正の整数を表わ′″ｆ）
上記のように１．１，４，４−テトラメチル−１，４ジ
ンクロロジシルエチレンかう同モル層の臭化アリルのグ
リニヤール試薬を反応させて中間体を製造させ、４−ク
ロロ−α−メチルスチレンのグリニヤール試薬とＴＨＦ
中反応させることにより単量体を製造する。上式で示し
た様に、本発明でした使用した単量体はＢｕＬ ｉで、
丁なわちアンオン重合法により、多分散度の小さい、そ
してかつ低分子量から高分子量の任意の分子量の集合体
を製造することが出来る。■ CH2 CH CH2 (in the formula, The Grignard reagent is reacted to produce an intermediate, and 4-chloro-α-methylstyrene is reacted with the Grignard reagent and THF.
Monomers are produced by medium reaction. As shown in the above formula, the monomer used in the present invention is BuLi,
By the anionic polymerization method, it is possible to produce an aggregate having a low polydispersity and having any molecular weight ranging from low to high molecular weight.
また、重合体はシリコン原子を２個有しているため、シ
リコン濃度は重合体に対して１８．５％（Ｗ／Ｗ）とな
り高いので、レジスト組成物は転写の際下層のサイドエ
ツチングされにくい条件でもドライエツチングに対して
極めて強い耐性を有する。In addition, since the polymer has two silicon atoms, the silicon concentration is high at 18.5% (W/W) relative to the polymer, so the resist composition is difficult to side-etch the underlying layer during transfer. It has extremely strong resistance to dry etching even under certain conditions.
Ｍ 上記一般式において、炭素に結合している几をメ
チル基とし、Ｘを酸素原子とし、！を２にすると、重合
体の構成単位の一般式は、ＣＨ２
（式中Ｘは正の整数を表わす）で示される。M In the above general formula, 几 bonded to carbon is a methyl group, X is an oxygen atom, and! When is set to 2, the general formula of the structural unit of the polymer is represented by CH2 (in the formula, X represents a positive integer).
上記（Ｖ）において使用した中間体、単量体、重合体は
次の様な方法で製造される。The intermediates, monomers, and polymers used in (V) above are produced by the following method.
ｔｈｅｒ
Ｍｇ、ＴＨＦ
ＣＨｌ
ＣＨ３−８ｉ−ＣＨｌ
ＣＨ２
Ｃ）（
Ｉ
ＣＨ２
（式中Ｘは正の整数を表わす）
上記のように１，３−ジンフロロブトラメチルジシロキ
サンから同モル景の臭化アリルのグリニヤール試薬を反
応させて中間体を製造させ、４−クロロ−α−メチルス
チレンのグリニヤール試薬とＴ ＨＦ中叉応させること
てより単量体を製造する。上式で示した様に、本発明で
した使用した単量体はＢｕＬｉで、すなわちアンオン重
合法により、多分散度の小さい、そしてかつ低分子量か
ら高分子量の任意の分子量の集合体を製造することが出
来る。ther Mg, THF CHl CH3-8i-CHl CH2 C) ( I CH2 (in the formula, X represents a positive integer) As mentioned above, allyl bromide with the same molar profile is obtained from 1,3-difluorobutramethyldisiloxane. The intermediate is prepared by reacting the Grignard reagent of 4-chloro-α-methylstyrene with the Grignard reagent in THF to prepare the monomer. The monomer used in this invention is BuLi, that is, by the anionic polymerization method, it is possible to produce an aggregate with a low polydispersity and any molecular weight from low to high molecular weight.
この重合体は一般の有機溶剤、例えばベンゼン、トルエ
ンキシレン、クロロベンゼン、アセトン、クロロホルム
等に可溶で、メタノール、エタノールなどには不溶であ
る。This polymer is soluble in common organic solvents such as benzene, toluene, xylene, chlorobenzene, acetone, and chloroform, and insoluble in methanol, ethanol, and the like.
また、重合体はシリコン原子を２個有しているため、シ
リコン濃度は重合体に対して１９．３％ＣＷ／Ｗ）とな
り高いので、レジスト組成物は転写の際下層のサイドエ
ツチングされに（い条件でもドライエツチングに対して
極めて強い耐性を有する。In addition, since the polymer has two silicon atoms, the silicon concentration is high (19.3% CW/W) with respect to the polymer, so the resist composition is prevented from side-etching the underlying layer during transfer ( Extremely strong resistance to dry etching even under harsh conditions.
上記本願第１発明に単連する１１ｇ２発明は、本願第り
発明におけるレジスト材料が、そのままで電子線、Ｘ線
、深紫外線イオンビームに対して極めて高感度であるが
、光架橋剤として知られているビスアジドを添加すると
紫外線に対しても高感度なレジストとなることに鑑みて
なされたものである。本願第２発明で用いられるビスア
ジドとしては、４，４′−ジアジドカルコン、２，６−
ジー′（４′−アジドベンザル）シクロヘキサノン、２
゜６−ジー（４′−アジドベンザル）−４−メチルシク
ロヘキサノン、２，６−ジー（４−アジドベンザル）−
４−ハイドロオキシンクロヘキサノンなどが挙げられる
。光架橋剤の添加量は、過少または過大であると紫外線
に対する感度が低下し、又過大に添加した組成物は０２
のドライエツチングに対する耐性を悪くてるので、重合
体に対して０．１〜３０重量％加えることが望ましい。The 11g2 invention that is connected to the first invention is that the resist material in the first invention is extremely sensitive to electron beams, X-rays, and deep ultraviolet ion beams as it is, but it is known as a photocrosslinking agent. This was done in view of the fact that adding bisazide, which contains bisazide, results in a resist that is highly sensitive to ultraviolet light. The bisazide used in the second invention of the present application includes 4,4'-diazide chalcone, 2,6-
Z'(4'-azidobenzal)cyclohexanone, 2
゜6-di(4'-azidobenzal)-4-methylcyclohexanone, 2,6-di(4-azidobenzal)-
Examples include 4-hydroxin clohexanone. If the amount of photocrosslinking agent added is too little or too much, the sensitivity to ultraviolet rays will decrease, and if the amount of photocrosslinking agent added is too much, the composition will be 0.2
Since this impairs the resistance to dry etching of the polymer, it is desirable to add it in an amount of 0.1 to 30% by weight based on the weight of the polymer.
また重合体は一般にネガ型レジストとして用いるとき高
分子量であれば高感度となるが現像時の膨潤により解像
度を損う。通例、分子量百方を越えるものは、高い解像
性を期待できない。一方、分子量を小さくすることは解
像性を向上させるが、感度は分子量に比例して低下して
実用性を失うだけでなく、分子量玉子以下では均一で堅
固な膜形成がむずかしくなるという問題がある。Furthermore, when a polymer is used as a negative resist, if the molecular weight is high, the sensitivity is generally high, but the resolution is impaired due to swelling during development. Generally, if the molecular weight exceeds 100, high resolution cannot be expected. On the other hand, reducing the molecular weight improves resolution, but not only does the sensitivity decrease in proportion to the molecular weight, making it impractical, but it also poses the problem that it becomes difficult to form a uniform and firm film below the molecular weight. be.
分子量分布の均一性も解像性に影響を与えることが知ら
れており、多分散度の小なる程良好な解像を示す。この
点、アニオン重合法から製造される場合は１分子量分別
せずに、直接多分散度の小さい、たとえば１．２もしく
はそル以下の重合体が得られるので、そのレジスト材料
は優れた解像性を有する。It is known that the uniformity of molecular weight distribution also affects resolution, and the smaller the polydispersity, the better the resolution. In this regard, when produced using an anionic polymerization method, a polymer with a small polydispersity, for example, 1.2 or less, can be obtained directly without single molecular weight fractionation, so the resist material has excellent resolution. have sex.
上記第１発明に重連てる第３発明は、上記Ｘａ１発明に
係わるスチレン系重合体をレジスト材料としてパターン
形成する方法であり、本願第１発明の重合体を２Ｉｍレ
ジスタ材料として使用するには、まず加工を施−「べき
基板上に第一層として厚い有機層をスピン塗布し、蒸発
、乾固させた後、本発明の重合体、組成物を厚い、有機
層の上にスピン塗布する。加熱、乾燥したのち所望のパ
ターンを電子線、Ｘ線イオンビームなどの放射線、また
は深紫外線、紫外線などの光を用いて描画１−１適当な
現（酸液を用いて現１壕を行なう。素子の加工の目的に
は、たとえば得られたパターンをマスクに第一層の厚い
有機層を０２を用いた反応性スパッタエツチングにより
エツチングすることが出来る。また、しかる後、微細パ
ターンが形成された厚い有機層をマスクに被加工材をエ
ツチングすることが出来る。又、この厚い有機層をイオ
ン打込みのマスクに用いることも出来る。或は、厚い有
機層が得られることを利用してリフトオフプロセスにも
適用出来る。A third invention that overlaps with the first invention is a method of forming a pattern using the styrene polymer according to the Xa1 invention as a resist material, and in order to use the polymer of the first invention as a 2Im resistor material, First, a thick organic layer is spin-coated as a first layer onto a substrate to be processed, and after evaporation and drying, the polymer composition of the present invention is spin-coated onto the thick organic layer. After heating and drying, a desired pattern is drawn using radiation such as an electron beam, an X-ray ion beam, or light such as deep ultraviolet rays or ultraviolet rays. For the purpose of device processing, for example, the first thick organic layer can be etched by reactive sputter etching using 02 using the obtained pattern as a mask. The workpiece can be etched using the thick organic layer as a mask. This thick organic layer can also be used as a mask for ion implantation. Alternatively, the thick organic layer can be used for the lift-off process. can also be applied.
上記第２発明に重連する第４発明は、上記第２発明に係
わる組成物をレジスト材料としてパターン形成を行なう
方法であり、本願第２発明の組成物を２層レジスト材料
として使用するには、まず加工を施すべき基板上に第一
層として厚い有機層をスピン塗布し、蒸発、乾固させた
後、本発明の重合体、組成物を厚い有機層の上にスピン
塗布する。加熱、乾燥したのち所望のパターンを電子線
、Ｘ線、イオンビームなどの放射線、または深紫外線、
紫外線などの光を用いて描画し、適当な現像液を用いて
現像を行なう。素子の加工の目的には、たとえば得られ
たパターンをマスクに第一層の厚い有機層を０２を用い
た反応性スパッタエツチングによりエツチングすること
か出来る。また、しかる後、微細パターンが形成された
厚い有機層をマスクに被加工材をエツチングすることか
出来る。A fourth invention that overlaps with the second invention is a method of forming a pattern using the composition according to the second invention as a resist material. First, a thick organic layer is spin-coated as a first layer on a substrate to be processed, and after evaporation and drying, the polymer or composition of the present invention is spin-coated on the thick organic layer. After heating and drying, the desired pattern is exposed to radiation such as electron beams, X-rays, ion beams, or deep ultraviolet rays.
Drawing is performed using light such as ultraviolet light, and development is performed using an appropriate developer. For the purpose of device processing, for example, the first thick organic layer can be etched by reactive sputter etching using 02 using the obtained pattern as a mask. After that, the workpiece can be etched using the thick organic layer on which the fine pattern is formed as a mask.
又、この厚い有機層をイオン打込みのマスクに用いるこ
とも出来る。或は、厚い有機層が得られることを利用し
てリフトオフプロセスにも適用出来る。This thick organic layer can also be used as a mask for ion implantation. Alternatively, it can also be applied to a lift-off process by taking advantage of the fact that a thick organic layer can be obtained.
（実施例１）
―
Ｈ２
鵞
Ｈ
Ｈ２
グリンヤール用マグネシウム７．０．９ （０，２９グ
ラム原子）オヨび乾燥ＴＨＥ’ｌＯｒＭを３００ｍＡフ
ラスコに仕込み、乾燥窒素ガスでフラスー内を置換した
。０．２ｍｌのエチルブロマイドを加え、加温してマグ
ネシウムを活性化させた。(Example 1) - H2 H2 Magnesium for Greenard 7.0.9 (0.29 gram atom) A 300 mA flask was charged with dry THE'1OrM, and the inside of the flask was replaced with dry nitrogen gas. 0.2 ml of ethyl bromide was added and heated to activate the magnesium.
