JPH01222255A - Resist composition - Google Patents
Resist compositionInfo
- Publication number
- JPH01222255A JPH01222255A JP4889488A JP4889488A JPH01222255A JP H01222255 A JPH01222255 A JP H01222255A JP 4889488 A JP4889488 A JP 4889488A JP 4889488 A JP4889488 A JP 4889488A JP H01222255 A JPH01222255 A JP H01222255A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- resist composition
- resist
- composition
- formula
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000004321 preservation Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 23
- -1 ester compound Chemical class 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007261 regionalization Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- UDEKCKABZJKCKG-UHFFFAOYSA-N cyclononanol Chemical compound OC1CCCCCCCC1 UDEKCKABZJKCKG-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000758 substrate 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
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、レジスト組成物に関し、特に０．８μｍ以下
のデザインルールに対応したレジスト組成物に係わる。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a resist composition, and particularly to a resist composition compatible with a design rule of 0.8 μm or less.
（従来の技術）
半導体素子の製造工程で使用されるフォトリソグラフィ
技術において、該半導体素子の高集積化に伴ってレジス
ト材料の解像寸法幅はますます微細化される傾向にある
。(Prior Art) In photolithography technology used in the manufacturing process of semiconductor devices, the resolution width of resist materials tends to become smaller and smaller as semiconductor devices become more highly integrated.
上述した要求を満たすレジスト材料として、最近、４以
上のヒドロキシ基を有するベンゾフェノンとナフトキノ
ンジアジドスルフォン酸とのエステル化合物を感光剤と
して含有するもの（特開昭６２−１５０２４５号）が提
案されている。かかる感光剤を使用した場合、解像性に
優れるのみならず、優れた耐熱性が得られることから、
ドライエツチング時のレジストへの加熱によるパターン
のだれが生じ難く、加工寸法制御性の良好なレジスト組
成物を調製できる。しかしながら、前記感光剤を含有し
たレジスト組成物は常温での暗反応性に富み、その結果
反応生成物がレジスト組成物内に析出し、パターン形成
時の欠陥の原因になりり易く、保存安定性に欠ける問題
があった。As a resist material satisfying the above-mentioned requirements, a resist material containing an ester compound of benzophenone having four or more hydroxyl groups and naphthoquinonediazide sulfonic acid as a photosensitizer has recently been proposed (Japanese Patent Laid-Open No. 150245/1983). When such a photosensitizer is used, it not only provides excellent resolution but also excellent heat resistance.
It is possible to prepare a resist composition in which pattern sag is less likely to occur due to heating of the resist during dry etching, and which has good processing dimension controllability. However, resist compositions containing the above-mentioned photosensitizers are highly reactive in the dark at room temperature, and as a result, reaction products precipitate within the resist composition, which tends to cause defects during pattern formation and has poor storage stability. There was a problem with this.
（発明が解決しようとする課題）
本発明は、上記課題を解決するためになされたもので、
解像性、耐熱性に優れるのみならず、保存安定性の優れ
たレジスト組成物を提供しようとするものである。(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems.
The present invention aims to provide a resist composition that not only has excellent resolution and heat resistance, but also has excellent storage stability.
［発明の構成］
（課題を解決するための手段）
本発明は、アルカリ可溶性樹脂、感光剤及び溶媒を含む
レジスト組成物をおいて、前記感光剤が下記一般式（１
）にて表わされる有機化合物からなり、かつ溶媒が少な
くともジメチルフォルムアミド又は脂肪族アルコールを
含有するものからなることを特徴とするレジスト組成物
である。[Structure of the Invention] (Means for Solving the Problems) The present invention provides a resist composition containing an alkali-soluble resin, a photosensitizer, and a solvent, wherein the photosensitizer has the following general formula (1).
), and the resist composition is characterized in that the solvent contains at least dimethylformamide or an aliphatic alcohol.
Ｒ７、Ｒ４
但し、式中のＲ１〜Ｒ１ｏのうち少なくとも１つは構造
式（ｎ）
で示される感光基を示し、残りは水素原子、ヒドロキシ
基であり、かつ上記構造式（ｎ）で表ゎされる感光基と
ヒドロキシ基の数の和が４以上である。R7, R4 However, at least one of R1 to R1o in the formula represents a photosensitive group represented by the structural formula (n), and the remaining are a hydrogen atom or a hydroxy group, and the group represented by the above structural formula (n) The sum of the number of photosensitive groups and hydroxyl groups is 4 or more.
