JPS63158541A - Formation of resist pattern - Google Patents
Formation of resist patternInfo
- Publication number
- JPS63158541A JPS63158541A JP30540586A JP30540586A JPS63158541A JP S63158541 A JPS63158541 A JP S63158541A JP 30540586 A JP30540586 A JP 30540586A JP 30540586 A JP30540586 A JP 30540586A JP S63158541 A JPS63158541 A JP S63158541A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- polymer
- resist material
- itaconic acid
- alkyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000015572 biosynthetic process Effects 0.000 title 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 itaconic acid ester Chemical class 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 20
- 238000010894 electron beam technology Methods 0.000 abstract description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 14
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 2
- IATDMJFAERWMOM-UHFFFAOYSA-N 3-(2,2,2-trifluoroethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC(F)(F)F IATDMJFAERWMOM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- BOASSOYETJYEJF-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-chloroprop-2-enoate Chemical compound FC(F)(F)COC(=O)C(Cl)=C BOASSOYETJYEJF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- ZTZJVAOTIOAZGZ-UHFFFAOYSA-N methyl 2-fluoroacrylate Chemical compound COC(=O)C(F)=C ZTZJVAOTIOAZGZ-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フッ素含有イタコン酸エステル重合体をレジ
スト材として用いることにより、電子線又はＸ線等の高
エネルギー線に対し、高感度、高解像性を有するポジ型
レジストパターンの形成方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention uses a fluorine-containing itaconic acid ester polymer as a resist material to provide high sensitivity and high resistance to high energy rays such as electron beams or X-rays. The present invention relates to a method for forming a positive resist pattern with high resolution.
電子線ポジ型レジストとしては、ポリメタクリル酸メチ
ル（以下ＰＭＭＡと略す）がよく知られている。ＰＭＭ
Ａは高解像性を有しているが、感度が低い。また、（メ
タ）アクリル酸又はその誘導体のモノ又はポリフルオロ
アルカノールとのエステルの重合体は、高感度化を目的
としている（特開昭５５−１８６３８号公報、特開昭６
０−２５４０４１号公報）が、解像性を重視すると感度
は満足されていない。Polymethyl methacrylate (hereinafter abbreviated as PMMA) is well known as an electron beam positive resist. PMM
A has high resolution but low sensitivity. In addition, polymers of esters of (meth)acrylic acid or its derivatives with mono- or polyfluoroalkanols are used for the purpose of increasing sensitivity (JP-A-55-18638, JP-A-6
No. 0-254041), but when emphasis is placed on resolution, the sensitivity is not satisfied.
また、ポリブテンスルホン（以下ＰＢ８と略す）は高感
度レジストとしてよく知られているが、感度及び寸法安
定性がよくない。Further, although polybutenesulfone (hereinafter abbreviated as PB8) is well known as a highly sensitive resist, its sensitivity and dimensional stability are poor.
一方、ポリイタコン醗エステルはポジ型レジストになる
（Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅａ Ｐｏｌｙｍ
ｅｒｓｃｉｅｎｃｅ、 ＬＱ、 ４６５１（１９８５）
、Ｊｏｕｒｎａｌ ｏｆ ＶａｃｕｕｍＳｃｉｅｎｃｅ
＆ Ｔｅｃｈｏｌｏｇｙ、 Ｂ１．１１６０（１９８
３）、 ＩＢＭＴｅｃｈｎｉｃａｌ Ｄｉｓｃｌｏｓｕ
ｒｅ Ｂｕｌｌｅｔｉｎ、１９．３２０８（１９７７）
、Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ ５ｏｃｉｅ
ｔｙ Ｓｙｍｐｏｓｉｕｍ。On the other hand, polyitacon ester becomes a positive resist (Journal of Applia Polym
ersscience, LQ, 4651 (1985)
, Journal of Vacuum Science
& Technology, B1.1160 (198
3), IBM Technical Disclosure
re Bulletin, 19.3208 (1977)
, American Chemical
ty Symposium.
Ｌす、１１９（１９８４）） が、感度は充分とはいえない。L.S., 119 (1984)) However, the sensitivity is not sufficient.
従って、微細パターン加工に用いるポジタイプのレジス
ト材としては、高感度、高解像性かつ感度及び寸法安定
性に優れた性能を有するレジスト材がないという状態に
ある。Therefore, as a positive type resist material used for fine pattern processing, there is no resist material that has high sensitivity, high resolution, and excellent performance in sensitivity and dimensional stability.
本発明は、そのような観点からなされたもので、その目
的は高感度、高解偉度でかつ安定性に優れたレジストパ
ターンを形成することにある。The present invention has been made from this point of view, and its purpose is to form a resist pattern with high sensitivity, high resolution, and excellent stability.