ＴＨＦ６０ｍｌを加え、氷水で冷却し、ｐ−クロロスチ
レン２７−ＯＩＩ（０，１９５モル）を４時間を要して
滴下した。滴下終了後さらに２時間室温で反応を続けた
。加温して還流状態にし、ジメチル了りルクロルシラン
２６．９ Ｎ （０，２モル）を３時間と要して滴下し
た。さらに２時間還流状態で反応させ、室温に冷却後、
約３００ｍ４の水に投入した。約５００ｍＡのエーテル
を加え、抽出を行ない、エーテル液を硫酸マグネシウム
で乾燥させた。エーテルを留出後、減圧蒸留で生成物を
得た収量２４．４Ｆ（収率６２％）沸点１１４℃７ｍｍ
Ｈｇ
（実施例２）
冨
Ｃｆ（。60 ml of THF was added, cooled with ice water, and p-chlorostyrene 27-OII (0,195 mol) was added dropwise over 4 hours. After the dropwise addition was completed, the reaction was continued for another 2 hours at room temperature. The mixture was heated to reflux, and 26.9 N (0.2 mol) of dimethylchlorosilane was added dropwise over a period of 3 hours. The reaction was further carried out under reflux for 2 hours, and after cooling to room temperature,
It was poured into about 300m4 of water. Approximately 500 mA of ether was added to perform extraction, and the ether solution was dried over magnesium sulfate. After distilling off the ether, the product was obtained by distillation under reduced pressure. Yield: 24.4F (yield: 62%); Boiling point: 114℃, 7mm.
Hg (Example 2) Tomi Cf (.
冨 Ｈ ０Ｈ。wealth H 0H.
実施例１で合成した単量体およびＴＨＦを水素化カルシ
ウムで予備乾燥した。はじめに、装置を減圧下であたた
めガラス装置を乾燥させた。その後単量体１１１１を仕
込み、窒素浴で凍結してから。The monomer synthesized in Example 1 and THF were pre-dried with calcium hydride. First, the glass device was dried by warming the device under reduced pressure. After that, monomer 1111 was charged and frozen in a nitrogen bath.
減圧し、温めて液状状態にもどした。この操作を４回く
り返して単量体を脱気した後、ｉＮ−ブチルリチウム（
１，６Ｍ：へキサン中）０．１ｍ４を加えて単量体を完
全脱水した。この時単量体は黄色を示した。その後、ｔ
きフラスコへ蒸留した。この時単量体は少量重合した。The pressure was reduced and the mixture was warmed to return to a liquid state. After repeating this operation four times to degas the monomer, iN-butyllithium (
0.1 m4 of 1,6 M in hexane was added to completely dehydrate the monomer. At this time, the monomer showed yellow color. After that, t
The mixture was distilled into a flask. At this time, a small amount of the monomer was polymerized.
ＴＨＦ５０ｍｌも同様に脱気、脱水を行ない重きフラス
コへ蒸留し；／ｃ。50 ml of THF was similarly degassed, dehydrated, and distilled into a heavy flask; /c.
室温にて重合フラスコへラバーストッパーからマイクロ
シリンジを用いてロープチルリチウム（１，６Ｍ：ヘキ
サン中）４０μｌを加え、すぐにアセトン−ドライ”ｒ
イス浴で冷却させて重合を開始させた。４時間後メタノ
ール１ｎ１！をシリクで加えて重合を停止し、常圧にし
て、重合体溶液を５００ｍＪのメタノール中に投入した
。重合体は白色粉末となって析出し、ろ過して分離した
。さらにＭ Ｅ Ｋ Ｉｃ溶解させメタノールに投入し
、コノ操作を４回行なった。収量８．３ｇ（収率７４％
）。Add 40 µl of rope chill lithium (1,6 M in hexane) to the polymerization flask at room temperature using a microsyringe through a rubber stopper, and immediately add acetone-dry lithium.
Polymerization was initiated by cooling in a chair bath. 4 hours later methanol 1n1! was added using a silica to stop polymerization, the pressure was brought to normal, and the polymer solution was poured into 500 mJ of methanol. The polymer precipitated as a white powder and was separated by filtration. Furthermore, M E K Ic was dissolved and added to methanol, and the same operation was performed four times. Yield: 8.3g (yield: 74%)
).
重量″Ｉ−均分子量（Ｍｗ）＝７８，０００数平均分子
４１ｋ（Ｎ缶）＝７２，９００多分敏Ｋ （Ｍｗ／Ｍｎ
） ＝ １．０７重合体の分析値は次の様になる
。Weight "I - Average molecular weight (Mw) = 78,000 Number average molecular weight 41k (N can) = 72,900 Molecular sensitivity K (Mw/Mn
) = 1.07 The analytical values of the polymer are as follows.
赤外線吸収スペクトル（ｃｍ−”）： １２５０（８ｉ
−Ｃ）。Infrared absorption spectrum (cm-”): 1250 (8i
-C).
９９０（アリル基）、１６３０（ベンゼン核）核磁気共
鳴スペクトル（δ） ｐＰｍ ：０．２〜０．５ （６
Ｈ。990 (allyl group), 1630 (benzene nucleus) nuclear magnetic resonance spectrum (δ) pPm: 0.2-0.5 (6
H.
メチル基）、０．８〜３．３（１５Ｈ，メチレン基）、
４．２〜５．３（３Ｈ，オレフィン基）。methyl group), 0.8 to 3.3 (15H, methylene group),
4.2-5.3 (3H, olefin group).
６．０〜７．５（４Ｈ，ベンゼン核） （実施例３） ＣＨｌ ０Ｈ。6.0-7.5 (4H, benzene nucleus) (Example 3) CHl 0H.
品 ＣＨ。Goods CH.
グリニヤール用マグネシウム７、０ ＃ （０，２９グ
ラム原子）オヨび乾燥ＴＨＦ１０ｍｚを３００ｍ４７ラ
スコに仕込み、乾燥チッソガスでフラスコ内を置換した
。０．２ｍｌのエチルブロマイドを改え、加温してマグ
ネシウムを活性化させた。ＴＨＦ６０ｍｌを加え、氷水
で冷却し、ｐ−クロロ−α−メチルスチレン２９．７．
９ （０，１９５モル）を４時間を要して滴下した。滴
下終了後さらに２時間室温で反応を続けた。加温して還
流状態にし、ジメチルアリルクロルシラン２６．９１１
（０，２モル）ヲ３時間を要して滴下した。さらに２時
間、還流状態で反応させ、室温に冷却後、約３０．０ｍ
ｌの水に投入した。約５００ｍ４のエーテルを加え、抽
出を行ない、エーテル液を硫酸マグネシウムで乾燥させ
た。エーテルを留出後、減圧蒸留で生成物を得た。収量
３５．２．９（収率８４％）沸点７６℃１０、４ ｍｍ
Ｈｊｉｏ
（実施例４）
ＣＨ３
瘍
「
ＣＨ。Magnesium for Grignard grade 7.0 # (0.29 gram atom) and 10 mz of dry THF were charged into a 300 m 47 flask, and the inside of the flask was replaced with dry nitrogen gas. 0.2 ml of ethyl bromide was added and heated to activate the magnesium. Add 60 ml of THF, cool with ice water, and add 29.7 ml of p-chloro-α-methylstyrene.
9 (0,195 mol) was added dropwise over a period of 4 hours. After the dropwise addition was completed, the reaction was continued for another 2 hours at room temperature. Heat to reflux and dimethylallylchlorosilane 26.911
(0.2 mol) was added dropwise over a period of 3 hours. The reaction was continued under reflux for another 2 hours, and after cooling to room temperature, approximately 30.0 m
1 of water. Approximately 500 m4 of ether was added for extraction, and the ether solution was dried over magnesium sulfate. After distilling off the ether, a product was obtained by distillation under reduced pressure. Yield 35.2.9 (yield 84%) Boiling point 76℃ 10, 4 mm
Hjio (Example 4) CH3 tumor "CH.
ＣＨ ＣＨ。CH CH.
実施例３で合成した単量体およびＴＨＦを水素化カルシ
ウムで予備乾燥した。はじめに、装置を減圧下であたた
めガラス装置を乾燥させた。その後単量体１１．？を仕
込み、液体窒素浴で凍結してから、減圧にし、温めて液
体状態にもどした。この操作を４回くり返して単量体中
に含まれる空気を脱気した後、ｎ−ブチルリチウム（１
，６Ｍ：ヘキサン中）０．１ｇＭを加えて単量体を完全
脱水した。この時単量体は黄色を示した。その後、重合
７２スコヘ蒸留した。ＴＨＦ５０ｍＪ も同様に脱気、
脱水を行ない重合フラスコへ蒸留した。室温にて重合フ
ラスコへラバーストッパーからマイクロシリンジを用い
てｎ−ブチルリチウム（１，６Ｍ： ヘキ”）−ン中）
８０ ＃Ｊを加え、すぐにアセトン−ドライアイス浴
で冷却させて重合を開始させた。The monomer synthesized in Example 3 and THF were pre-dried with calcium hydride. First, the glass device was dried by warming the device under reduced pressure. Then monomer 11. ? was charged and frozen in a liquid nitrogen bath, then reduced pressure and warmed to return to a liquid state. After repeating this operation four times to degas the air contained in the monomer, n-butyllithium (1
, 6M in hexane) was added to completely dehydrate the monomer. At this time, the monomer showed yellow color. Thereafter, the polymerization was distilled into 72 sco. Degas THF50mJ in the same way.
It was dehydrated and distilled into a polymerization flask. Add n-butyllithium (1,6M hexane) to the polymerization flask at room temperature using a microsyringe from a rubber stopper.
80 #J was added and immediately cooled in an acetone-dry ice bath to initiate polymerization.
４時間後、メタノール１ｍｊをシリンジで加えて重合を
停止し、常圧にもどし、重合体溶液を５００ｍＪのメタ
ノール中に投入した。重合体は白色粉末となって析出し
、ろ過して分離した。さらにＭＥＫＫ溶解させメタノー
ルに投入し、この操作を４回行なった。収量１１９（収
率はは／ｌ′ｆ、１ｏ。After 4 hours, 1 mJ of methanol was added using a syringe to stop the polymerization, the pressure was returned to normal, and the polymer solution was poured into 500 mJ of methanol. The polymer precipitated as a white powder and was separated by filtration. Further, MEKK was dissolved and added to methanol, and this operation was repeated four times. Yield: 119 (yield: /l'f, 1o.
％である）。%).
軟化点 １６４〜１６５℃
重量平均分子せ（Ｍｗ）＝ ４１．４００゜数平均分子
量（Ｍ口）＝３９．４００
多分散度（Ｍｗ／Ｍ ｎ ） ＝ １．０５重合体の分
析値は次の様になる。Softening point 164-165°C Weight average molecular weight (Mw) = 41.400° Number average molecular weight (M) = 39.400 Polydispersity (Mw/Mn) = 1.05 The analytical values of the polymer are as follows. It will be like that.
赤外線吸収スペクトル（Ｃ１ｒＬ−１） ：１２５０
（８１−Ｃ）、９９０（アリル基）、ｌＧ２０（ベンゼ
ン核）核磁気共鳴スペクトル（δ） ｐｐｍ ： ０．
０〜０．８（９Ｈ，メチル基）、１．０〜２．０（４Ｈ
，メチレン基）、４．５〜６．０（３Ｈ，オレフィン基
）。Infrared absorption spectrum (C1rL-1): 1250
(81-C), 990 (allyl group), lG20 (benzene nucleus) nuclear magnetic resonance spectrum (δ) ppm: 0.
0-0.8 (9H, methyl group), 1.0-2.0 (4H
, methylene group), 4.5 to 6.0 (3H, olefin group).
６．２〜７．３（４Ｈ，ベンゼン核） （実施例５） ＣＨ３ ０Ｈ。6.2-7.3 (4H, benzene nucleus) (Example 5) CH3 0H.