上記アルカリ可溶性樹脂は、アルカリ溶液に可溶なもの
ならいかなるものでよく、例えばフェノール類とホルム
アルデヒドとの縮合によって得られるノボラック樹脂が
挙げられる。前記フェノール類トしては、例えばフェノ
ール、０−クロロフェノール、ｔｓ−’）ロロフェノー
ル、ｐ−クロロフェノール、■−クレゾール、３．５−
キシレゾール、２．５−キシレゾール、ｐ−クレゾール
、ビスフェノールＡ、４−クロロ−３−クレゾール等を
挙げることができる。The alkali-soluble resin may be any resin as long as it is soluble in an alkaline solution, such as novolac resins obtained by condensation of phenols and formaldehyde. Examples of the phenols include phenol, 0-chlorophenol, ts-')lolophenol, p-chlorophenol, ■-cresol, 3.5-
Examples include xyresol, 2.5-xyresol, p-cresol, bisphenol A, and 4-chloro-3-cresol.
これらのうち１種又は２種以上のものとホルマリンを縮
合させるこによって、前記ノボラック樹脂が得られる。The novolak resin can be obtained by condensing one or more of these with formalin.
また、アルカリ可溶性樹脂は前記ノボラック樹脂に限ら
ず、ポリ（ｐ−ビニルフェノール）、ポリ（ｐ−イソプ
ロペニルフェノール）、ポリ（１１１−イソプロペニル
フェノール）、ｐ−ヒドロキシスチレンとメタクリル酸
メチルとの共重合体、ｐ−ヒドロキシスチレンとアクリ
ル酸メチルとの共重合体、ｐ−ヒドロキシスチレンとメ
タクリル酸との共重合体、ｐ−イソプロペニルフェノー
ルとアクリル酸メチルとの共重合体など構造単位に芳香
族環とヒドロキシ基を有する樹脂等を使用できる。In addition, the alkali-soluble resins are not limited to the novolac resins mentioned above, but also include poly(p-vinylphenol), poly(p-isopropenylphenol), poly(111-isopropenylphenol), p-hydroxystyrene and methyl methacrylate. Polymers with aromatic structural units, such as copolymers of p-hydroxystyrene and methyl acrylate, copolymers of p-hydroxystyrene and methacrylic acid, copolymers of p-isopropenylphenol and methyl acrylate, etc. A resin having a ring and a hydroxy group can be used.
特に、ポリ（ｐ−ビニルフェノール）、ｐ−ビニルフェ
ノールとメタクリル酸メチルとの共重合体をアルカリ可
溶性樹脂として用いることが望ましい。In particular, it is desirable to use poly(p-vinylphenol) or a copolymer of p-vinylphenol and methyl methacrylate as the alkali-soluble resin.
これらの樹脂は、単独でも２種以上の混合系でも使用す
ることが可能である。These resins can be used alone or in a mixed system of two or more.
上記一般式（Ｉ）にて表わされる感光剤としては、例え
ば２．３．４．４°−テトラヒドロキシベンゾフェノン
−１，２−ナフトキノンジアジドスルフォン酸エステル
、２．２ ’ 、４．４°−テトラヒドロキシベンゾフ
ェノン−１，２−ナフトキノンジアジド−５−スルフォ
ン酸エステル、２，２′ 、３．４．４°−ペンタヒド
ロキシベンゾフェノン−１，２−ナフトキノンジアジド
−５−スルフォン酸エステル等を挙げることができ、特
に２．３，４．４ ’−テトラヒドロキシベンゾフェノ
ン−１，２−ナフトキノンジアジド−５−スルフォン酸
エステルはレジスト組成物の安定性を向上できることか
ら有効である。かかる感光剤の含有量は、レジスト組成
物の全固形分総量に対して１０〜３０重量％とすること
が望ましい。この理由は、感光剤の含有量を１０重量％
未満にするとレジスト組成物の感度、解像度等が低下す
る恐れがあり、かといつてその含有量が３０重量％を越
えると特定の組成の溶媒を使用しても常温での保存時に
おいてレジスト組成物中に反応生成物が沈澱、析出する
恐れがあるからである。Examples of the photosensitizer represented by the above general formula (I) include 2.3.4.4°-tetrahydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid ester, 2.2', 4.4°-tetra Examples include hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2',3.4.4°-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. In particular, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester is effective because it can improve the stability of the resist composition. The content of the photosensitizer is preferably 10 to 30% by weight based on the total solid content of the resist composition. The reason for this is that the content of photosensitizer is 10% by weight.
