JPH0263052A - Positive photosensitive resin composition and process for preparing resist pattern using the composition - Google Patents
Positive photosensitive resin composition and process for preparing resist pattern using the compositionInfo
- Publication number
- JPH0263052A JPH0263052A JP21536688A JP21536688A JPH0263052A JP H0263052 A JPH0263052 A JP H0263052A JP 21536688 A JP21536688 A JP 21536688A JP 21536688 A JP21536688 A JP 21536688A JP H0263052 A JPH0263052 A JP H0263052A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- photosensitive resin
- positive photosensitive
- resin composition
- resist pattern
- 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
- 239000011342 resin composition Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 title description 4
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 10
- 239000010419 fine particle Substances 0.000 abstract description 9
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract description 5
- 229930003836 cresol Natural products 0.000 abstract description 5
- -1 for example Chemical compound 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 229920001225 polyester resin Polymers 0.000 abstract description 3
- 239000004645 polyester resin Substances 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003504 photosensitizing agent Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-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
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical class [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 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
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポジ型感光性樹脂組成物に関し、さらに詳しく
は１．２−キノンジアジド化合物の溶解性に優れたポジ
型感光性樹脂組成物およびこれを用いたレジストパター
ンの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a positive photosensitive resin composition, and more particularly to a positive photosensitive resin composition having excellent solubility of a 1,2-quinonediazide compound, and a positive photosensitive resin composition thereof. This invention relates to a method of manufacturing a resist pattern using the method.
ポジ型感光性樹脂組成物は、該組成物を基板上に塗布、
乾燥させた後、露光、現像して得られるレジストパター
ンが、現像によるレジストの膨ｉｆ４がなく、１μｍ以
下の微細パターンを形成することができるため広く用い
られている。A positive photosensitive resin composition is prepared by coating the composition on a substrate,
A resist pattern obtained by drying, exposing, and developing is widely used because there is no expansion if4 of the resist due to development and a fine pattern of 1 μm or less can be formed.
しかしながら、前記ポジ型感光性樹脂組成物には、例え
ば溶剤として酢酸−２−エトキシエチル、アルカリ水溶
液可溶性樹脂としてクレゾールなどのノボラック樹脂、
１．２−キノンジアジド化合物としてナフトキノンジア
ジド系感光剤などが用いられるが、該樹脂組成物を製造
した後、経口とともに製造時にはみられない微粒子が発
生する欠点がある。However, the positive photosensitive resin composition includes, for example, 2-ethoxyethyl acetate as a solvent, a novolak resin such as cresol as an alkaline aqueous solution-soluble resin,
As the 1.2-quinonediazide compound, a naphthoquinonediazide-based photosensitizer is used, but after producing the resin composition, there is a drawback that fine particles not seen during production are generated as well as when the resin composition is produced.
樹脂組成物中の微粒子の発生を抑える方法として、１，
２−キノンジアジド化合物の合成に用いられるポリヒド
ロキシ化合物の水酸基の一部をアシル化する方法（特開
昭６２−１７８５６２号公報）、モノオキシモノカルボ
ン酸エステルを溶剤として用いる方法（特開昭６２−１
２３４４４号公報）、アミド系溶剤であるジメチルホル
ムアミドを用いる方法（特開昭６２−２８０８４４号公
報）などが提案されているが、これらの方法においては
１，２−キノンジアジド化合物などの感光剤の溶解性が
考慮されていない。As a method for suppressing the generation of fine particles in a resin composition, 1.
A method of acylating a part of the hydroxyl group of a polyhydroxy compound used in the synthesis of a 2-quinonediazide compound (JP-A-62-178562), a method of using monooxymonocarboxylic acid ester as a solvent (JP-A-62-178562); 1
23444) and a method using dimethylformamide, an amide solvent (Japanese Patent Application Laid-open No. 62-280844), but these methods require dissolution of photosensitizers such as 1,2-quinonediazide compounds. Gender is not taken into account.