Ｃ！：
グリ二ヤール用マグネシウム５．３．９ （０，２６グ
ラム原子）および乾燥テトラヒドロフラン（ＴＨＦ）２
０ｍｌを５ｏｏｔｎｌフラスコに仕込み、乾燥チッソガ
スでフラスコ内を置換した。０．２ｍｌのエチルブロマ
イドを加え、加温してマグネシウムを活性化させた。ｐ
−クロａ−α−メチルスチレン３０．４１／ （０，２
０モｈ） ／ＴＨＦ （４０ｎｉＡ：） ヲ２時間を
要して滴下した。滴下終了後さらに２時間室温で反応を
続けた。ガラスフィルターを用いて反応溶液をろ過し未
反応のマグネシウムを除いた。溶液を５００ｎ−の７シ
スコに仕込み、加已して還流状態にし、ジメチルクロロ
メチルクロロシラン２８．（５ｙ（０，２０モル）を１
時間を要して滴ＦＬ７ｔ。さらに３時間、還流状ｆ４で
反応させ、室温に冷許後、約３００ ｍａｌ：の冷水に
投入した。C! : Magnesium for Grignard 5.3.9 (0,26 gram atom) and dry tetrahydrofuran (THF) 2
0ml was placed in a 5ootnl flask, and the inside of the flask was replaced with dry nitrogen gas. 0.2 ml of ethyl bromide was added and heated to activate the magnesium. p
-Chloa-α-methylstyrene 30.41/ (0,2
0 moh)/THF (40 nA:) was added dropwise over a period of 2 hours. After the dropwise addition was completed, the reaction was continued for another 2 hours at room temperature. The reaction solution was filtered using a glass filter to remove unreacted magnesium. The solution was charged into a 500 n-7 cisco, heated to reflux, and dimethylchloromethylchlorosilane 28. (5y (0.20 mol) to 1
It took a while to drop FL7t. The reaction was continued at reflux f4 for another 3 hours, and after cooling to room temperature, it was poured into about 300 ml of cold water.
約５００ ＩＩ！のニーデルを加え、抽出を行ない、エ
ーテル層を硫酸マグネシウムで乾燥させた。エーテルを
留出後、減圧蒸留で生成物を得た。収量３５．０＃（７
８％）節点１０２℃／ １． □ ｒｒｕｎＨｇ０中間
体の分析値は次の様になる。About 500 II! of needle was added to perform extraction, and the ether layer was dried with magnesium sulfate. After distilling off the ether, a product was obtained by distillation under reduced pressure. Yield 35.0# (7
8%) Node 102℃/1. □ The analysis value of rrunHg0 intermediate is as follows.
赤外線吸収スペクトルＣｃｍ−”） ：１２５０（Ｓｉ
−Ｃ）。Infrared absorption spectrum Ccm-”): 1250 (Si
-C).
１６２０．１３９０，９００ （ビニＩＪ）？”ｙ）
、７４０（ＣＨｇＣ１
核磁気共鳴スペクトル（すｐｐｍ ：０．１６ （６Ｈ
。1620.1390,900 (Vini IJ)? ”y)
, 740 (CHgC1 nuclear magnetic resonance spectrum (ppm: 0.16 (6H
.
メチル基）、１．９５（２Ｈ，メチレン基）。methyl group), 1.95 (2H, methylene group).
２．６０（３Ｈ，メチル基）、４．８〜５．２（２Ｈ，
オレフィン）、７．２〜７．４（４Ｈ，ベンゼン核）。2.60 (3H, methyl group), 4.8-5.2 (2H,
olefin), 7.2-7.4 (4H, benzene nucleus).
（実施例６） ＣＨ３ ＣＨ２ ＣＨ，−８ｉ−ＣＨ。(Example 6) CH3 CH2 CH, -8i-CH.
ＣＨ２ ＣＨ ＣＨ。CH2 CH CH.
グリニヤール用マグネシウム２．９９ （０，１２グラ
ム原子）とＴＨＦｌｏｍＪを３００ｍ１プラスコに仕込
み、乾燥チッソガスで置換した。実施例５で製造した中
間体２２．４１（０，１モル）をＴＨＦ４０ｒＭに溶解
させた溶液を室温にて滴下した。ドライヤーを用いて少
し加温して反応を開始し始めたらドライヤーでの加温を
止め室温にてさらに滴下し続けた。滴下時間は３時間を
要した。Magnesium for Grignard 2.99 (0.12 gram atom) and THFlomJ were charged into a 300 ml plastic and replaced with dry nitrogen gas. A solution of intermediate 22.41 (0.1 mol) produced in Example 5 dissolved in 40 rM THF was added dropwise at room temperature. When the mixture was heated a little using a dryer and the reaction started, the heating using the dryer was stopped and further dropwise addition was continued at room temperature. The dropping time required 3 hours.
さらに２時間室温にて反応させた。還流するまで加温し
た後、アリルジメチルクロロシラン１３．５ｇ（（１１
モル）、ＴＨＦ（４０ｍ１）溶液を３０分を要して滴下
した。滴下終了後さらに１５時間還流温度で反応を続け
た。反応終了後、ＴＨＦを留去し、室温に冷去後エチル
エーテル（２００ｍＪ）を加えた。冷水（４００ｍｌ）
に投入し、抽出した。The reaction was further continued for 2 hours at room temperature. After heating to reflux, 13.5 g of allyldimethylchlorosilane ((11
A THF (40 ml) solution was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction was continued at reflux temperature for another 15 hours. After the reaction was completed, THF was distilled off, and after cooling to room temperature, ethyl ether (200 mJ) was added. Cold water (400ml)
and extracted.
エーテル層を硫酸マグネシウムで乾燥した後、エーテル
を留出し、減圧蒸留で単量体を得た。収量１６．０！Ｉ
（５６％）単量体の分析値は次の様になる。After drying the ether layer with magnesium sulfate, the ether was distilled off, and a monomer was obtained by distillation under reduced pressure. Yield 16.0! I
(56%) The analysis value of the monomer is as follows.
赤外線吸収スペクトル（ｃｍ−”） ：１２５０（Ｓｉ
−Ｃ）、１６２５．１３９０．９００（ビニリデン）
核磁気共鳴スペクトル（δ）ｐｐｍ：
０．２〜１．２（１２Ｈ，メチル基、ＣＨｓ−８ｉ）０
．４〜０．６（２Ｈ，メチレン基８ｉ−ＣＨ２−ｓｉ）
、２．１〜２．２（４Ｈ，メチレン基。Infrared absorption spectrum (cm-”): 1250 (Si
-C), 1625.1390.900 (vinylidene) Nuclear magnetic resonance spectrum (δ) ppm: 0.2-1.2 (12H, methyl group, CHs-8i) 0
．． 4-0.6 (2H, methylene group 8i-CH2-si)
, 2.1-2.2 (4H, methylene group.
ＣＨ２−ｖｉｎｙｌ 、主鎖） ５．３〜６．５ （３
Ｎ 、ビニル基）、６．６〜８．０（４Ｈ，ベンゼン核
）。CH2-vinyl, main chain) 5.3-6.5 (3
N, vinyl group), 6.6-8.0 (4H, benzene nucleus).
（実施例７） ＯＨ。(Example 7) Oh.
ＣＨ。CH.
Ｃ）（３−８ｊ −ＣＨ３ ＣＨ２ ＣＨ ＣＨ。C) (3-8j -CH3 CH2 CH CH.
実施例６で合成した重合体およびＴＨＦを水素化カルシ
ウムで予備乾燥し友。以下に述べる重合反応はすべて高
真空下で行なった。実施例らで製造した単量体１１．？
を１００ｍ１！枝付きフラスコに仕込み、枝をラバーセ
プタムで封をし、フラスコを高真空ラインに接続した。The polymer synthesized in Example 6 and THF were pre-dried with calcium hydride. All polymerization reactions described below were performed under high vacuum. Monomer 11 produced in Examples. ?
100m1! A flask with a branch was placed, the branch was sealed with a rubber septum, and the flask was connected to a high vacuum line.
液体窒素浴で凍結してから、減圧にし、液体状態にもど
した。この操作を４回（り返して単量体中に含まれる空
気を脱気した後、ｎ−ブチルリチウム（１，６Ｍ：ヘキ
サン中）０．５ｍＪを加えて単量体を完全脱水した。It was frozen in a liquid nitrogen bath and then returned to a liquid state by applying vacuum. After repeating this operation four times to remove air contained in the monomer, 0.5 mJ of n-butyllithium (1,6M in hexane) was added to completely dehydrate the monomer.
・ その後、同様の枝付きフラスコへ蒸留した。ＴＨＦ
５０ｎｌも同様に脱気、脱水を行ない重合フラスコへ蒸
留した。室温にてラバーセプタムからミクロシリンジを
用いてｎ−ブチルリチウム（１，６Ｍ：へキサン中）８
０μｌを加え、すぐにアセトン−ドライアイス浴で冷却
させて重合を行なった。・Then, it was distilled into a similar side flask. THF
50 nl was similarly degassed and dehydrated and distilled into a polymerization flask. n-Butyllithium (1,6M in hexane) 8 using a microsyringe through a rubber septum at room temperature.
0 μl was added and immediately cooled in an acetone-dry ice bath to perform polymerization.
２時間後、メタノール１ｍｌをシリジンを用いて加えて
重合を停止し、常圧にもどし、重合体溶液を５００ｍ１
のメタノール中に投申し友。重合体は白色固体となって
析出し、ろ過して分離した。After 2 hours, 1 ml of methanol was added using silydine to stop the polymerization, the pressure was returned to normal, and the polymer solution was diluted to 500 ml.
of methanol. The polymer precipitated as a white solid and was separated by filtration.
さらにベンゼン１００ｍＡ！に溶解させ、メタノール５
００１Ｍに投入した。この操作を３回くり返した後、減
圧下５０℃で乾燥した。Furthermore, benzene 100mA! Dissolve in methanol 5
I put it into 001M. After repeating this operation three times, it was dried at 50° C. under reduced pressure.
重量平均分子量（Ｍｙ） ＝ ４３ 、０００数平均分
子量（Ｍｎ）＝４１，３００
多分散度（Ｍｗ／Ｍ ｎ ） ＝ １．０３重合体の分
析値は次の様になる。Weight average molecular weight (My) = 43, 000 number average molecular weight (Mn) = 41,300 Polydispersity (Mw/Mn) = 1.03 The analytical values of the polymer are as follows.
赤外線吸収スペクトル（ｃｔ−’） ：１２５０（８ｉ
−Ｃ）、９５０（アリル基）。Infrared absorption spectrum (ct-'): 1250 (8i
-C), 950 (allyl group).
１６３０（ベンゼン核）
核磁気共鳴スペクトル（δ）ｐｐｍ：
０．３〜０．６（６Ｈ，メチル基）、０．５〜０．６（
２Ｈ，メチレン基）、０．５〜０．８（６Ｈ。1630 (benzene nucleus) Nuclear magnetic resonance spectrum (δ) ppm: 0.3-0.6 (6H, methyl group), 0.5-0.6 (
2H, methylene group), 0.5-0.8 (6H.
メチル基及びメチレン基）、５．２〜６．５（アリル基
） 、 ６．７〜７−８（４Ｈ，ベンゼン核）この重合
体は一つの単位の中にシリコン原子を２個有しているた
めシリコン含有量は重合体全体に対して１９．４％（Ｗ
／Ｗ）となる。This polymer has two silicon atoms in one unit. Therefore, the silicon content is 19.4% (W
/W).
（実施例８） なる中間体は次の様な方法で合成した。(Example 8) The intermediate was synthesized by the following method.