If the content is less than 30% by weight, the sensitivity, resolution, etc. of the resist composition may decrease, and if the content exceeds 30% by weight, the resist composition may deteriorate when stored at room temperature even if a solvent with a specific composition is used. This is because there is a possibility that the reaction product will precipitate or precipitate inside.
上記溶媒の必須成分であるジメチルフォルムアミドとし
ては、純度が９９％以上でアミン含有量が極力少ないも
のを用いることが望ましい。かかる溶媒の他の成分とし
ては、エチルセロソルブアセテート、ブチルセロソルブ
アセテート、メチルセロソルブアセテート、エチルセロ
ソルブ、メチルセロソルブ等のセロソルブ系のものが望
ましい。As dimethylformamide, which is an essential component of the above solvent, it is desirable to use one with a purity of 99% or more and an amine content as low as possible. Other components of the solvent are preferably cellosolve-based solvents such as ethyl cellosolve acetate, butyl cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve, and methyl cellosolve.
また、必要に応じて塗布性、溶解性、安定性を高めるた
めにキシレン、酢酸ブチル、ジメチルスルフオキシド、
γ−ブチルラクトン、ジオキサン、界面活性剤等を配合
してもよい。こうした溶媒において、前記ジメチルフォ
ルムアミドの含有量は１〜３０重量％の範囲とすること
が望ましい。ジメチルフォルムアミドの含有量を１重量
％未満にするとレジスト組成物の保存安定性を充分向上
できず、かといってその含有量が３０重量％を越えると
レジスト組成物の解像性、耐熱性、パターンの基板等へ
の密着性、塗布性が悪化する恐・れがある。In addition, xylene, butyl acetate, dimethyl sulfoxide,
γ-Butyl lactone, dioxane, surfactant, etc. may be blended. In such a solvent, the content of dimethylformamide is preferably in the range of 1 to 30% by weight. If the content of dimethylformamide is less than 1% by weight, the storage stability of the resist composition cannot be sufficiently improved, while if the content exceeds 30% by weight, the resolution, heat resistance, and There is a risk that the adhesion and coating properties of the pattern to the substrate etc. may deteriorate.
より好ましいジメチルフォルムアミドの含有量は、１５
〜２５重量％の範囲である。A more preferable content of dimethylformamide is 15
-25% by weight.
上記別の溶媒の必須成分である脂肪族アルコールとして
は、例えばメタノール、エタノール、プロパツール、イ
ソプロピルアルコール、ブタノール、ペンチルアルコー
ル、ペンタノール、シクロペンタノール、ヘキサノール
、ヘプタツール、シクロヘキサノール、ヘプタツール、
シクロヘプタツール、オクタツール、ノナノール、シク
ロノナノール、ブテニルアルコール、シクロペンテニル
アルコール、ドデシルアルコール、エチレンジオール、
グリセリン等を挙げることができる。特に、レジスト組
成物の塗布特性を良好な維持させる観点から脂肪族アル
コールとしてメタノール、エタノール、プロパツール、
イソプロピルアルコール、ブタノール、ペンタノールが
肴効であり、中でもイソプロピルアルコールが好適であ
菖。かかる溶媒の他の成分としては、エチルセロソルブ
アセテート、ブチルセロソルブアセテート、メチルセロ
ソルブアセテート、エチルセロソルブ、メチルセロソル
ブ等のセロソルブ系のものが望ましい。また、必要に応
じて塗布性、溶解性、安定性を高めるためにキシレン、
酢酸ブチル、γ−ブチルラクトン、ジメチルフォルムア
ミド、ジオキサン、界面活性剤等を配合してもよい。こ
うした溶媒において、前記脂肪族アルコールの含有量は
１〜５０重量％の範囲とすることが望ましい。脂肪族ア
ルコールの含有量を１重量％未満にするとレジスト組成
物の保存安定性を充分向上できず、かといってその含有
量が５０重量％を越えると感光剤の溶解量が低下しぞ塗
布性が悪化する恐れがある。より好ましい脂肪族アルコ
ール、の含有量は、５〜３０重量％の範囲である。Examples of the aliphatic alcohol that is an essential component of the above-mentioned other solvent include methanol, ethanol, propatool, isopropyl alcohol, butanol, pentyl alcohol, pentanol, cyclopentanol, hexanol, heptatool, cyclohexanol, heptatool,
cycloheptatool, octatool, nonanol, cyclononanol, butenyl alcohol, cyclopentenyl alcohol, dodecyl alcohol, ethylenediol,
Glycerin and the like can be mentioned. In particular, methanol, ethanol, propatool,