本発明の目的は、前記従来技術の欠点を除去し、１．２
−キノンジアジド化合物の溶解性に優れた溶剤を用いて
微粒子の発生のないポジ型感光性樹脂組成物およびこれ
を用いたレジストパターンの製造法を提供することにあ
る。The purpose of the present invention is to eliminate the drawbacks of the prior art and 1.2
- To provide a positive photosensitive resin composition that does not generate fine particles by using a solvent with excellent solubility of a quinonediazide compound, and a method for producing a resist pattern using the same.
本発明者らは、鋭意研究した結果、前記微粒子の発生は
、樹脂や感光剤の溶剤に対する溶解性不足に起因し、樹
脂や感光剤に対して良溶解性の溶剤を用いることによっ
て微粒子の経口増加を抑えることができることを見出し
、本発明に到達した。As a result of extensive research, the present inventors found that the generation of fine particles is due to insufficient solubility of resins and photosensitizers in solvents. We have discovered that the increase can be suppressed, and have arrived at the present invention.
すなわち、本発明は、アルカリ水溶液可溶性樹脂と、１
．２−キノンジアジド化合物と、溶剤とを含むポジ型感
光性樹脂組成物において、全溶剤に対して２重量％以上
のＮ−メチルピロリドンを含有する溶剤を用いてなるポ
ジ型感光性樹脂組成物およびこの組成物を基板上に塗布
、乾燥後、露光、現像するレジストパターンの製造法に
関する。That is, the present invention provides an alkaline aqueous solution-soluble resin;
．． A positive photosensitive resin composition containing a 2-quinonediazide compound and a solvent, and a positive photosensitive resin composition using a solvent containing N-methylpyrrolidone in an amount of 2% by weight or more based on the total solvent; The present invention relates to a method for producing a resist pattern, in which a composition is applied onto a substrate, dried, exposed, and developed.
本発明に用いられるアルカリ水溶液可溶性樹脂は、水酸
化ナトリウム、水酸化カリウム、水酸化テトラメチルア
ンモニウム、コリン等の５重■％以下のアルカリ水溶液
に可溶な樹脂である。これらの樹脂としては、例えばフ
ェノール、クレゾール、キシレノールなどのフェノール
類と、ホルムアルデヒドとを縮合させて得られるノボラ
ック樹脂、アセトンピロガロール樹脂、アクリル酸ポリ
マー、アクリル酸とスチレンなどの共重合体樹脂、マレ
イン酸などを用いたポリエステル樹脂などが用いられる
。The alkali aqueous solution-soluble resin used in the present invention is a resin soluble in an alkali aqueous solution of 5% by weight or less, such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, etc. These resins include, for example, novolac resin obtained by condensing phenols such as phenol, cresol, and xylenol with formaldehyde, acetone pyrogallol resin, acrylic acid polymer, copolymer resin of acrylic acid and styrene, and maleic acid. A polyester resin using, for example, is used.
前記アルカリ水溶液可溶性樹脂は、その被膜に耐熱性を
保持させるため、ＪＩＳＫ ２２０７の測定法に基づ
く軟化温度が１３５〜１６５°Ｃの範囲であることが好
ましい。軟化温度が低すぎると耐熱性が不充分であり、
また高すぎると現在の工業的設備では合成が難しい場合
がある。ノボラック樹脂の軟化温度の調整は、公知の方
法によって行うことができる。The alkaline aqueous solution-soluble resin preferably has a softening temperature in the range of 135 to 165°C based on the measurement method of JISK 2207 in order to maintain heat resistance in the coating. If the softening temperature is too low, the heat resistance will be insufficient,
Moreover, if it is too high, it may be difficult to synthesize with current industrial equipment. The softening temperature of the novolac resin can be adjusted by a known method.