１１フラスコにグリニヤール試薬用金属マグネシウム１
４．６．９ （０，６グラム原子）及び乾燥エチルエー
テル２００ｆｆｌＪを仕込んだ。さらにエチルブロマイ
ド０．５ｍ４を加え、少し温めてマグネシウムを活性化
させた。アリルブロマイド６０．５９（０，５モル）、
エチルエーテル４ＱＱｍＪ溶液を４時間を要して滴下し
た。さらに、室温で２時間反応させた。反応溶液中に、
１，１，４．４−テトラメチル−１，４−ジクロロジシ
リハエチレン１０８．５１ （０，５モル）、 ｘチル
ニーチル１１００ｆ溶液を１時間を要して滴下した滴下
後、反応溶液を還流するまで加熱し、還流状態で１５時
間反応をさせた。室温に冷却後、反応溶液をガラスフィ
ルターを用いてろ過をした。ろ過からエチルエーテルを
留出した後、残留物を減圧蒸留して中間体を得た。収量
３２．９（２５）％％ ｂｐ９４〜１００’Ｃ／１７ｍ
ｍＨｇ
中間の分析結果は次の様になる。11 Metallic magnesium for Grignard reagent in flask 1
4.6.9 (0.6 gram atom) and 200 fflJ of dry ethyl ether. Furthermore, 0.5 m4 of ethyl bromide was added and heated slightly to activate the magnesium. Allyl bromide 60.59 (0.5 mol),
Ethyl ether 4QQmJ solution was added dropwise over a period of 4 hours. Further, the reaction was continued for 2 hours at room temperature. In the reaction solution,
A solution of 1,1,4,4-tetramethyl-1,4-dichlorodisilyhaethylene 108.51 (0.5 mol) and x-Tilnityl 1100f was added dropwise over a period of 1 hour. After the dropwise addition, the reaction solution was refluxed. The reaction mixture was heated to 150°C and reacted under reflux for 15 hours. After cooling to room temperature, the reaction solution was filtered using a glass filter. After distilling off ethyl ether from the filtration, the residue was distilled under reduced pressure to obtain an intermediate. Yield 32.9(25)%% bp94-100'C/17m
mHg Intermediate analysis results are as follows.
赤外吸収スペクトル（ｃｍ−”） ： １６３０ （
アリル基） 、 ８１０ （８ｉ −Ｃ，８ｉ−ＣＪに
帰属する大きなピーク）
核磁気共鳴スペクトル（δ）ｐｐｍ：０．１（６ｆ（。Infrared absorption spectrum (cm-”): 1630 (
Allyl group), 810 (large peaks belonging to 8i-C, 8i-CJ) Nuclear magnetic resonance spectrum (δ) ppm: 0.1 (6f(.
ＣＨｓ Ｃ１−８ｉ）。CHs C1-8i).
ＣＨ３ ＣＨ。CH3 CH.
０．５（６Ｈ，ＣＨ２＝ＣＨ−ＣＨ２−８ｉ ）。0.5 (6H, CH2=CH-CH2-8i).
ＣＨ３
０，５〜１．０ （４Ｈ、８１−ＣＨ２−ＣＨ，）１．
９ （２Ｈ、ＣＨ，−Ｃ＝ Ｃ） 、 ４．７〜６．０
（３Ｈ。CH3 0.5-1.0 (4H, 81-CH2-CH,)1.
9 (2H, CH, -C=C), 4.7-6.0
(3H.
ｃＨ，＝ＣＨ−） （実施例９） ＣＨ３ ＣＨ。cH, =CH-) (Example 9) CH3 CH.
ＣＨ。CH.
ＣＨ，−８ｉ−ＣＨ３
ＣＨ２
ＣＨ
ＣＨ３
５００ｍｌフラスコ中にグリニヤール用金属マグネシウ
ム７．０ｇ（０，２９グラム原子）及び乾燥ＴＨＦ１０
＋ｎＪを仕込み、さらに０．１ｍｌのエチルグロマ・イ
ドを刃口え、カロ熱してマグネシウムをｆ６性化させた
。室温にて４−クロロ−α−メチルスチレン２９．７ｇ
を４時間を要して滴ドした。さらに１時間室温にて反応
させた後に、加熱して還流させた。製造した中間体４４
．１．９ （０，２モル）を１時間を要して滴下した。CH, -8i-CH3 CH2 CH CH3 In a 500 ml flask, 7.0 g (0,29 gram atoms) of Grignard metal magnesium and 10 dry THF
+nJ was charged, and 0.1 ml of ethylglomeroid was added to the blade, and the magnesium was heated to f6. 29.7 g of 4-chloro-α-methylstyrene at room temperature
It took 4 hours to administer the solution dropwise. After reacting for an additional hour at room temperature, the mixture was heated to reflux. Manufactured intermediate 44
．． 1.9 (0.2 mol) was added dropwise over a period of 1 hour.
さらに３時間、還流温度で反応させた室温に冷却させて
、反応溶液を水中（ｓｏｏｍｇ） に投入した。エチ
ルエーテル３００ ｍｌで抽出した後、エーテル層を硫
虐マグネシウムで乾燥後、エーテルを留出した。残留物
を減圧蒸留して単量体を得た。牧童２４．７９（４５％
）。ｂｐｌ １０〜１１２℃ｌ Ｃ０２ｍｍＨｇ０単量
体の分針結果は次の様になる
赤外吸収スペクトル（ｒｘ−”） ：１６３０ （アリ
ル基）。The reaction was continued at reflux temperature for an additional 3 hours, cooled to room temperature, and the reaction solution was poured into water (soomg). After extraction with 300 ml of ethyl ether, the ether layer was dried over magnesium sulfate, and the ether was distilled off. The residue was distilled under reduced pressure to obtain a monomer. Shepherd 24.79 (45%
). bpl 10-112℃l C02mmHg0 The minute hand result of the monomer is as follows: Infrared absorption spectrum (rx-''): 1630 (allyl group).
１６００（べ／ゼン核） １２５０（Ｓｉ−Ｃ）、８１
５（８ｉ −Ｃ）
核磁気共鳴スペクトル（δ）ｐｐｍ：０１１（６Ｆ（。1600 (be/zen nucleus) 1250 (Si-C), 81
5(8i-C) Nuclear magnetic resonance spectrum (δ) ppm: 011 (6F(.
ＣＨｓ Ｃｆ（。CHs Cf(.
０．３（６Ｈ，ムｒａｔ ）ｅｏ、５〜０．９（４Ｈ
ｓＳＩＣＨ＊■
ＣＨ２ＣＨ２８ｉ）。0.3 (6H, murat)eo, 5-0.9 (4H
sSICH*■ CH2CH28i).
１．６〜１．８（２Ｈ，ＣＨ意−ＣＨ，）。1.6-1.8 (2H, CH -CH,).
ＣＨｌ ２．３ （３Ｈ、ｃＨ，：ｃ −）。CHl 2.3 (3H, cH,:c-).
ＣＨ。CH.
４．７〜６．０（５Ｈ，ＣＨ，＝Ｃ−及びＣＨ、＝ＯＨ
−）。4.7-6.0 (5H, CH, =C- and CH, =OH
-).
７．６（４Ｈ，ベンゼン核） （実施例１０） ＣＨｓ ＣＨ。7.6 (4H, benzene nucleus) (Example 10) CHs CH.
ＣＨ。CH.
ｅ）（３−８ｉ −ＣＨ３ ＣＨ。e) (3-8i -CH3 CH.
ＣＨ ＣＨ。CH CH.
実施例９で製造した単量体およびＴｆ（Ｆを水素化カル
シウムで予備乾燥した。以下に述べる重合反応はすべて
高真空下が行なった。実施例９で製造した単量体１１．
９を１００ｍ！枝付きフラスコに仕込み、枝を２バーセ
プタムで封をし、フラスコを高真空ラインに接続した。The monomers produced in Example 9 and Tf(F) were predried with calcium hydride. All polymerization reactions described below were carried out under high vacuum. Monomers produced in Example 9 11.
9 for 100m! A flask with a branch was charged, the branch was sealed with a 2-bar septum, and the flask was connected to a high vacuum line.
液体窒素浴で凍結してから、減圧にし、液体状態にもど
した。この操作を４回（り返して単量体中に含°まれろ
空気を脱気した後、ｎ−ブチルリチウム（１，６Ｍ：ヘ
キサン中）０．５ｍｌ、を加えて単量体を完全脱水した
。It was frozen in a liquid nitrogen bath and then returned to a liquid state by applying vacuum. After repeating this operation four times to remove air contained in the monomer, 0.5 ml of n-butyllithium (1,6M in hexane) was added to completely dehydrate the monomer. did.
その後、同様の枝付きフラスコへ蒸留した。ＴＨＦ５０
ｍｌも同様に脱気、脱水を行ない重合フラスコへ蒸留し
た。室温にてラバーセグタムからミクロシリンジを用い
てｎ−ブチルリチウム（１，６Ｍ：ヘキサン中）８０μ
ノを加え、すぐにアセトン−ドライアイス浴で冷却させ
て重合を行なった。It was then distilled into a similar side flask. THF50
ml was similarly degassed and dehydrated and distilled into a polymerization flask. 80μ of n-butyllithium (1,6M in hexane) using a microsyringe from a rubber segment at room temperature.
was added and immediately cooled in an acetone-dry ice bath to carry out polymerization.
２時間後、メタノール１ｍＡ’をシリンジを用いて加え
て重合を停止し、常圧にもどし、重合体溶液を５００ｍ
１：のメタノール中に膜中した。重合体は白色固体とな
って析出し、ろ過して分離した。さらにベンゼン１００
ｒｌｌに溶解させ、メタノール５００ｍ１に投入した。After 2 hours, 1 mA' of methanol was added using a syringe to stop the polymerization, the pressure was returned to normal, and the polymer solution was heated to 500 mA.
The membrane was placed in 1:1 methanol. The polymer precipitated as a white solid and was separated by filtration. Plus 100 benzene
rll and poured into 500 ml of methanol.
この操作を３回くり返した後、減圧下５０℃で乾燥した
。After repeating this operation three times, it was dried at 50° C. under reduced pressure.
重量平均分子量（Ｍｗ）＝４１，３００数平均分子量（
Ｍｎ）＝３７．５００
多分散度（Ｍｗ／Ｍｎ ） ” １．１０重合体の分析
値は次の様になる。Weight average molecular weight (Mw) = 41,300 number average molecular weight (
Mn)=37.500 Polydispersity (Mw/Mn) 1.10 The analytical values of the polymer are as follows.
赤外線吸収スペクトル（ＣＩ！Ｌ−”） ：１２５０
（Ｓ １−Ｃ） 。Infrared absorption spectrum (CI!L-”): 1250
(S1-C).
９５０（アリル基）、１６３０（ベンゼン核）核磁気共
鳴スペクトル（δ）ｐｐｍ：０．３−０．６（６Ｈ，メ
チル基） 、 ０．５−０．６ （４Ｈ，メチレン基）
、 ０．５−０．８ （６Ｈ、メチル基）。950 (allyl group), 1630 (benzene nucleus) nuclear magnetic resonance spectrum (δ) ppm: 0.3-0.6 (6H, methyl group), 0.5-0.6 (4H, methylene group)
, 0.5-0.8 (6H, methyl group).
ｔ、７−２．５（５Ｈ，メチル基及びメチレン基）。t, 7-2.5 (5H, methyl group and methylene group).
５．２−６．５（アリル基） 、 ６．７−７．８ （
４Ｈ。5.2-6.5 (allyl group), 6.7-7.8 (
4H.
ベンゼン咳）。benzene cough).
（実施例１１） なる中間体は次の様な方法で合成した。(Example 11) The intermediate was synthesized by the following method.
１１フラスコにグリニヤール試薬用金属マグネシウム１
４．６ Ｊ （０，６グラム原子）及び乾燥エチルエー
テル２００ｍｔを仕込んだ。さらにエチルブロマイド０
．５ｍＡ：を加え、少し温めてマグネシウムを活性化さ
せた。アリルブロマイド６０．５．９（０，５モル）、
エチルエーテル４００ ｍｌ溶液を４時間を要して滴下
した。さらに、室温で２時間反応させた。反応溶液中に
、１．３−ジクロロテトラメチルジシロキサン１０１．
６＃ （０，５モル上エチルエーテル１００ｍＪ溶液を
１時間を要して滴Ｆした。滴下代、反応溶液を還流する
まで加熱し、ｉ流状悪で１５時間反応をさせた。室温に
冷却後、反応溶液をガンスフイルターを用いてろ過をし
た。11 Metallic magnesium for Grignard reagent in flask 1
4.6 J (0.6 gram atom) and 200 mt of dry ethyl ether were charged. In addition, 0 ethyl bromide
．． 5 mA was added and the mixture was slightly warmed to activate the magnesium. allyl bromide 60.5.9 (0.5 mol),
A 400 ml solution of ethyl ether was added dropwise over a period of 4 hours. Further, the reaction was continued for 2 hours at room temperature. In the reaction solution, 1.3-dichlorotetramethyldisiloxane 101.