Isopropyl alcohol, butanol, and pentanol are effective as appetizers, and isopropyl alcohol is particularly suitable. Other components of the solvent are preferably cellosolve-based solvents such as ethyl cellosolve acetate, butyl cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve, and methyl cellosolve. Also, if necessary, xylene,
Butyl acetate, γ-butyl lactone, dimethylformamide, dioxane, surfactants, etc. may be blended. In such a solvent, the content of the aliphatic alcohol is preferably in the range of 1 to 50% by weight. If the content of aliphatic alcohol is less than 1% by weight, the storage stability of the resist composition cannot be sufficiently improved, while if the content exceeds 50% by weight, the amount of dissolved photosensitizer will decrease and the coating properties will be affected. may worsen. The more preferable content of aliphatic alcohol is in the range of 5 to 30% by weight.
（作用）
本発明によれば、アルカリ可溶性樹脂及び−般式（１）
にて表わされる感光剤を含む構成とすることによって、
アルカリ現像が可能で、かつ該感光剤による優れた解像
性、耐熱性を有するレジスト組成物を得ることができる
。(Function) According to the present invention, the alkali-soluble resin and the general formula (1)
By having a configuration including a photosensitizer represented by
It is possible to obtain a resist composition that is capable of alkaline development and has excellent resolution and heat resistance using the photosensitive agent.
また、溶剤として少なくとも゛ジメチルフォルムアミド
を含有するものを使用することによって、常温でのレジ
スト組成物の保存において感光剤の暗反応により生じた
生成物を該ジメチルフォルムアミドにより溶解できる。Furthermore, by using a solvent containing at least dimethylformamide, the dimethylformamide can dissolve the products generated by the dark reaction of the photosensitizer during storage of the resist composition at room temperature.
その結果、パターン形成時の欠陥の原因となる反応生成
物の沈澱、析出を抑制した保存安定性の高いレジスト組
成物を得ることができる。As a result, it is possible to obtain a resist composition with high storage stability that suppresses precipitation and precipitation of reaction products that cause defects during pattern formation.
更に、別の溶剤として少なくとも脂肪族アルコールを含
有するものを使用することによって、常温でのレジスト
組成物の保存において感光剤にアルコールが関与して感
光剤同志ではなく、感光剤とアルコールとの暗反応を生
じさせることができるため、パターン形成時の欠陥の原
因となる感光剤同志の反応生成物の沈澱、析出を抑制し
た保存安定性の高いレジスト組成物を得ることができる
。Furthermore, by using a solvent containing at least an aliphatic alcohol as another solvent, when the resist composition is stored at room temperature, the alcohol is involved in the photosensitizer and the photosensitizer and alcohol do not interact with each other; Since the reaction can occur, it is possible to obtain a resist composition with high storage stability that suppresses precipitation and precipitation of reaction products between photosensitizers that cause defects during pattern formation.
（発明の実施例） 以下、本発明の実施例を詳細に説明する。(Example of the invention) Examples of the present invention will be described in detail below.
レジスト組成物調製例１
アルカリ可溶性樹脂としてノボラック樹脂７０９、ビニ
ルフェノール樹脂３ｇ及び下記第１表に示す感光剤２７
９を同第１表に示す溶媒２５０ｇで混合溶解した後、０
．２μｍのフィルタで濾過して８種のレジスト組成物を
調製した。Resist Composition Preparation Example 1 Novolak resin 709, vinyl phenol resin 3 g, and photosensitizer 27 shown in Table 1 below as alkali-soluble resins.