ノボラ、り樹脂は、塩酸、蓚酸等の触媒の存在下で、フ
ェノール類とホルムアルデヒドとを６０〜１２０°Ｃの
温度で数時間反応させた後、水分および未反応フェノー
ル類を減圧下で加熱して除去することによって合成する
ことができる。Novola resin is produced by reacting phenols and formaldehyde at a temperature of 60 to 120°C for several hours in the presence of a catalyst such as hydrochloric acid or oxalic acid, and then heating water and unreacted phenols under reduced pressure. It can be synthesized by removing it.
本発明に用いられる１、２−キノンジアジド化合物とし
ては、１．２−ベンゾキノンジアジド−４−スルホン酸
エステル、１．２−ナフトキノンジアジド−４−スルホ
ン酸エステル、１，２−ナフトキノンジアジド−５−ス
ルホン酸エステル等が挙げられる。Examples of the 1,2-quinonediazide compound used in the present invention include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5-sulfonic acid ester. Examples include acid esters.
これらの化合物は、既に公知の化合物であり、モノまた
はポリヒドロキシ化合物と、１，２−ベンゾキノンジア
ジド−４−スルホニルクロライド、１．２−ナフトキノ
ンジアジド−４−スルホニルクロライド、１，２−ナフ
トキノンジアジド−５スルホニルクロライドなどとをジ
オキサン、テトラヒドロフラン、アセトン、メチルエチ
ルケトン、水、セロソルブ等の溶媒に溶かし、反応の促
進のために塩基性触媒を用いて脱塩酸反応を行って合成
することができる。前記塩基性触媒としては、炭酸ナト
リウム、炭酸カリウム、水酸化ナトリウム、水酸化カリ
ウム等の無機塩基、トリエチルアミン、トリエタノール
アミン、ジエチルアミン等の有機塩基が通常用いられる
。また合成温度には特に制限はないが、主生成物の安定
性、反応速度等の点からＯ〜４０゛Ｃの範囲が好ましい
。さらに合成反応は黄色光下または赤色光下で行なうこ
とが好ましい。These compounds are already known compounds, and include mono- or polyhydroxy compounds, 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, and 1,2-naphthoquinonediazide-4-sulfonyl chloride. It can be synthesized by dissolving 5-sulfonyl chloride or the like in a solvent such as dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, water, or cellosolve, and performing a dehydrochlorination reaction using a basic catalyst to promote the reaction. As the basic catalyst, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine, triethanolamine and diethylamine are usually used. The synthesis temperature is not particularly limited, but is preferably in the range of 0 to 40°C from the viewpoint of stability of the main product, reaction rate, etc. Furthermore, the synthesis reaction is preferably carried out under yellow light or red light.
前記モノまたはポリヒドロキシ化合物としては、トリヒ
ドロキシフェニルメチルケＩ・ンなどのトリヒドロキシ
フェニルアルキルケトン、トリヒドロキシベンゾフェノ
ン、テトラヒドロキシベンゾフェノン、没食子酸メチル
、没食子酸プロピルなどの没食子酸エステルなどが挙げ
られる。モノまたはポリヒドロキシ化合物と上記１．２
−キノンジアジド−４−スルホニルクロライド等との反
応割合は、モノまたはポリヒドロキシ化合物１モルに対
し、１モルからポリヒドロキシ化合物の水酸基数のモル
数と同じモル数だけの１．２−キノンジアジド化合物が
通常用いられる。Examples of the mono- or polyhydroxy compound include trihydroxyphenylalkyl ketones such as trihydroxyphenylmethylken, trihydroxybenzophenone, tetrahydroxybenzophenone, and gallic acid esters such as methyl gallate and propyl gallate. Mono- or polyhydroxy compound and 1.2 above
-The reaction ratio with quinonediazide-4-sulfonyl chloride etc. is usually from 1 mole to 1 mole of 1,2-quinonediazide compound equal to the number of moles of hydroxyl groups of the polyhydroxy compound per mole of the mono- or polyhydroxy compound. used.