本発明者らは、このような背景をもとに鋭意研究を重ね
、本発明を完成するに至った。Based on this background, the present inventors have conducted extensive research and have completed the present invention.
即ち、本発明は下記一般式
（但し、Ａは共重合可能な二重結合を有する単量体から
導かれた構成単位を示し、Ｒ，は炭素数１〜５のフッ素
置換アルキル基％ Ｒ，は水素又はＲ，と同一のフッ素
置換アルキル基を示す。ｍは正の整数、ｎは０又は正の
整数を示す。ｎ ７ｍは０〜９９である。）で示される
フッ素含有イタコン酸エステル重合体をレジスト材とし
て用いることを特徴とするレジストパターンの形成方法
に関する。That is, the present invention is based on the following general formula (where A represents a structural unit derived from a monomer having a copolymerizable double bond, and R represents a fluorine-substituted alkyl group having 1 to 5 carbon atoms. represents hydrogen or the same fluorine-substituted alkyl group as R, m is a positive integer, n is 0 or a positive integer, and n7m is 0 to 99. The present invention relates to a method for forming a resist pattern characterized by using a combination as a resist material.
本発明のレジスト材であるフッ素含有イタコン愼エステ
ル単量体の例としては、イタコン酸ジー２、２．２−
トリフルオロエチルエステル、イタコン酸ジー２．２．
へ３−テトラフルオロプロピルエステル、イタコン酸ジ
ー２．２．ム４．４．４へキサフルオロブチルエステル
、イタコン酸２，２．２−トリフルオロエチルエステル
、イタコン酸２．２．１５−テトラフルオログロビルエ
ステル、イタコン酸２．ｉ４゜４．４へキサフルオロブ
チルエステル等を挙げることができる。このフッ素含有
イタコン酸エステル単量体は、例えば以下の方法によっ
て製造することができる。As an example of the fluorine-containing itaconic ester monomer that is the resist material of the present invention, itaconic acid di-2,2.2-
Trifluoroethyl ester, itaconic acid di-2.2.
to 3-tetrafluoropropyl ester, itaconic acid di 2.2. 4.4.4 hexafluorobutyl ester, itaconic acid 2,2.2-trifluoroethyl ester, itaconic acid 2.2.15-tetrafluoroglobyl ester, itaconic acid 2. Examples include i4°4.4 hexafluorobutyl ester. This fluorine-containing itaconic acid ester monomer can be produced, for example, by the following method.
イタコン酸ジアルキルエステル単量体の場合には、ベン
ゼン中でイタコン酸と過剰の調整すべきエステルに対応
するアルコールを硫酸を触媒として還流することにより
得られる。In the case of the itaconic acid dialkyl ester monomer, it is obtained by refluxing itaconic acid and an excess of the alcohol corresponding to the ester to be prepared in benzene using sulfuric acid as a catalyst.
イタコノ酸モノアルキルエステル単量体の場合には、ク
ロロホルム中でイタコン酸無水物と５当量の調整すべき
エステルに対応するアルコールを還流することにより得
られる。In the case of itaconic acid monoalkyl ester monomers, it is obtained by refluxing itaconic anhydride and 5 equivalents of the alcohol corresponding to the ester to be prepared in chloroform.
本発明の重合体はフッ素含有イタコン酸エステル単量体
あるいはフッ素含有イタコン酸エステル単量体と共重合
可能な二重結合を有する単量体を塊状重合、溶液重合、
乳化重合等の公知の方法によって製造することができる
。重合開始剤としては、過酸化水素、退散化ベンゾイル
等の過酸化物、アゾビスイソブチロニトリル、アゾビス
ジメチルバレロニトリル等のアゾ化合物、過硫酸カリウ
ム等の過硫酸塩等を使用することができる。The polymer of the present invention is produced by bulk polymerization, solution polymerization,
It can be produced by a known method such as emulsion polymerization. As a polymerization initiator, hydrogen peroxide, peroxides such as degenerated benzoyl, azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, persulfates such as potassium persulfate, etc. can be used. can.
また箋共重合可能な単量体としては、例えば、メタクリ
ル酸メチル、メタクリル酸２゛〜ヒドロキシエチル、メ
タクリル酸グリシジル等のメタクリ／Ｌ’１ｌｌ−ステ
ル類、α−クロロアクリル酸メチル。Examples of copolymerizable monomers include methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylate/L'11-sters such as glycidyl methacrylate, and methyl α-chloroacrylate.