After mixing and dissolving 9 with 250 g of the solvent shown in Table 1, 0
．． Eight types of resist compositions were prepared by filtering through a 2 μm filter.
また、アルカリ可溶性樹脂としてノボラック樹脂７０ｇ
、ビニルフェノール樹脂３ｇ及び下記第２表に示す割合
（全固形分総量に対する含有割合）で配合した２、３，
４．４ ’−テトラヒドロキシベンゾフェノン−１，２
−ナフトキノンジアジド−５−スルフォン酸エステル（
感光剤）を同第２表に示す溶媒２５０ｇで混合溶解した
後、０．２μｍのフィルタで濾過して３種のレジスト組
成物を調製した。In addition, 70g of novolak resin is used as an alkali-soluble resin.
, 2, 3, blended with 3 g of vinyl phenol resin and the proportions shown in Table 2 below (content proportion relative to the total solid content).
4.4'-tetrahydroxybenzophenone-1,2
-naphthoquinonediazide-5-sulfonic acid ester (
Photosensitizer) was mixed and dissolved in 250 g of the solvent shown in Table 2, and then filtered through a 0.2 μm filter to prepare three types of resist compositions.
しかして、上記第１表に示す８種のレジスト組成物を夫
々３０℃の温度下で長期間保存した時のレジスト組成物
内に析出した析出物の数を月数との関係で調べたところ
、第１図に示す結果を得た。However, when we investigated the number of precipitates deposited in the resist compositions when each of the eight types of resist compositions listed in Table 1 were stored at a temperature of 30°C for a long period of time in relation to the number of months, we found that The results shown in Figure 1 were obtained.
なお、第１図中のｔ−ｅは夫々試料Ｎｌｌ〜Ｇのレジス
ト組成物の特性線である。Note that t-e in FIG. 1 are characteristic lines of the resist compositions of samples Nll to G, respectively.
また、上記第２表に示す３種のレジスト組成物を夫々３
０℃の温度下で長期間保存した時のレジスト組成物内に
析出した析出物の数を月数との関係で調べたところ、第
２図に示す結果を得た。なお、第２図中の７〜９は夫々
試料嵐７〜９のレジスト組成物の特性線である。In addition, three types of resist compositions shown in Table 2 above were used at 30% each.
The number of precipitates deposited in the resist composition when stored for a long period of time at a temperature of 0° C. was investigated in relation to the number of months, and the results shown in FIG. 2 were obtained. Note that 7 to 9 in FIG. 2 are characteristic lines of the resist compositions of samples Arashi 7 to 9, respectively.
実施例１
上記第１表及び第２表に示す試料Ｎａｌ〜９のレジスト
組成物を調製直後にウェハ上に厚さ１．５μｍ塗布した
後、９０℃で５分間ベーキングしてレジスト膜を形成し
た。つづいて、これらレジスト膜にＮ、 Ａ−０，４５
のＧ線ステッパを用いて２００ｓＷ／ｄの条件でパター
ン露光を行なった後、２．３８％のテトラメチルアンモ
ニウムヒドロキサイド水溶液で現像してレジストパター
ンを形成した。Example 1 The resist compositions of samples Nal to 9 shown in Tables 1 and 2 above were coated on a wafer to a thickness of 1.5 μm immediately after preparation, and then baked at 90° C. for 5 minutes to form a resist film. . Next, these resist films were coated with N, A-0,45
After pattern exposure was carried out under the condition of 200 sW/d using a G-line stepper, a resist pattern was formed by developing with a 2.38% tetramethylammonium hydroxide aqueous solution.
また、上記第１表及び第２表に示す９種のレジスト組成
物を夫々３０℃の温度下でＢか月間保存した後、これら
レジスト組成物を用いて前記と同様なレジスト膜の形成
、パターン露光、現像処理を行なってレジストパターン
を形成した。Further, after each of the nine resist compositions shown in Tables 1 and 2 above was stored for B months at a temperature of 30°C, a resist film similar to that described above was formed and patterned using these resist compositions. A resist pattern was formed by exposure and development.
しかして、調製直後及びＢか月間保存後のレジスト組成
物を用いた場合の各レジスト膜の感度、並びに調製直後
のレジスト組成物からなるレジスト膜と８か月間保存後
のレジスト組成物からなるレジスト膜との間の解像性の
低下の有無を調べた。Therefore, the sensitivity of each resist film when using the resist composition immediately after preparation and after storage for B months, as well as the resist film consisting of the resist composition immediately after preparation and the resist composition after storage for 8 months, The presence or absence of a decrease in resolution between the film and the film was investigated.