本発明に用いられる溶剤には、Ｎ−メチルピロリドンが
全溶剤に対して２重量％以上、好ましくは２〜５０重量
％、より好ましくは３〜３０重量％用いられる。Ｎ−メ
チルピロリドンの使用割合が２重量％未満では１．２−
キノンジアジド化合物を溶解する効果が小さい。In the solvent used in the present invention, N-methylpyrrolidone is used in an amount of 2% by weight or more, preferably 2 to 50% by weight, more preferably 3 to 30% by weight based on the total solvent. If the proportion of N-methylpyrrolidone used is less than 2% by weight, 1.2-
The effect of dissolving quinonediazide compounds is small.
本発明に用いられるＮ−メチルピロリドン以外の溶剤と
しては、例えばアセトン、メチルエチルケトン、メチル
イソブチルケトン、シクロヘキサノン等のケトン系溶剤
、トルエン、キシレン等の芳香族系溶剤、メチルセロソ
ルブ、メチルセロソルブアセテ−１−、エチルセロソル
ブアセテート等のセロソルブ系溶剤、酢酸−２−エトキ
シエチル、酢酸エチル、酢酸ブチル、酢酸イソアミル等
のエステル系溶剤、メタノール、エタノール、プロパツ
ール等のアルコール系溶剤等が挙げられる。これらの溶
剤は単独でまたは２種以上混合して用いられる。Solvents other than N-methylpyrrolidone used in the present invention include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic solvents such as toluene and xylene, methyl cellosolve, methyl cellosolve acetate-1- , cellosolve solvents such as ethyl cellosolve acetate, ester solvents such as 2-ethoxyethyl acetate, ethyl acetate, butyl acetate, and isoamyl acetate, and alcohol solvents such as methanol, ethanol, and propatool. These solvents may be used alone or in combination of two or more.
本発明のポジ型感光性樹脂組成物は、シリコン、アルミ
ニ、ラム、石英、ガラスなどの基板上にロールコータ、
スピンナーなどを用いて通常の方法によって塗布、乾燥
されて被膜とされる。該被膜は、所望のフォトマスクを
介して水銀灯照射等の公知の手段によって露光され、露
光部分の感光剤が光化学的に分解してアルカリ水溶液に
可溶となり、アルカリ水溶液で現像され、レジストパタ
ーンとされる。該アルカリ水溶液としては、例えば水酸
化ナトリウム、水酸化カリウム、水酸化テトラメチルア
ンモニウム、コリン等の５重量％以下の水溶液が用いら
れる。The positive photosensitive resin composition of the present invention can be coated on a substrate such as silicon, aluminum, ram, quartz, or glass using a roll coater.
It is applied by a conventional method using a spinner or the like and dried to form a film. The film is exposed to light by a known means such as mercury lamp irradiation through a desired photomask, and the photosensitizer in the exposed area is photochemically decomposed and becomes soluble in an alkaline aqueous solution, and is developed with an alkaline aqueous solution to form a resist pattern. be done. As the alkaline aqueous solution, for example, an aqueous solution of 5% by weight or less of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, etc. is used.
本発明になる感光性樹脂組成物は、目的に応じて副次的
な成分、例えば貯蔵安定性を向上させるために熱重合防
止剤、基板との密着性を向上させるために密着性向上剤
等を含有していてもよい。The photosensitive resin composition of the present invention may contain secondary components depending on the purpose, such as a thermal polymerization inhibitor to improve storage stability, an adhesion improver to improve adhesion to a substrate, etc. may contain.