A solution of 100 mJ of 6# (0.5 molar ethyl ether) was added dropwise over a period of 1 hour. During the addition, the reaction solution was heated until reflux, and the reaction was allowed to proceed for 15 hours with poor flow. Cooled to room temperature. After that, the reaction solution was filtered using a Gance filter.
ろ過からエチルエーテルを留出した後、残留物を減圧蒸
留して中間体を得た。収量１９．５ＩＩ（１６％）ｂｐ
ｔｓｓ−１６２℃。After distilling off ethyl ether from the filtration, the residue was distilled under reduced pressure to obtain an intermediate. Yield 19.5II (16%) bp
tss-162℃.
中間の分析結Ｐ、は次の様になる
赤外吸収スペクトｋ（ｃｍ−’）：１６１０（アリル基
）。The intermediate analytical result P has the following infrared absorption spectrum k (cm-'): 1610 (allyl group).
１０３０（Ｓ！−０−８ｉ）、８１０（８ｉ−Ｃ，ｄｉ
−（Ｊに帰属する大さなビーク）０
（実施例１２）
ＣＨ，−８ｉ−ＣＨ。1030 (S!-0-8i), 810 (8i-C, di
-(Large peak attributed to J) 0 (Example 12) CH, -8i-CH.
５００ ｍｌフラスコ中にグリニヤール用金属マグネシ
ウム７．０Ｎ（０，２９グラム原子）及び乾燥’ｌ’Ｈ
Ｆ１０ｒＭを仕込み、さらに０１１ｍ１のエチルブロマ
イドを加え、加熱してマグネシウムを活性化させた。室
温にて４−り四ローα−メチルスチレン２９．７Ｎを４
時間を要して滴下した。さらに１時間室温にて反応させ
た後に、加熱して還流させた。製造した中間体５６．３
１ （０，２モル）を１時間を要して滴下した。さらに
３時間、還流温度で反応させた。室温に冷却させて、反
応溶液を水中（５００ｍｌ）に投入した。エチルエーテ
ル３００ｍＡ！で抽出した後、エーテル層を硫酸マグネ
シウムで乾燥後、エーテルを留出した。残留物を減圧蒸
留して単量体を得た。収量１９．７ＩＩ（３４％）ｏ
ｂｐ１０４−１０６℃ Ｉ Ｑ、７ｍｍＨｇ 。Grignard metallic magnesium 7.0N (0,29 g atom) and dry 'l'H in a 500 ml flask
10 rM of F was charged, 0.11 ml of ethyl bromide was added, and the magnesium was activated by heating. At room temperature, 29.7N of 4-ri4ro α-methylstyrene was
It took some time to drip. After reacting for an additional hour at room temperature, the mixture was heated to reflux. Produced intermediate 56.3
1 (0.2 mol) was added dropwise over a period of 1 hour. The reaction was continued at reflux temperature for an additional 3 hours. After cooling to room temperature, the reaction solution was poured into water (500 ml). Ethyl ether 300mA! After extraction, the ether layer was dried over magnesium sulfate, and the ether was distilled off. The residue was distilled under reduced pressure to obtain a monomer. Yield 19.7II (34%)o
bp104-106°C IQ, 7mmHg.
単量体の分析結果は次の様になる。The monomer analysis results are as follows.
赤外吸収スペクトル（ｅｌｌ−” ） ：１６３０ （
アリル基）。Infrared absorption spectrum (ell-”): 1630 (
allyl group).
１６００（ベンゼン核）、１２５０（Ｓｉ−Ｃ）。1600 (benzene nucleus), 1250 (Si-C).
１０４０（８ｉ−０−８ｉ）、８１５（８ｉ−Ｃ）核磁
気共鳴スペクトル（δ）ｐｐｍ：ｏ、１ＣＨ。1040 (8i-0-8i), 815 (8i-C) nuclear magnetic resonance spectrum (δ) ppm: o, 1CH.
（実施例１３） Ｈｓ ＣＨ，−８ｉ−ＣＨ。(Example 13) Hs CH, -8i-CH.
０Ｈ。0H.
ＣＨ ＣＨ。CH CH.
重合反応はすべて高真空下で行なった水素化カルシウム
で予備乾燥したＴＨＰ４０ｍｊ’およびα−メチルスチ
レン１８ ＩＩ（０，０１モル）、さらに金属ナトリウ
ムｌｊ’（０，０３５グラム原子）をラバーセプタムで
封がしである枝付き１００ｍＪフラスコに仕込んだ。室
温で１２時間かくはんし友。紫色の溶液になり金属ナト
リウムがほぼな（なった。真空ラインを乾燥チッソガス
と接続し、開始剤溶液を真空からチッソ下にした。All polymerization reactions were carried out under high vacuum. THP40mj' predried with calcium hydride and α-methylstyrene 18 II (0,01 mol), and metallic sodium lj' (0,035 gram atom) were sealed with a rubber septum. The mixture was placed in a 100 mJ flask with a branch. Stir at room temperature for 12 hours. The solution turned purple and was almost free of sodium metal. The vacuum line was connected to dry nitrogen gas, and the initiator solution was brought from vacuum to nitrogen.
実施例１２で製造し次単憬体１１ｇを１００ｍＪ枝付き
フラスコに仕込み、枝をラバーセプタムで封をし、フラ
スコを高真空ラインに接続し次液体窒素浴で凍結してか
ら、減圧にし、液体状態にもどした。この操作を４回く
り返して単量体中に含まれる空気を脱気し友後、ｎ−ブ
チルリチウム（１，♂ヤヘキサン中）０．５ｍＡを加え
て単量体を完全脱水した。その後、同様の枝付きフラス
コへ蒸留した。ＴＨＦ５０ｍｌも同様に脱気、脱水を行
ない重合フラスコへ蒸留した。室温にてラバーセプタム
からミク党シリンジを用いて、先に製造した開始剤溶液
１．５ｍＡ！を加え、すぐにア七トンードライアイス浴
で冷却させて重合を行なった。６時間後、メタノール１
ｍｊをシリンジを用いて加えて重合を停止し、常圧にも
どし、重合体容液を５００ｍＡ’のメタノール中に膜中
した。重合体は白色固体となって析出し、ろ過して分離
した。さらにベンゼン１００ｍｊ’に溶解させ、メタノ
ール５００ｔＭに投入した。この操作を３回（り返した
後、減圧下５０℃で乾燥した。11 g of the monomer prepared in Example 12 was placed in a flask with a 100 mJ branch, the branch was sealed with a rubber septum, the flask was connected to a high vacuum line, and the flask was frozen in a liquid nitrogen bath, and the pressure was reduced to remove the liquid. Returned to condition. This operation was repeated four times to remove air contained in the monomer, and then 0.5 mA of n-butyllithium (in 1,♂yahexane) was added to completely dehydrate the monomer. It was then distilled into a similar side flask. 50 ml of THF was similarly degassed and dehydrated, and then distilled into the polymerization flask. 1.5 mA of the initiator solution prepared earlier using a Mikuto syringe from a rubber septum at room temperature! was added and immediately cooled in a dry ice bath to carry out polymerization. After 6 hours, methanol 1
Polymerization was stopped by adding mj using a syringe, the pressure was returned to normal, and the polymer solution was poured into a membrane in methanol at 500 mA'. The polymer precipitated as a white solid and was separated by filtration. Furthermore, it was dissolved in 100 mj' of benzene and poured into 500 tM of methanol. After repeating this operation three times, it was dried at 50° C. under reduced pressure.
重量平均分子量（Ｍｗ）＝ ３７，６００数平均分子量
（八（ｎ）−、＝３３，３００多分散度（Ｍｗ／’Ｊ’
ｎ ） ＝ １−１３重合体の分析値は次の様になる。Weight average molecular weight (Mw) = 37,600 Number average molecular weight (8(n)-, = 33,300 Polydispersity (Mw/'J'
The analytical values of the n) = 1-13 polymer are as follows.
赤外線吸収スペクトル（Ｃ：ＩＬ−’） ：１６２０
（ベンゼン核）、１２５０（Ｓｉ−Ｃ）、１０４０（Ｓ
ｉ−０−８ｉ）。Infrared absorption spectrum (C:IL-'): 1620
(benzene nucleus), 1250 (Si-C), 1040 (S
i-0-8i).
９５０（アリル基）。950 (allyl group).
（実施例１４）
実施例２で製造した重合・体０．４２．９と２．６−ジ
ー（４−アジドベンザルシクロヘキサノン）。(Example 14) Polymer 0.42.9 and 2.6-di(4-azidobenzalcyclohexanone) produced in Example 2.
０．０４２！Ｉ をキシｖンＢ、２ｍｉに溶解し、十分
攪拌した後、０．２μｍのフィルターで３遇し試料溶液
とした。この溶液をシリコン基板上にスピン塗布（１０
００ｒｐｍ）Ｌ、８０℃、３０分間乾燥を行な、：＆
った。紫外線露光装置（カスパー卆＝！ａ ２００１
ｐ）にて、クロムマスクを介して露光を行なった。メチ
ルイングチルケトン（ＭＩＢＫ）に１分間浸漬して現像
を行なった後、イングロパノールにて１分間リンスを行
なった。乾燥したのち、被照射部の膜厚を触針法により
測定した初期膜厚は０．２５μｍであった。微細なパタ
ーンを解像しているか否かは種々の寸法のラインアンド
スペースのパターンを描画し、現像処理によって得られ
たレジスｌを光学顕微鏡、走査型電子顕微鏡で観察する
ことにょって調べた。0.042! I was dissolved in Xin V, 2mi, thoroughly stirred, and filtered three times through a 0.2 μm filter to obtain a sample solution. This solution was spin-coated onto a silicon substrate (10
Drying was carried out at 80° C. for 30 minutes at 00 rpm). Ultraviolet exposure equipment (Kasper 卆=!a 2001
In p), exposure was performed through a chrome mask. After development was performed by immersion in methyl ing thyl ketone (MIBK) for 1 minute, rinsing was performed for 1 minute with ingropanol. After drying, the initial film thickness of the irradiated area was measured using a stylus method and was 0.25 μm. Whether or not fine patterns were resolved was determined by drawing line-and-space patterns of various dimensions and observing the resist l obtained by development using an optical microscope and a scanning electron microscope. .
その結果得られた感度曲線を第１図に示す。本実施例の
感度はゲル化点（Ｄｇ）が約１秒であることがわかる。The sensitivity curve obtained as a result is shown in FIG. It can be seen that the sensitivity of this example is that the gel point (Dg) is about 1 second.
同露光装置ｉでひろ（用いられているフォトレジストあ
るシプレー社人Ｚ−１３５０Ｊの適正露光量は７秒であ
る。また得られたパターン布の多分散度が小さく、その
友め前記重合体とビスアジドとの組成物をレジストとし
て用いた時得られるパターンの解像度は優れている。The appropriate exposure amount for the photoresist used in the same exposure device i, Shipley Z-1350J, is 7 seconds.Also, the polydispersity of the resulting patterned cloth is small, and it is similar to the polymer described above. The resolution of the pattern obtained when the composition with bisazide is used as a resist is excellent.
（実施例ノタフ
実施例４で製造した重合体０．４２．９と２，６−ジー
（４′−アジドベンザルシクロヘキサノン）０．０４２
１１をキシレン８．２ｍｔ ＶＣ＠解し、十分攪液とし
た。この溶液をシリコン基板上にスピン塗布（１０００
ｒｐｍ）Ｌ、８０°Ｃ１３０分間乾燥番行なった。紫外
〜１露露光置（カスパー社２００１ｐ）を用いて、クロ
ムマスクを介して露光を行なった。(Example Notaf 0.42.9 of the polymer produced in Example 4 and 0.042 of 2,6-di(4'-azidobenzalcyclohexanone)
No. 11 was dissolved in 8.2 mt VC of xylene to obtain a sufficiently stirred solution. This solution was spin-coated onto a silicon substrate (1000
Drying was carried out at 80° C. for 130 minutes. Exposure was performed through a chrome mask using an ultraviolet to 1 exposure exposure setting (Kasper Inc. 2001p).