その結果を下記第３表に示す。The results are shown in Table 3 below.
第１図から明らかなように、一般式（１）で表わされる
感光剤を含み、かつ溶媒中にジメチルフォルムアミドを
含有するレジスト組成物（試料慮２．４．８）はジメチ
ルフォルムアミドを含まない溶媒で溶解したレジスト組
成物（試料１ｋｌ 、 ３．５）に比べて長期間保存に
おいての析出物の数が著しく少ないことがわかる。As is clear from FIG. 1, the resist composition containing the photosensitizer represented by the general formula (1) and dimethylformamide in the solvent (sample consideration 2.4.8) contains dimethylformamide. It can be seen that the number of precipitates during long-term storage is significantly smaller than that of the resist composition (sample 1kl, 3.5cm) dissolved in no solvent.
第２図から明らかなように、ジメチルフォルムアミドを
含有する溶媒を用いた場合でも使用する感光剤が全固形
分総量に対して１０〜３０重量％の範囲から逸脱するレ
ジスト組成物（試料）ＪＱ８）では長期間保存において
の析出物の数が増大することがわかる。As is clear from FIG. 2, resist composition (sample) JQ8 in which the photosensitizer used deviates from the range of 10 to 30% by weight based on the total solid content even when a solvent containing dimethylformamide is used. ), it can be seen that the number of precipitates increases during long-term storage.
第３表から明らかなように、所定のアルカリ可溶性樹脂
と一般式（１）で表わされる感光剤をジメチルフォルム
アミドを含有する溶媒で溶解し、かつ感光剤の配合割合
が全固形分総量に対して１０〜３０重量％の範囲でジメ
チルフォルムアミドの溶媒中の含有割合が１〜３０重量
％の範囲としたレジスト組成物（試料Ｎ１２．４．６．
９ ）は、Ｂか月間の保存後にも感度低下が少なく、か
つ解像性の低下がなく良好なレジストパターンを形成で
きることがわかる。これに対し、ジメチルフォルムアミ
ドを含まない溶媒で溶解したレジスト組成物（試料Ｎ１
１１．３．５）では８か月間の保存後において感度低下
、解像性の低下を生じる。また、ジメチルフォルムアミ
ドが１〜３０重量％を外れる溶媒を使用したレジスト組
成物（試料Ｎ１１７ ）では６か月間の保存後において
感度低下、解像性の低下を生じ、しかもパターンの密着
不良、耐熱性の劣化を招く。更に、ジメチルフォルムア
ミドを含有する溶媒を用いた場合でも使用する感光剤が
全固形分総量に対して１０〜３０重量％の範囲から逸脱
するレジスト組成物（試料ＮＱｇ ）では６か月間保存
において感度低下、解像性の低下を生じ、しかも析出物
の多さに起因する塗布不良も生じる。As is clear from Table 3, the specified alkali-soluble resin and the photosensitizer represented by the general formula (1) are dissolved in a solvent containing dimethylformamide, and the blending ratio of the photosensitizer is relative to the total solid content. A resist composition (Sample N12.4.6.
9) shows that even after storage for B months, a good resist pattern can be formed with little decrease in sensitivity and no decrease in resolution. In contrast, a resist composition (sample N1) dissolved in a solvent not containing dimethylformamide
11.3.5) causes a decrease in sensitivity and resolution after storage for 8 months. In addition, a resist composition (sample N117) using a solvent containing dimethylformamide outside of 1 to 30% by weight showed a decrease in sensitivity and resolution after storage for 6 months, as well as poor pattern adhesion and heat resistance. leading to sexual deterioration. Furthermore, even when a solvent containing dimethylformamide is used, a resist composition (sample NQg) in which the amount of the photosensitizer used deviates from the range of 10 to 30% by weight based on the total solid content has a low sensitivity after storage for 6 months. In addition, poor coating results due to the large amount of precipitates.