α−クロロアクリル酸２．２．２− トリフルオロエチ
ルエステル、α−クロロアクリルｆｌｌ ２．２．１３
−テトラプロピルエステル、α−クロロアクリル酸λ２
、３．４．４．４−へキサフルオロブチルエステル、α
−フルオロアクリル酸メチル等のα−ハロゲノアクリル
酸エステル類、メタクリル酸等の不飽和カルボン酸類、
メタクリルアミド等の酸アミド類、メタクリロニトリル
等を挙げることができる。α-chloroacrylic acid 2.2.2-trifluoroethyl ester, α-chloroacrylic full 2.2.13
-tetrapropyl ester, α-chloroacrylic acid λ2
, 3.4.4.4-hexafluorobutyl ester, α
- α-halogenoacrylic acid esters such as methyl fluoroacrylate, unsaturated carboxylic acids such as methacrylic acid,
Examples include acid amides such as methacrylamide, methacrylonitrile, and the like.
本発明のフッ素含有イタコン酸エステル重合体をレジス
ト材として用いて電子線描画等によるパターンを形成す
る際の便用法には格別の限定はなく慣用の方法に従って
行うことができる。There is no particular limitation on the convenient method for forming a pattern by electron beam drawing or the like using the fluorine-containing itaconic acid ester polymer of the present invention as a resist material, and the method can be carried out according to a conventional method.
本発明のフッ素含有イタコン酸エステル重合体をレジス
ト材として用いる場合の塗布溶媒としては、ポリマーを
溶解し、均一な皮膜を形成しうる溶媒であれば特に限定
されず、例えば、キシレン。When using the fluorine-containing itaconic acid ester polymer of the present invention as a resist material, the coating solvent is not particularly limited as long as it can dissolve the polymer and form a uniform film, such as xylene.
トルエン、ベンゼン、テトラヒドロフラン、エチレング
リコールモノエチルエーテル、エチレングモノメチルエ
ーテルアセテート、クロロベンゼン等が挙げられる。現
像液は特に限定されず、−例として上記溶媒とアルコー
ルとの混合溶媒、ケトン系溶媒とアルコールとの混合溶
媒を用いることができる。塗布、プレベーク、露光、現
像等その他の手法は常法に従うことができる。Examples include toluene, benzene, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene monomethyl ether acetate, and chlorobenzene. The developing solution is not particularly limited, and for example, a mixed solvent of the above-mentioned solvent and alcohol, or a mixed solvent of a ketone solvent and alcohol can be used. Other methods such as coating, pre-baking, exposure, and development can be carried out by conventional methods.
以下、実施例により本発明を更に詳しく説明するが、本
発明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
なお、実施例における電子線感応性試験は以下の方法に
て行った。In addition, the electron beam sensitivity test in Examples was conducted by the following method.
レジスト溶液全シリコンウェハ上にスピンコードし、［
１５μｍの塗膜を得た。真空下で、１００”Ｃにて３０
分間プレベークを行った後、該塗膜の所望部分に加速電
圧２０ ＫＶの電子線を種々のドーズ量で照射した。次
いで、２４℃にて浸漬法による現像を行い、照射部を選
択的に除去した。線量と現像後の残膜厚との関係を描い
た感度曲線図より感度及びコントラスト（以下、γ値と
いう）を評価した。Spin code the resist solution onto the entire silicon wafer and [
A coating film of 15 μm was obtained. 30 at 100”C under vacuum
After prebaking for a minute, desired portions of the coating were irradiated with an electron beam at an accelerating voltage of 20 KV at various doses. Next, development was performed by dipping at 24° C. to selectively remove the irradiated areas. Sensitivity and contrast (hereinafter referred to as γ value) were evaluated from a sensitivity curve diagram depicting the relationship between dose and residual film thickness after development.
さらに、解像度については、１μｍＬ＆ｓのパターン形
状により、評価を行った。Furthermore, the resolution was evaluated using a pattern shape of 1 μmL&s.
ここで、感度（以下、Ｓ値という）とは、残膜厚がゼロ
となる照射量の値で示される。また、γ値とは、感度曲
線のＳ値に対応する接線上で膜厚が減少しはじめる点に
対する照射量をＤｌとした式、度は高い。Here, the sensitivity (hereinafter referred to as S value) is indicated by the value of the irradiation amount at which the residual film thickness becomes zero. Further, the γ value is a formula in which the irradiation amount at the point where the film thickness begins to decrease on the tangent line corresponding to the S value of the sensitivity curve is Dl, and the degree is high.