メチルイソブチルケトン（ＭＩＢＫ）に１分間浸漬して
現像を行なった後、イソプロパツールにて１分間リンス
を行なった。乾燥したのち被照射部の膜厚を触針法によ
り測定した。初期膜厚は０．２５μｍであった。微、褌
なパターンを解像しているか否かは種々の寸法のライン
アンドスペースのパターンを描１１可シ、現像処理によ
って得られ次レジスト像を光学顕微鏡、走査型電子顕微
鏡、鏡で観察することによって調べた。After developing by immersing it in methyl isobutyl ketone (MIBK) for 1 minute, it was rinsed with isopropanol for 1 minute. After drying, the film thickness of the irradiated area was measured using a stylus method. The initial film thickness was 0.25 μm. Whether or not fine and loincloth patterns are resolved can be determined by drawing line-and-space patterns of various dimensions11.Then, the resist image obtained through development processing is observed using an optical microscope, scanning electron microscope, or mirror. I investigated this by.
その結果得られた感度曲線を７Ｘ２図に示す。本実施例
の感度はゲル化点（Ｄａ）が約１秒であることがわかる
。同露光装置でひろく用いられているフォトレジストで
あるシプレー社ＡＺ−１３５０Ｊ（１μｍ厚）の適正露
光量は７秒であった。また得られ次パターンは５．０秒
の露光において、解像度も初期膜厚が薄いことが反映し
、サブミクロ（実施例１６）
実施例７で製造した重合体０．４２Ｎと２，６−ジー（
４−アジドベンザルシクロヘキサノン）０．０２１，９
をキシレン４．２ｍｌに溶解し、十分攪拌した後、
０．２μｍのフィルターでろ過し試料溶液とした。この
溶液をシリコン基板上にスピン塗布Ｃ３０Ｃ５０００ｒ
ｐ、、８０℃、３０分間乾燥を行った。紫外線露光装置
（ＭＡＮＮ４８００Ｄ８Ｗ（ＧＣＡ社製））を用いて、
クロムマスクラ介して行なった。The sensitivity curve obtained as a result is shown in the 7X2 diagram. It can be seen that the sensitivity of this example is that the gel point (Da) is about 1 second. The appropriate exposure amount for Shipley's AZ-1350J (1 μm thick), a photoresist widely used in the same exposure apparatus, was 7 seconds. In addition, the resolution of the obtained next pattern was reflected in the thin initial film thickness at 5.0 second exposure, and the resolution was submicro (Example 16).
4-azidobenzalcyclohexanone) 0.021,9
After dissolving in 4.2 ml of xylene and stirring thoroughly,
It was filtered through a 0.2 μm filter to obtain a sample solution. Spin coat this solution onto a silicon substrate C30C5000r
p, Drying was performed at 80° C. for 30 minutes. Using an ultraviolet exposure device (MANN4800D8W (manufactured by GCA)),
It was done through chrome maskra.
メチルイソブチルケトン（ＭＩＢＫ）に１分間浸漬して
現像を行なった後、イソプロパツールにて１分間リンス
を行なった。乾燥したのち被照射部の膜厚を触針法によ
り測定した。初期膜厚は０．２５μｍであった。微細な
パターンを解像しているか否かは種々の寸法のラインア
ンドスペースのパターンを描出し、現像処理によって得
られたレジスト像を光学顕微鏡、走査型電子顕微鏡で観
察することによって調べた。After developing by immersing it in methyl isobutyl ketone (MIBK) for 1 minute, it was rinsed with isopropanol for 1 minute. After drying, the film thickness of the irradiated area was measured using a stylus method. The initial film thickness was 0.25 μm. Whether fine patterns were resolved or not was determined by drawing line-and-space patterns of various sizes and observing resist images obtained by development using an optical microscope or a scanning electron microscope.
感度曲線からゲル化点（Ｄｇ） が約３秒であること
がわかった。紫外線露光でひろく用いられているフォト
レジストであるシグレー社ＭＰ−１３００（１μｍ厚）
の適正露光量は０．３５秒であった。It was found from the sensitivity curve that the gel point (Dg) was about 3 seconds. Shigley MP-1300 (1 μm thick), a photoresist widely used for ultraviolet exposure
The appropriate exposure amount was 0.35 seconds.
（実施例１７）
実施例１０で製造した重合体０．４２ＩＩと２．６−ジ
ー（４−アジドベンザルシクロヘキサノン）０．０２１
１１をキシレン８．２ｍｌに溶解し、十分攪拌した後、
０．２μｍのフィルターでろ過し試料溶液とした。この
溶液をシリコン基板上にスピン塗布（３０００ｒｐｍ）
ｌ、、８０℃、３０分間乾燥を行なった。紫外線露光装
置（ＭＡＮＮ４８００ＤＳＷ（ＧＣＡ社製））を用いて
、クロムマスクを介して露光を行なった。メチルイソブ
チルケトン（ＭＩＢＫ）に１分間浸漬して現像を行なっ
た後、イソプロパツールにて１分間リンスを行なった。(Example 17) Polymer 0.42II produced in Example 10 and 2,6-di(4-azidobenzalcyclohexanone) 0.021
After dissolving 11 in 8.2 ml of xylene and stirring thoroughly,
It was filtered through a 0.2 μm filter to obtain a sample solution. Spin coat this solution onto the silicon substrate (3000 rpm)
1. Drying was performed at 80° C. for 30 minutes. Exposure was performed through a chrome mask using an ultraviolet exposure device (MANN4800DSW (manufactured by GCA)). After developing by immersing it in methyl isobutyl ketone (MIBK) for 1 minute, it was rinsed with isopropanol for 1 minute.
乾燥したのち被照射部の膜厚を触針法により測定した。After drying, the film thickness of the irradiated area was measured using a stylus method.
初期膜厚は０．２５μｍであった。微細なパターンを解
像しているか否かは種々の寸法のラインアンドスペース
のパターンを描画し、現像処理によって得られたレジス
ト像を光学顕微鏡、走査型電子顕微鏡で観察することに
よって調べた。The initial film thickness was 0.25 μm. Whether fine patterns were resolved or not was determined by drawing line-and-space patterns of various sizes and observing the resist images obtained by development using an optical microscope or a scanning electron microscope.
感度曲線からゲル化点（Ｄｉ）が約０．４０秒であるこ
とがわかった。同露光装置でひろ（用いられているフォ
トレジストであるシプレー社ＭＰ−１３００（１μｍ厚
）の適正露光量は０．３５秒であった。It was found from the sensitivity curve that the gel point (Di) was about 0.40 seconds. Using the same exposure apparatus, the appropriate exposure amount for the photoresist used, Shipley's MP-1300 (1 μm thick), was 0.35 seconds.
（実施例１８）
実施例１３で製造した重合体０．４２Ｊと２．６−ジー
（４−アジドベンザルシクロヘキサノン）０．０２１＃
をキシレン８−２ ｍｌに溶解し、十分攪拌した後、０
．２μｍのフィルターでろ過し試料溶液とした。この溶
液をシリコン基板上にスピン塗布（３０００ｒｌ）ｍ）
Ｌ、、８０℃、３０分間乾燥を行なった。紫外線露光装
置（ＭＡＮＮ４８００ＤＳＷ（ＧＣＡ社！！！ｌ））を
用いて、クロムマスクを介して露光を行なった。メチル
イソブチルケトン（ＭＩＢＫ）に１分間浸漬して現像を
行なった後、インプロパツールにて１分間リンスを行な
った。乾燥したのち被照射部の膜厚を触針法により測定
した。初期膜厚は０．２０μｍであった。微細なパター
ンを解像しているか否かは種々の寸法のラインアンドス
ペースのパターンを描画し、現像処理によって得られた
レジスト像を光学顕微鏡、走査型電子顕微鏡で観察する
ことによって調べた。(Example 18) 0.42J of the polymer produced in Example 13 and 0.021# of 2.6-di(4-azidobenzalcyclohexanone)
was dissolved in 8-2 ml of xylene, thoroughly stirred, and then
．． It was filtered through a 2 μm filter to obtain a sample solution. Spin coat this solution onto a silicon substrate (3000 ml)
L, Drying was performed at 80° C. for 30 minutes. Exposure was performed through a chrome mask using an ultraviolet exposure device (MANN4800DSW (manufactured by GCA!!!l)). After developing by immersing it in methyl isobutyl ketone (MIBK) for 1 minute, it was rinsed with an inproper tool for 1 minute. After drying, the film thickness of the irradiated area was measured using a stylus method. The initial film thickness was 0.20 μm. Whether fine patterns were resolved or not was determined by drawing line-and-space patterns of various sizes and observing the resist images obtained by development using an optical microscope or a scanning electron microscope.
感度曲線からゲル化点（Ｄｉ） が約０．４２秒であ
ることがわかった。同露光装置でひろく用いられている
フォトレジストであるシグレー社ＭＰ−１３００（１μ
ｍ厚）の適正露光量は０．３５秒であった。From the sensitivity curve, it was found that the gel point (Di) was approximately 0.42 seconds. Sigley's MP-1300 (1μ
The appropriate exposure amount for the film (thickness: m) was 0.35 seconds.
（実施例１９）
次にシリコン基板上にノボラック樹脂を主成分とするレ
ジスト材料（ＡＺ−１３５０Ｊ）を厚さ１．５μｍ塗布
し、２５０℃において１時間焼きしめを行なった。しか
る後、上記実施例１４．１５で調整した溶液をスピン塗
布し、８０℃にて３０分乾燥を行なって０．２５μｍ
厚の均一な塗膜をえた。(Example 19) Next, a resist material (AZ-1350J) containing novolac resin as a main component was applied onto a silicon substrate to a thickness of 1.5 μm, and baked at 250° C. for 1 hour. After that, the solution prepared in Example 14.15 above was applied by spin coating, and dried at 80°C for 30 minutes to form a layer of 0.25 μm.
A coating film with uniform thickness was obtained.
この基板を紫外線露光装置にてクロムマスクを介して５
．０秒露光した。ＭＩＢＫに浸漬して１分間現像を行な
ったのち、インプロパツールにて１分間リンスを行なっ
た。この基板を平行板の反応性スパッタエツチング装置
（アネル、＜社ｇＤｇＭ−４５１）にて、０２５ ｓｃ
ｃｍ 、 ２０ｐａ＊０．１６Ｖ％’／ｉの条件で７分
間エツチングを行なった。走査型電子顕微鏡で観察した
債果、；≧＝＆二黛＝葉子、、−のパターンが下層に正
確に転写されていることがわかった。This substrate was exposed through a chrome mask using an ultraviolet exposure device.
．． Exposure was made for 0 seconds. After immersing it in MIBK and developing it for 1 minute, it was rinsed for 1 minute with an inproper tool. This substrate was etched at 025 sc using a parallel plate reactive sputter etching device (Anel, Inc. DgM-451).
Etching was performed for 7 minutes under the conditions of cm, 20 pa*0.16 V%'/i. It was found that the pattern of bond fruit, ;≧=&二黛= leaf,, - observed with a scanning electron microscope was accurately transferred to the lower layer.
（実施例２０）
シリコン基板上にノボラック樹脂を主成分とするレジス
ト材料（ＭＰ−１３００（シブプレー社製））を厚さ１
．５μｍ塗布し、２５０℃において１時間焼きしめを行
なった。しかる後、実施例１６で調整した溶液をスピン
塗布し、８０℃にて３０分間乾燥を行なって０．２５μ
ｍ厚の均一な塗膜をえた。(Example 20) A resist material (MP-1300 (manufactured by Sivplay)) containing novolac resin as the main component was deposited on a silicon substrate to a thickness of 1
．． It was applied to a thickness of 5 μm and baked at 250° C. for 1 hour. After that, the solution prepared in Example 16 was applied by spin coating, and dried at 80°C for 30 minutes to give a thickness of 0.25μ.
A uniform coating film of m thickness was obtained.