レジスト組成物調製例２
アルカリ可溶性樹脂としてノボラック樹脂７０ｇ、ビニ
ルフェノール樹脂３ｇ及び下記第４表に示す感光剤２７
９を同第４表に示す溶媒２５０ｇで混合溶解した後、０
．２μｍのフィルタで濾過して９種のレジスト組成物を
調製した。Resist Composition Preparation Example 2 70 g of novolak resin, 3 g of vinylphenol resin, and photosensitizer 27 shown in Table 4 below as alkali-soluble resin
After mixing and dissolving 9 with 250 g of the solvent shown in Table 4, 0
．． Nine types of resist compositions were prepared by filtering through a 2 μm filter.
しかして、上記９種のレジスト組成物について調製直後
の析出物の数、並びに３０℃の温度下で６か月間保存し
た後の析出物の数を調べた。その結果を同第４表に併記
した。The number of precipitates immediately after preparation and the number of precipitates after storage at a temperature of 30° C. for 6 months were investigated for the above nine resist compositions. The results are also listed in Table 4.
実施例２
上記第４表に示す９種の・レジスト組成物を調製直後に
ウェハ上に厚さ１．５μｍ塗布した後、９０℃で５分間
ベーキングしてレジスト膜を形成した。Example 2 Immediately after preparation, nine types of resist compositions shown in Table 4 were coated on a wafer to a thickness of 1.5 μm, and then baked at 90° C. for 5 minutes to form a resist film.
つづいて、これらレジスト膜にＮ、 Ａ−０，４５のＧ
線ステッパを用いて２００ａ＋Ｗ／ｍの条件でパターン
露光を行なった後、２．３８％のテトラメチルアンモニ
ウムヒドロキサイド水溶液で現像してレジストパターン
を形成した。Next, these resist films were coated with N, A-0, 45G.
After pattern exposure was performed using a line stepper under the condition of 200a+W/m, development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution to form a resist pattern.
また、上記第４表に示す９種のレジスト組成物を夫々３
０℃の温度下で６か月間保存した後、これらレジスト組
成物を用いて前記と同様なレジスト膜の形成、パターン
露光、現像処理を行なってレジストパターンを形成した
。In addition, 30% of each of the 9 types of resist compositions shown in Table 4 above were used.
After being stored at a temperature of 0° C. for 6 months, these resist compositions were used to form a resist film, pattern exposure, and development in the same manner as described above to form a resist pattern.
しかして、調製直後及びＢか月間保存後のレジスト組成
物を用いた場合の各レジスト膜の感度、並びに調製直後
のレジスト組成物からなるレジスト膜とＢか月間保存後
のレジスト組成物からなるレジスト膜との間の解像性の
低下の有無を調べた。Therefore, the sensitivity of each resist film when using the resist composition immediately after preparation and after storage for B months, and the resist film consisting of the resist composition immediately after preparation and the resist composition after storage for B months. The presence or absence of a decrease in resolution between the film and the film was investigated.
その結果を下記第５表に示す。The results are shown in Table 5 below.
上記第４表から明らかなように、一般式（Ｉ）で表わさ
れる感光剤を含み、かつ溶媒中に脂肪族アルコールを含
有するレジスト組成物（試料Ｎｌ！１２．１３．１５．
１６．１８．１９）は脂肪族アルコールを含まない溶媒
で溶解したレジスト組成物（試料Ｎａ１ｌ。As is clear from Table 4 above, the resist compositions (Sample Nl!12.13.15.
16.18.19) is a resist composition (sample Na11) dissolved in a solvent containing no aliphatic alcohol.
１４．１７）に比べて長期間保存においての析出物の数
が著しく少ないことがわかる。It can be seen that the number of precipitates during long-term storage is significantly smaller than in 14.17).
上記第５表から明らかなように、所定のアルカリ可溶性
樹脂と一般式（１）で表わされる感光剤を脂肪族アルコ
ールを含有する溶媒で溶解したレジスト組成物（試料Ｎ
ａ１２．１３．１５．１Ｂ、 １ｇ、１９）は、Ｂか月
間の保存後にも感度低下が少なく、かつ解像性の低下が
なく良好なレジストパターンを形成できることがわかる
。これに対し、脂肪族アルコールを含まない溶媒で溶解
したレジスト組成物（試料ＮｃＬｌ１％１４．１７）で
はＢか月間の保存後において感度低下、解像性の低下を
生じる。なお、試料Ｎａ１ｌ〜１９のレジスト組成物は
いずれも１３５℃以上で良好な耐熱性が得られた。As is clear from Table 5 above, the resist composition (Sample N
It can be seen that a12.13.15.1B, 1g, 19) shows little decrease in sensitivity even after storage for B months, and can form a good resist pattern without deterioration in resolution. On the other hand, the resist composition (sample NcLl 1% 14.17) dissolved in a solvent containing no aliphatic alcohol suffers from a decrease in sensitivity and resolution after being stored for B months. In addition, all of the resist compositions of samples Na11 to 19 had good heat resistance at 135° C. or higher.