［実施例〕 以下、本発明を実施例により詳しく説明する。[Example〕 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
２．３．４−トリヒドロキシベンゾフェノン１モルと、
１，２−ナフトキノン−（２）−ジアジド−５−スルホ
ニルクロライド２．８モルとを反応させた感光剤（以下
、感光剤Ａとする）４ｇを、酢酸−２−エトキシエチル
９０ｇとＮ−メチルピロリドンＬｏｇからなる溶剤に溶
解した。感光剤Ａは２０°Ｃ下で３０分以内に溶解した
。またその後にタレゾールノボラック樹脂（群栄化学工
業社製、ＰＳＦ２８０３）を２０ｇ加えても相溶した。Example 1 1 mole of 2.3.4-trihydroxybenzophenone,
4 g of a photosensitizer (hereinafter referred to as photosensitizer A) prepared by reacting 2.8 moles of 1,2-naphthoquinone-(2)-diazido-5-sulfonyl chloride with 90 g of 2-ethoxyethyl acetate and N-methyl It was dissolved in a solvent consisting of pyrrolidone Log. Photosensitizer A dissolved within 30 minutes at 20°C. Further, even when 20 g of Talesol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., PSF2803) was added afterwards, the mixtures were compatible.
実施例２
２．３，４．４’−テトラヒドロキシベンゾフェノン１
モルと、１．２−ナフトキノン−（２）−ジアジド−５
−スルホニルクロライド３．２モルとを反応させた感光
剤（以下、感光剤Ｂとする）５ｇを、酢酸−２−エトキ
シエチル８０ｇとＮ−メチルピロリドン２０ｇからなる
溶剤に溶解した。Example 2 2.3,4.4'-tetrahydroxybenzophenone 1
moles and 1,2-naphthoquinone-(2)-diazide-5
- 5 g of a photosensitizer reacted with 3.2 moles of sulfonyl chloride (hereinafter referred to as photosensitizer B) was dissolved in a solvent consisting of 80 g of 2-ethoxyethyl acetate and 20 g of N-methylpyrrolidone.
感光剤は２０°Ｃ下で２０分以内に溶解した。またその
後に実施例１で用いたクレゾールノボラック樹脂２０ｇ
を加えても相溶した。The photosensitizer dissolved within 20 minutes at 20°C. After that, 20 g of the cresol novolak resin used in Example 1
They were compatible even when added.
実施例３
メタクレゾールとパラクレゾールとの重量比（メタクレ
ゾール／パラクレゾール）を５５／４５として得られ、
軟化温度が１５０°Ｃのクレゾールノボラック樹脂２０
ｇおよび実施例２で得た感光剤８５ｇを、酢酸−２−エ
トキシエチル９０ｇとＮ−メチルピロリドン１０ｇから
なる溶剤に溶解して得られたポジ型感光性樹脂組成物を
０．２μｍのテフロンフィルタで濾過した。得られたポ
ジ型感光性樹脂組成物をシリコンウェーハ上に３００、
Ｏｒｐｍで３０秒間回転塗布し、９０″Ｃで２０分間対
流式乾燥機内で乾燥し、厚さ１μｍの感光膜を得た。次
いで感光膜を露光装置ＬＤ−５０１０ｉ（日立製作所社
製）を用いてフォトマスクを介して６００ミリ秒間露光
し、２．３８重量％のテトラメチルアンモニウム水溶液
で２３℃で６０秒間現像した後、脱イオン水で６０秒間
リンスした。Example 3 Obtained with a weight ratio of metacresol and para-cresol (metacresol/para-cresol) of 55/45,
Cresol novolac resin 20 with a softening temperature of 150°C
A positive photosensitive resin composition obtained by dissolving 85 g of the photosensitizer obtained in Example 2 and 90 g of 2-ethoxyethyl acetate and 10 g of N-methylpyrrolidone was filtered through a 0.2 μm Teflon filter. It was filtered with The obtained positive photosensitive resin composition was placed on a silicon wafer for 300 min.
Orpm for 30 seconds and dried in a convection dryer at 90"C for 20 minutes to obtain a photoresist film with a thickness of 1 μm.Then, the photoresist film was coated using an exposure device LD-5010i (manufactured by Hitachi, Ltd.). It was exposed for 600 milliseconds through a photomask, developed with a 2.38% by weight aqueous tetramethylammonium solution at 23° C. for 60 seconds, and then rinsed with deionized water for 60 seconds.