この基板を紫外線露光装置（ＭＡＮＮ４８００ＤＳＷ（
ＧＣＡ社製））を用いクロムマスクを介して４．０秒露
光した。ＭＩＢＫ／ｎ−ＢｕＯＨ（５０／１００Ｖ／Ｖ
）に１分間浸漬して現像を行なっ几のち、インプロパツ
ールにて１分間リンスを行なった。この基板を平行平板
の反応性スパッタエツチング装置（アネルバ社製Ｄｈｍ
Ｍ−４５１）を用い１発明が解決しようとする問題点の
項でのべ九条件つまりＯ！２ｓＣＣｍ、 ３．０ＰａＯ
，１６Ｗ／ｃ！ｉ の条件で７分間エツチングを行な
った。走査型゛成子顕微鏡で観察した結果、サブミクロ
ンの上層のパターンが下）−レジスト材料により正確に
転写されより垂直なパターンが形成されていることがわ
かった。This substrate was exposed to ultraviolet exposure equipment (MANN4800DSW).
(manufactured by GCA)) was exposed for 4.0 seconds through a chrome mask. MIBK/n-BuOH (50/100V/V
) for 1 minute for development, and then rinsed for 1 minute using an inproper tool. This substrate was etched using a parallel plate reactive sputter etching device (Dhm manufactured by Anelva).
M-451) in the section of the problem to be solved by one invention, a total of nine conditions, that is, O! 2sCCm, 3.0PaO
,16W/c! Etching was performed for 7 minutes under the conditions of i. As a result of observation using a scanning electron microscope, it was found that the submicron pattern of the upper layer was accurately transferred by the lower resist material, forming a more vertical pattern.
（実施例２１）
シリコン基板上にノボラック樹脂を主成分とするレジス
ト材料（ＭＰ−１３００（シブプレー社製））を厚さ１
．５μｍ塗布し、２５０℃において１時間焼きしめを行
なった。しかる後、上記実施例１７で調製した溶液をス
ピン塗布し、８０℃にて３０分間乾燥を行なって０．２
５μｍ厚の均一な塗膜をえ友。この基板を紫外線露光装
置（ＭＡＮＮ。(Example 21) A resist material (MP-1300 (manufactured by Sivplay)) containing novolac resin as the main component was deposited on a silicon substrate to a thickness of 1
．． It was applied to a thickness of 5 μm and baked at 250° C. for 1 hour. Thereafter, the solution prepared in Example 17 above was applied by spin coating and dried at 80°C for 30 minutes to give a coating of 0.2
Creates a uniform coating film with a thickness of 5 μm. This substrate was exposed to ultraviolet exposure equipment (MANN).
４Ｂ００ＤＳＷ（ＧＣＡ社製））を用いクロムマスクを
介して０．３５秒露光した。ＭＩＢＫ／ｎ−ＢｕＯＨ（
５０／１００Ｖ／Ｖ）に１分間浸漬して現像を行なった
のち、インプロパツールにて１分間リンスを行なった。4B00DSW (manufactured by GCA)) and exposed for 0.35 seconds through a chrome mask. MIBK/n-BuOH (
50/100V/V) for 1 minute to perform development, and then rinsed for 1 minute with an inproper tool.
この基板を平行平板の反応性スパッタエツチング装置（
アネルバ社ｇＤＥＭ−４５１）を用い、０２５ｓｃｃｍ
、 ２．Ｑｐａ Ｏ，１６Ｗ／ｃｒ／ｌ の条件で７
分間エツチングを行なった。走査型電子顕微鏡で観察し
た結果、サブミクロンの上層のパターンが下層に正確に
転写されていることがわかった。This substrate was etched using a parallel plate reactive sputter etching system (
Anelva gDEM-451), 025sccm
, 2. Qpa O, 7 under the condition of 16W/cr/l
Etching was performed for a minute. Observation using a scanning electron microscope revealed that the submicron pattern of the upper layer was accurately transferred to the lower layer.
（実施例２２〕
シリコン基板上にノボラヴク樹脂を主成分とするレジス
ト材料（ＭＰ−１３００（シラプレー社１ｋ））を厚さ
１，５μｍ塗布し、２５０℃において１時間焼きしめを
行なった。しかる後、上記実施例１８で調整した溶液を
スピン塗布し、８０℃にて３０分間乾燥を行なって０．
２５μｍ厚の均一な塗膜をえた。この基板を紫外線露光
装置（カスパー２００１１））を用いクロムマスクを介
して３．５秒露光Ｌ７’ｃ。ＭＩＢＫ／ｎ−ＢｕＯＨ（
７０／１００Ｖ／Ｖ）に１分間浸漬して現像を行なフた
のち、インプロパツールにて１分間リンスを行なった。(Example 22) A resist material (MP-1300 (Silapray 1K)) containing Novoravuk resin as the main component was applied to a thickness of 1.5 μm on a silicon substrate, and baked at 250° C. for 1 hour. After that. , the solution prepared in Example 18 above was applied by spin coating, and dried at 80°C for 30 minutes to obtain a 0.
A uniform coating film with a thickness of 25 μm was obtained. This substrate was exposed L7'c for 3.5 seconds through a chrome mask using an ultraviolet exposure device (Kasper 20011). MIBK/n-BuOH (
70/100V/V) for 1 minute to perform development, and then rinsed for 1 minute with an inproper tool.
この基板を平行平板の反応性スパッタエツチング装置（
アネルバ社製ＤＥＭ−４５１）を用い、０２５ｓｅｃｍ
、２．０ＰａＯ，１６Ｗ／ｃ、ｆｆｌ （７）条件で
７分間エラｆ ７ クラ行なった。走査型電子顕微鏡で
観察した結果、サブミクロンの上層のパターンが下層に
正確に転写されていることがわかった。This substrate was etched using a parallel plate reactive sputter etching system (
025 sec using Anelva DEM-451)
, 2.0 PaO, 16 W/c, and ffl (7). Observation using a scanning electron microscope revealed that the submicron pattern of the upper layer was accurately transferred to the lower layer.
鞠膣。Ball vagina.
本願第１および第２発明の重合体や組成物はドライエツ
チングに対して極めて強く、２００〜２０００１程度の
膜厚があれば、１．５／Ｊｍ程度の厚い有機ノーをエツ
チングするためのマスクになり得る。したがって、パタ
ーン形成用のレジスト膜は薄くてよい。また、下地に厚
い有機層があると電子ビーム露光においては、近接効果
が低減されるため、光学露光においては、反射波の悪影
２ｊが低減されるために、高解像度のパターンが容易に
得られる。また他の露光法においても高解像度のパター
ンが容易に得られた。The polymers and compositions of the first and second inventions of the present application are extremely resistant to dry etching, and a film thickness of about 200 to 20001 can be used as a mask for etching an organic layer as thick as 1.5/Jm. It can be. Therefore, the resist film for pattern formation may be thin. In addition, when there is a thick organic layer on the base, the proximity effect is reduced in electron beam exposure, and in optical exposure, the negative shadow of reflected waves 2j is reduced, making it easier to obtain high-resolution patterns. It will be done. High-resolution patterns were also easily obtained using other exposure methods.
−Ｉル谷ド辿」張組 ・” −−ｒｌ−・パー゛
□屏値、爬社１９に茎埴ゐ。-Iru Valley Tracing "Zhanggumi ・"--rl-・Part □ Screening value, 19th-century stucco.
また、本願第１発明の実施例７における重合体はシリコ
ン原子２個を有しているためシリコン濃度は重合体に対
して１９．４％（ｖＶ／νＶ）となり、高いので、レジ
スト組成物はドライエツチングに対して極めて強＜、２
０００Ａ程度の膜厚があれば、１、５ ｕｔｎ程度の厚
い有機層をエツチングするためのマスクになり得る。し
たがって、パターン形成用のレジスト膜は薄くてよい。In addition, since the polymer in Example 7 of the first invention of the present application has two silicon atoms, the silicon concentration is 19.4% (vV/νV) with respect to the polymer, which is high. Extremely strong against dry etching <2
A film thickness of about 1,000 Å can be used as a mask for etching an organic layer as thick as 1.5 utn. Therefore, the resist film for pattern formation may be thin.
また、下地に厚い有機層があると電子ビーム露光におい
ては、近接効果が低減され′るため、光学露光において
は、反射波の悪影響の低減されるために、高解像度のパ
ターンが容易に得られる。また他の露光法においても高
解像度のパターンが容易に得られる。In addition, when there is a thick organic layer on the base, the proximity effect is reduced in electron beam exposure, and in optical exposure, the negative effects of reflected waves are reduced, making it easier to obtain high-resolution patterns. . Also, high-resolution patterns can be easily obtained using other exposure methods.
さらに、本ＪＩ！第１発明の実施例１０における重合体
はシリコン原子２個を有しているためシリコンａ度は重
合体に対して１８．５％（Ｗ／Ｗ）となり、高いので、
レジスト組成物はドライエツチングに対して極めて強＜
、２０００Ａ’程度の膜厚があれば、１．５μｍ８度の
厚い有機層をエツチングするためのマスクになり得る。In addition, this JI! Since the polymer in Example 10 of the first invention has two silicon atoms, the silicon a degree is 18.5% (W/W) with respect to the polymer, which is high.
The resist composition is extremely resistant to dry etching.
, 2000 A' can be used as a mask for etching a thick organic layer of 1.5 μm and 8 degrees.
したがって、パターン形成用のレジスト膜は薄（でよい
。また、下地に厚い有機層があると電子ビーム露光にお
いては、近接効果が低減されるため、光学露光において
は、反射波の悪影響が低減されるために、高解像度のパ
ターンが容易に得られる。また他の露光法においても高
解像度のパターンが容易に得られる。Therefore, the resist film for pattern formation can be thin. Also, if there is a thick organic layer underneath, the proximity effect will be reduced in electron beam exposure, so the negative effects of reflected waves will be reduced in optical exposure. Therefore, high-resolution patterns can be easily obtained.High-resolution patterns can also be easily obtained using other exposure methods.
加えて、本願第１発明の実施例１３における重合体はシ
リコン原子２個を有しているためシリコン濃度は重合体
に対して１９．３％（Ｗ／Ｗ）となり高いのでレジスト
組成物はドライエツチングに対して極めて強（，２００
〜ｚｏｏｏ＆ 程度の膜厚があれば、１．５μｍ程度の
厚い有機層をエツチングするためのマスクになり得る。In addition, since the polymer in Example 13 of the first invention of the present application has two silicon atoms, the silicon concentration is high at 19.3% (W/W) with respect to the polymer, so the resist composition is dry. Extremely strong against etching (200
If the film has a thickness of about ~zooo&, it can be used as a mask for etching an organic layer as thick as about 1.5 μm.
したがって、パターン形成用のレジスト膜は薄（でよい
。また。Therefore, the resist film for pattern formation may be thin.
下地に厚い有機層があると電子ビーム露光においては、
近接効果が低減されるため、光学露光においては、反射
波の悪影響が低減されるために、高解像度のパターンが
容易に得られる。また他の露光法においても高解像度の
パターンが容易に得られる。When there is a thick organic layer underneath, electron beam exposure
Since the proximity effect is reduced, high-resolution patterns can be easily obtained in optical exposure because the negative effects of reflected waves are reduced. Also, high-resolution patterns can be easily obtained using other exposure methods.
第１図は本発明の実施例１４の組成物（重合体２．６−
ジー（４−アシドベンザルシクロヘキサノン（１０ｗｔ
％）を加えたもの）の０７ｇ度特性を示すグラフ、第２
図は本発明の実施例１５の組成物（重合体に２，６−ジ
ー（４′−アジドベンザルシフαヘキサノン（１９ｗｔ
％）を加えたもの）のＵＶ感度特性を示すグラフである
。FIG. 1 shows the composition of Example 14 of the present invention (polymer 2.6-
G (4-acidobenzalcyclohexanone (10wt)
%)) graph showing the 07g degree characteristics, 2nd
The figure shows the composition of Example 15 of the present invention (polymer and 2,6-di(4'-azidobenzalsifu α-hexanone) (19 wt.
%) is a graph showing UV sensitivity characteristics.
Claims (27)
チレン系重合体。(1) A styrenic polymer containing both silicon and allyl groups in its constituent units.