［発明の効果］
以上詳述した如く、本発明によれば解像性、耐熱性に優
れるのみならず、保存安定性の優れ、微細パターンの形
成に際して析出物による欠陥発生を抑制し得る０、８μ
ｍ以下のデザインルールに対応した高性能、高信頼性の
レジスト組成物を提供できるものである。[Effects of the Invention] As detailed above, the present invention not only has excellent resolution and heat resistance, but also has excellent storage stability and can suppress the occurrence of defects due to precipitates when forming fine patterns. 8μ
It is possible to provide a high-performance, highly reliable resist composition that is compatible with design rules of m or less.
第１図は試料Ｎｎ１−８のレジスト組成物における保存
月数と析出物の数との関係を示す特性図、第２図は試料
Ｎｌ１７〜９のレジスト組成物における保存月数と析出
物の数との関係を示す特性図である。
出願人代理人 弁理士 鈴江武彦Figure 1 is a characteristic diagram showing the relationship between the number of months of storage and the number of precipitates for the resist compositions of samples Nn1-8, and Figure 2 shows the relationship between the number of months of storage and the number of precipitates for the resist compositions of samples Nl17-9. FIG. Applicant's agent Patent attorney Takehiko Suzue
Claims (2)
ジスト組成物をおいて、前記感光剤が下記一般式（Ｉ）
にて表わされる有機化合物からなり、かつ溶媒が少なく
ともジメチルフォルムアミドを含有するものからなるこ
とを特徴とするレジスト組成物。 ▲数式、化学式、表等があります▼（ I ） 但し、式中のＲ＿１〜Ｒ＿１＿０のうち少なくとも１つ
は構造式（II） ▲数式、化学式、表等があります▼（II） で示される感光基を示し、残りは水素原子、ヒドロキシ
基であり、かつ上記構造式（II）で表わされる感光基と
ヒドロキシ基の数の和が４以上である。(1) A resist composition containing an alkali-soluble resin, a photosensitizer, and a solvent, wherein the photosensitizer has the following general formula (I).
1. A resist composition comprising an organic compound represented by: and a solvent containing at least dimethylformamide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) However, at least one of R_1 to R_1_0 in the formula is the structural formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) Photosensitive group The remainder are hydrogen atoms and hydroxy groups, and the sum of the numbers of photosensitive groups and hydroxy groups represented by the above structural formula (II) is 4 or more.
するもの用いることを特徴とする請求項１記載のレジス
ト組成物。(2) The resist composition according to claim 1, wherein a solvent containing at least an aliphatic alcohol is used as a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4889488A JPH01222255A (en) | 1988-03-02 | 1988-03-02 | Resist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4889488A JPH01222255A (en) | 1988-03-02 | 1988-03-02 | Resist composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01222255A true JPH01222255A (en) | 1989-09-05 |
Family
ID=12815978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4889488A Pending JPH01222255A (en) | 1988-03-02 | 1988-03-02 | Resist composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01222255A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358823A (en) * | 1991-04-09 | 1994-10-25 | Hoechst Aktiengesellschaft | Radiation-sensitive composition containing esterification product of (1,2-naphthoquinone-2-diazide)-sulfonic acid with 2,3,4,4'-tetrahydroxybenzophenone and a di- or tri-hydroxybenzophenone |
-
1988
- 1988-03-02 JP JP4889488A patent/JPH01222255A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358823A (en) * | 1991-04-09 | 1994-10-25 | Hoechst Aktiengesellschaft | Radiation-sensitive composition containing esterification product of (1,2-naphthoquinone-2-diazide)-sulfonic acid with 2,3,4,4'-tetrahydroxybenzophenone and a di- or tri-hydroxybenzophenone |
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