〔詳細は「フッ素化合物の最先端応用技術」■シーエム
シー、昭和５６年４月２４日発行、１５９〜１４０頁を
参照〕
実施例１
真空脱気されたフラスコ内に、イタコン酸ジー２．２．
２−１７フルオロエチルエステル５−０９と４酸化ベン
ゾイル８ＸＩＦ’９を仕込み、該フラスコを６０℃にて
２４時間攪拌した後、反応生成物を石油エーテル中にそ
そぎ込み、重合物を沈殿させ、濾過、乾燥を行い、ポリ
イタコン酸ジー２．２゜２−トリフルオロエチルエステ
ルを得た。重量平均分子量は、ＧＰＯ測定の結果、ポリ
スチレン換算で、４５Ｘ１０’であった。[For details, refer to "Cutting-Edge Application Technology of Fluorine Compounds," CMC, published on April 24, 1981, pages 159-140.] Example 1 In a vacuum degassed flask, itaconic acid di 2.2 ．．
After charging 2-17 fluoroethyl ester 5-09 and benzoyl tetroxide 8XIF'9 and stirring the flask at 60°C for 24 hours, the reaction product was poured into petroleum ether to precipitate the polymer, and filtered. , and drying to obtain polyitaconic acid di-2.2°2-trifluoroethyl ester. As a result of GPO measurement, the weight average molecular weight was 45×10' in terms of polystyrene.
次に、電子線感応性試験を行ったところ、現像液として
メチルイソブチルケトン／インプロビルアルコールを用
いた場合、Ｓ値及びγ値がそれぞれ８μＣ／ｃｙｄ 、
２−５であるポジタイプのパターンが形成された。また
、１μｍＬ＆ｓの解像パターンは良好であった。Next, an electron beam sensitivity test was conducted, and when methyl isobutyl ketone/improvyl alcohol was used as the developer, the S value and γ value were 8 μC/cyd, respectively.
A positive type pattern of 2-5 was formed. Moreover, the resolution pattern of 1 μmL&s was good.
実施例２
イタコン酸−）−２，２，２−）リフルオロエチルエス
テル１５９．α−クロロアクリル酸２．２．２−）リフ
ルオロエチルエステルｔ ５９ 、３ｉ４酸化ヘンゾイ
ル９×１０−４９をフラスコ内に仕込み、実施例１に従
い、重合体を得た。重量平均分子量は、ＧＰＣ測定の結
果、ポリスチレン換算でａ２Ｘ１０５であった。Example 2 Itaconic acid-)-2,2,2-)lifluoroethyl ester 159. α-Chloroacrylic acid 2.2.2-)lifluoroethyl ester t 59 , 3i4 henzoyl oxide (9×10 −49 ) was charged into a flask, and according to Example 1, a polymer was obtained. As a result of GPC measurement, the weight average molecular weight was a2×105 in terms of polystyrene.
次に、電子線感応性試験を行ったところ、現像液として
メチルイソブチルケトン／イソプロピルアルコールを用
いた場合、Ｓ値及びγ値がそれぞれ２μｃ／ａ／ｌ 、
五５であるポジタイプのパターンが形成された。ま
た、１μｍＬ＆ｓの解像パターンは良好であった。Next, an electron beam sensitivity test was conducted, and when methyl isobutyl ketone/isopropyl alcohol was used as the developer, the S value and γ value were 2 μc/a/l, respectively.
A positive type pattern of 55 was formed. Moreover, the resolution pattern of 1 μmL&s was good.
実施例３
イタコン酸２．２．２−トリフルオロエチルエステル五
８９．メタクリル酸メチル１．２ ｇ、過酸化ベンゾイ
ル１． ＯＸ １０−”９をフラスコ内に仕込み、実施
例１に従い、重合体を得た。重量平均分子量は、ＧＰＣ
測定の結果、ポリスチレン換算で７．８ Ｘ１０５であ
った。Example 3 Itaconic acid 2.2.2-trifluoroethyl ester 589. Methyl methacrylate 1.2 g, benzoyl peroxide 1. OX 10-''9 was charged into a flask to obtain a polymer according to Example 1.The weight average molecular weight was determined by GPC
The measurement result was 7.8 x 105 in terms of polystyrene.
次に、電子線感応性試験を行ったところ、現像液トシテ
、エチレングリコールモノエチルエーテルアセテート／
インプロビルアルコールを用いた場合、Ｓ値及びγ値が
それぞれ４μΦ侃、五３であるポジタイプのパターンが
形成された。Next, an electron beam sensitivity test was conducted, and it was found that the developer solution, ethylene glycol monoethyl ether acetate/
When Improvil alcohol was used, a positive type pattern with S value and γ value of 4 μΦ侃 and 53, respectively, was formed.