０を含む整数、ｎは０、１または２を表わし、ｍは１、
２または３を表わし、ｎ＋ｍは３であり、ｐとｚとは整
数を表わす）で示される特許請求の範囲第１項記載のス
チレン系重合体(2) The above structural unit is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ x represents -O- or -(CH_2)-_p, l is an integer including 0, and n represents 0, 1 or 2. , m is 1,
2 or 3, n+m is 3, and p and z are integers) according to claim 1.
３を表わし、ｎは整数で０〜２を表わし、ｎ＋ｍは３で
ある。ｘは正の整数を表わす）で示され、 多分散度は１．２以下、重量平均分子量は３千ないし１
００万である特許請求の範囲第１項記載の重合体(3) The above structural unit has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, m is an integer from 1 to
3, n is an integer and represents 0 to 2, and n+m is 3. x represents a positive integer), the polydispersity is 1.2 or less, and the weight average molecular weight is 3,000 to 1.
The polymer according to claim 1 which is 1,000,000
もしくは３を表わし、ｎは整数で０、１もしくは２を表
わし、ｎ＋ｍは３である。ｘは正の整数を表わす）で示
される特許請求の範囲第１項記載の重合体。(4) The above structural unit has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, and m is an integer of 1 or 2.
or 3, where n is an integer and represents 0, 1 or 2, and n+m is 3. 2. The polymer according to claim 1, wherein x represents a positive integer.
である特許請求の範囲第４項記載の重合体。(5) Polydispersity is 1.2 or less, weight average molecular weight is 3,000 to 1 million,
The polymer according to claim 4, which is
第１項記載の重合体。(6) The polymer according to item 1 of the claimed scope, in which the above constituent elements are represented by the general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (in the formula, x represents a positive integer).
囲第１項記載の重合体。(7) The polymer according to claim 1, in which the structural unit is represented by the general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (in the formula, x represents a positive integer).
囲第１項記載の重合体(8) The polymer according to claim 1, in which the above-mentioned structural unit is represented by the general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (in the formula, x represents a positive integer)
チレン系重合体とビスアジドとの組成物。(9) A composition of a styrenic polymer containing both silicon and allyl groups in its constituent units and bisazide.
３を表わし、ｎは整数で０〜２を表わし、ｎ＋ｍは３で
ある。ｘは正の整数を表わす）で示され、 多分散度は１．２以下、重量平均分子量は３千ないし１
００万である特許請求の範囲第９項記載の組成物。(10) The structural unit of the above polymer has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, and m is an integer from 1 to
3, n is an integer and represents 0 to 2, and n+m is 3. x represents a positive integer), the polydispersity is 1.2 or less, and the weight average molecular weight is 3,000 to 1.
10,000,000.
もしくは３を表わし、ｎは整数で０、１もしくは２を表
わし、ｎ＋ｍは３である。ｘは正の整数を表わす）で示
される特許請求の範囲第９項記載の組成物。(11) The structural unit of the above polymer has a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a lower alkyl group, m is an integer of 1 or 2
or 3, where n is an integer and represents 0, 1 or 2, and n+m is 3. 10. The composition according to claim 9, wherein x represents a positive integer.
％である特許請求の範囲第１０項または第１１項記載の
組成物。(12) The composition according to claim 10 or 11, wherein the amount of hisazide is 0.3 to 30% by weight based on the polymer.
囲第９項記載の組成物。(13) The composition according to claim 9, in which the constitutional unit of the polymer is represented by the general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (in the formula, x represents a positive integer).
囲第９項記載の組成物。(15) The composition according to claim 9, in which the constitutional unit of the polymer is represented by the general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (in the formula, x represents a positive integer).
このレジスト層をマスクに上記有機膜を選択エッチング
するパターン形成方法において、上記レジスト層に、構
成単位にケイ素およびアリル基の両方を含むスチレン系
重合体を使用するパターン形成方法。(16) selectively covering the organic film on the substrate with a resist layer;
A pattern forming method in which the organic film is selectively etched using this resist layer as a mask, wherein a styrenic polymer containing both silicon and allyl groups as structural units is used in the resist layer.
３を表わし、ｎは整数で０〜２を表わし、ｎ＋ｍは３で
ある。ｘは正の整数を表わす）で示される構成単位から
なり、 多分散度は１．２以下、 重量平均分子量は３千ないし１００万である重合体を用
いる特許請求の範囲第１６項記載のパターン形成方法。(17) The above resist has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, m is an integer from 1 to
3, n is an integer and represents 0 to 2, and n+m is 3. x represents a positive integer), the pattern according to claim 16 uses a polymer having a polydispersity of 1.2 or less and a weight average molecular weight of 3,000 to 1,000,000. Formation method.
もしくは３を表わし、ｎは整数で０、１もしくは２を表
わし、ｎ＋ｍは３である。ｘは正の整数を表わす）で示
される構成単位からなるケイ素原子とアリル基を有する
スチレン系重合体を用いる特許請求の範囲第１６項記載
のパターン形成方法。(18) The above resist has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, and m is an integer of 1 or 2.
or 3, where n is an integer and represents 0, 1 or 2, and n+m is 3. 17. The pattern forming method according to claim 16, which uses a styrenic polymer having a silicon atom and an allyl group consisting of a structural unit represented by (x represents a positive integer).
なるケイ素原子とアリル基を有するスチレン系重合体と
ビスアジドとの組成物を用いる特許請求の範囲第１６項
記載のパターン形成方法。(19) The above-mentioned resist includes a general formula ▲ mathematical formula, chemical formula, table, etc. 17. The pattern forming method according to claim 16, using the composition.
なるケイ素原子とアリル基を有するスチレン系重合体を
用いる特許請求の範囲第１６項記載のパターン(20) The above-mentioned resist includes a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, x represents a positive integer) A patent that uses a styrene-based polymer having a silicon atom and an allyl group consisting of a structural unit Pattern according to claim 16
るケイ素原子とアリル基を有するスチレン系重合体を用
いる特許請求の範囲第１６項記載のパターン形成方法。(21) The above-mentioned registers include general formulas ▲ mathematical formulas, chemical formulas, tables, etc. The pattern forming method according to item 16.
このレジスト層をマスク上上記有機膜を選択エッチング
するパターン形成方法において、上記レジスト層に、構
成単位にケイ素およびアリル基の両方を含むスチレン系
重合体とビスアジドとを有する組成物を使用するパター
ン形成方法。(22) selectively covering the organic film on the substrate with a resist layer;
In the pattern forming method of selectively etching the organic film on the resist layer as a mask, the pattern forming method uses, in the resist layer, a composition containing a styrene polymer containing both silicon and allyl groups as constituent units and bisazide. Method.
３を表わし、ｎは整数で０〜２を表わし、ｎ＋ｍは３で
ある。ｘは正の整数を表わす）で示される構成単位から
なり、 多分散度は１．２以下、 重量平均分子量は３千ないし１００万である重合体とビ
スアジドとの組成物を用いる特許請求の範囲第２２条記
載のパターン形成方法。(23) The above resist has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, m is an integer from 1 to
3, n is an integer and represents 0 to 2, and n+m is 3. (x represents a positive integer), the polydispersity is 1.2 or less, and the weight average molecular weight is 3,000 to 1,000,000, and uses a composition of a polymer and bisazide. The pattern forming method described in Article 22.
もしくは３を表わし、ｎは整数で０、１もしくは２を表
わしｎ＋ｍは３である。ｘは正の整数を表わす）で示さ
れる構成単位からなるケイ素原子とアリル基を有するス
チレン系重合体とビスアジドとの組成分を用いを特許請
求の範囲第２２項記載のパターン形成方法。(24) The above resist has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, R represents a lower alkyl group, and m is an integer of 1 or 2.
or 3, where n is an integer and represents 0, 1 or 2, and n+m is 3. 23. The pattern forming method according to claim 22, which uses a composition of a styrene polymer having a silicon atom and an allyl group consisting of a structural unit represented by (x represents a positive integer) and bisazide.
ケイ素原子とアリル基を有するスチレン系重合体を用い
る特許請求の範囲第２２項記載のパターン形成方法。(25) The above-mentioned resist includes the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, x represents an integer). The pattern forming method according to scope 22.
なるケイ素とアリル基を有するスチレン系重合体とビス
アジドとの組成物を用いる特許請求の範囲第２２項記載
のパターン形成方法。(26) The above-mentioned resist includes the general formula ▲ mathematical formula, chemical formula, table, etc. 23. The pattern forming method according to claim 22, using the composition.
なるケイ素原子とアリル基を有するスチレン系重合体と
ビスアジドとの組成物を用いる特許請求の範囲第２２項
記載のパターン形成方法。(27) The above-mentioned resist includes a general formula ▲ mathematical formula, chemical formula, table, etc. 23. The pattern forming method according to claim 22, using the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP245886A JPS63258909A (en) | 1985-01-09 | 1986-01-09 | Styrene polymer containing silicon atoms and allyl groups, composition therefrom and its use |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP163685 | 1985-01-09 | ||
| JP60-1637 | 1985-01-09 | ||
| JP60-1636 | 1985-01-09 | ||
| JP163785 | 1985-01-09 | ||
| JP27034285 | 1985-11-29 | ||
| JP60-270342 | 1985-11-29 | ||
| JP245886A JPS63258909A (en) | 1985-01-09 | 1986-01-09 | Styrene polymer containing silicon atoms and allyl groups, composition therefrom and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63258909A true JPS63258909A (en) | 1988-10-26 |
| JPH0583563B2 JPH0583563B2 (en) | 1993-11-26 |
Family
ID=27453453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP245886A Granted JPS63258909A (en) | 1985-01-09 | 1986-01-09 | Styrene polymer containing silicon atoms and allyl groups, composition therefrom and its use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63258909A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH037294A (en) * | 1989-01-13 | 1991-01-14 | Agency Of Ind Science & Technol | Production of organic silicon compound and novel organic silicon compound |
| DE10064092A1 (en) * | 2000-12-21 | 2002-07-11 | Wacker Chemie Gmbh | Thermoplastic silicone block copolymer, useful as release coatings, includes hard-segment polymer block and soft-segment, silicone polymer block |
| DE10064074A1 (en) * | 2000-12-21 | 2002-08-01 | Wacker Chemie Gmbh | Thermoplastic silicone block copolymer, useful as release coatings, includes hard-segment polymer block and soft-segment, silicone polymer block |
| WO2007026010A3 (en) * | 2005-09-01 | 2007-06-14 | Freescale Semiconductor Inc | Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and material for coupling a dielectric layer and a metal layer in a semiconductor device |
| US7803719B2 (en) | 2006-02-24 | 2010-09-28 | Freescale Semiconductor, Inc. | Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device |
-
1986
- 1986-01-09 JP JP245886A patent/JPS63258909A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH037294A (en) * | 1989-01-13 | 1991-01-14 | Agency Of Ind Science & Technol | Production of organic silicon compound and novel organic silicon compound |
| DE10064092A1 (en) * | 2000-12-21 | 2002-07-11 | Wacker Chemie Gmbh | Thermoplastic silicone block copolymer, useful as release coatings, includes hard-segment polymer block and soft-segment, silicone polymer block |
| DE10064074A1 (en) * | 2000-12-21 | 2002-08-01 | Wacker Chemie Gmbh | Thermoplastic silicone block copolymer, useful as release coatings, includes hard-segment polymer block and soft-segment, silicone polymer block |
| WO2007026010A3 (en) * | 2005-09-01 | 2007-06-14 | Freescale Semiconductor Inc | Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and material for coupling a dielectric layer and a metal layer in a semiconductor device |
| US7691756B2 (en) | 2005-09-01 | 2010-04-06 | Nxp B.V. | Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and material for coupling a dielectric layer and a metal layer in a semiconductor device |
| US7951729B2 (en) | 2005-09-01 | 2011-05-31 | Nxp B.V. | Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereor, and material for coupling a dielectric layer and a metal layer in a semiconductor device |
| US7803719B2 (en) | 2006-02-24 | 2010-09-28 | Freescale Semiconductor, Inc. | Semiconductor device including a coupled dielectric layer and metal layer, method of fabrication thereof, and passivating coupling material comprising multiple organic components for use in a semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0583563B2 (en) | 1993-11-26 |
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