また、１μｍＬ＆８の解像パターンは良好であった。Moreover, the resolution pattern of 1 μmL & 8 was good.
本発明のフッ素含有イタコン酸エステル重合体は、電子
線やＸ線の照射により主鎖崩壊反応を起こしやすく、被
照射部は照射されていない部分に比べて溶剤に対しての
溶解性が大きく向上する。The fluorine-containing itaconic acid ester polymer of the present invention easily undergoes a main chain collapse reaction when irradiated with electron beams or X-rays, and the irradiated area has significantly improved solubility in solvents compared to the non-irradiated area. do.
ポリメタクリル酸メチルにおいても、これら放射線によ
り主鎖崩壊を起こすが、本発明のフッ素含有イタコン酸
エステル重合体は、カルボニル基を分子内に２個含有し
、かつフッ素が含有されているために、崩壊反応を起こ
しやすく、その結果感度が上昇する。Even in polymethyl methacrylate, the main chain collapses due to these radiations, but the fluorine-containing itaconic acid ester polymer of the present invention contains two carbonyl groups in the molecule and fluorine, so It is easy to cause decay reactions, resulting in increased sensitivity.
Claims (2)
導かれた構成単位を示し、Ｒ＿１は炭素数１〜５のフッ
素置換アルキル基、Ｒ＿２は水素又はＲ＿１と同一のフ
ッ素置換アルキル基を示す。ｍは正の整数を、ｎは０又
は正の整数を示す。ｎ／ｍは０〜９９である。） で示されるフッ素含有イタコン酸エステル重合体をレジ
スト材として用いることを特徴とするレジストパターン
の形成方法。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, A indicates a constitutional unit derived from a monomer having a copolymerizable double bond, and R_1 is a fluorine containing 1 to 5 carbon atoms. Substituted alkyl group, R_2 represents hydrogen or the same fluorine-substituted alkyl group as R_1. m represents a positive integer, n represents 0 or a positive integer. n/m is 0 to 99.) A method for forming a resist pattern, characterized in that a fluorine-containing itaconic acid ester polymer is used as a resist material.
は炭素数１〜５のアルキル基又はフッ素置換アルキル基
を示す。） である特許請求の範囲第１項記載のレジストパターンの
形成方法。(2) A is a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X represents a methyl group or a halogen atom, and R_3
represents an alkyl group having 1 to 5 carbon atoms or a fluorine-substituted alkyl group. ) A method for forming a resist pattern according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30540586A JPS63158541A (en) | 1986-12-23 | 1986-12-23 | Formation of resist pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30540586A JPS63158541A (en) | 1986-12-23 | 1986-12-23 | Formation of resist pattern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63158541A true JPS63158541A (en) | 1988-07-01 |
Family
ID=17944732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30540586A Pending JPS63158541A (en) | 1986-12-23 | 1986-12-23 | Formation of resist pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63158541A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6593058B1 (en) | 1998-09-23 | 2003-07-15 | E. I. Du Pont De Nemours And Company | Photoresists, polymers and processes for microlithography |
| US6849377B2 (en) | 1998-09-23 | 2005-02-01 | E. I. Du Pont De Nemours And Company | Photoresists, polymers and processes for microlithography |
| JP2014044414A (en) * | 2012-08-01 | 2014-03-13 | Sumitomo Chemical Co Ltd | Resist composition and method for producing resist pattern |
| US20160170300A1 (en) * | 2014-12-15 | 2016-06-16 | Sumitomo Chemical Company, Limited | Photoresist composition and method for producing photoresist pattern |
-
1986
- 1986-12-23 JP JP30540586A patent/JPS63158541A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6593058B1 (en) | 1998-09-23 | 2003-07-15 | E. I. Du Pont De Nemours And Company | Photoresists, polymers and processes for microlithography |
| US6849377B2 (en) | 1998-09-23 | 2005-02-01 | E. I. Du Pont De Nemours And Company | Photoresists, polymers and processes for microlithography |
| US7276323B2 (en) | 1998-09-23 | 2007-10-02 | E. I. Du Pont De Nemours And Company | Photoresists, polymers and processes for microlithography |
| JP2014044414A (en) * | 2012-08-01 | 2014-03-13 | Sumitomo Chemical Co Ltd | Resist composition and method for producing resist pattern |
| US20160170300A1 (en) * | 2014-12-15 | 2016-06-16 | Sumitomo Chemical Company, Limited | Photoresist composition and method for producing photoresist pattern |
| US9740102B2 (en) * | 2014-12-15 | 2017-08-22 | Sumitomo Chemical Company, Limited | Photoresist composition and method for producing photoresist pattern |
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