レジストパターンとして０．７μｍの線幅のパターンが
得られた。A pattern with a line width of 0.7 μm was obtained as a resist pattern.
次にこの感光性樹脂組成物を４０°Ｃに３０日間保存し
たところ、目視では微粒子の発生は認められなかった。Next, when this photosensitive resin composition was stored at 40°C for 30 days, no generation of fine particles was observed visually.
比較例１
実施例２で用いた感光剤Ｂ５ｇを酢酸−２−エトキシエ
チル１００ｇの溶剤に溶解したが、２０°Ｃ下では１日
経過後もわずかの不溶物があった。Comparative Example 1 5 g of the photosensitizer B used in Example 2 was dissolved in 100 g of 2-ethoxyethyl acetate in a solvent, but a small amount of insoluble matter remained at 20° C. even after one day had passed.
比較例２
比較例１で得た溶液に実施例３で用いた樹脂を２０ｇ溶
解し、得られたポジ型感光性樹脂組成物を０．２μｍの
テフロンフィルタで濾過した。Comparative Example 2 20 g of the resin used in Example 3 was dissolved in the solution obtained in Comparative Example 1, and the resulting positive photosensitive resin composition was filtered through a 0.2 μm Teflon filter.
得られたポジ型感光性樹脂組成物を４０″Ｃに３０日間
保存したところ、濾過直後には認められなかった微粒子
が目視で認められた。When the obtained positive photosensitive resin composition was stored at 40''C for 30 days, fine particles that were not observed immediately after filtration were visually observed.
本発明のポジ型感光性樹脂組成物は、１．２キノンジア
ジド化合物の溶剤に対する溶解性が優れるため、微粒子
の経口増加がなく、写真工業、印刷工業、電子工業等の
分野に広く使用することができる。Since the positive photosensitive resin composition of the present invention has excellent solubility of the 1.2 quinone diazide compound in solvents, there is no increase in the amount of fine particles ingested, and it can be widely used in fields such as the photographic industry, the printing industry, and the electronic industry. can.
Claims (1)
ジド化合物と、溶剤とを含むポジ型感光性樹脂組成物に
おいて、全溶剤に対して２重量％以上のＮ−メチルピロ
リドンを含有する溶剤を用いてなるポジ型感光性樹脂組
成物。 ２、請求項１記載のポジ型感光性樹脂組成物を基板上に
塗布、乾燥後、露光、現像するレジストパターンの製造
法。[Claims] 1. In a positive photosensitive resin composition containing an alkaline aqueous solution-soluble resin, a 1,2-quinonediazide compound, and a solvent, N-methylpyrrolidone is added in an amount of 2% by weight or more based on the total solvent. A positive photosensitive resin composition containing a solvent. 2. A method for producing a resist pattern, which comprises applying the positive photosensitive resin composition according to claim 1 onto a substrate, drying it, exposing it to light, and developing it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21536688A JPH0263052A (en) | 1988-08-30 | 1988-08-30 | Positive photosensitive resin composition and process for preparing resist pattern using the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21536688A JPH0263052A (en) | 1988-08-30 | 1988-08-30 | Positive photosensitive resin composition and process for preparing resist pattern using the composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0263052A true JPH0263052A (en) | 1990-03-02 |
Family
ID=16671103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21536688A Pending JPH0263052A (en) | 1988-08-30 | 1988-08-30 | Positive photosensitive resin composition and process for preparing resist pattern using the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0263052A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0625568A1 (en) * | 1993-05-18 | 1994-11-23 | Sumitomo Chemical Company, Limited | Cleaning solution for apparatuses contacted with quinone diazide photosensitizers and cleaning method using the same |
| KR100225207B1 (en) * | 1991-01-24 | 1999-10-15 | 마쯔모또 에이찌 | I-ray sensitive positive resist composition and pattern forming method using the same |
-
1988
- 1988-08-30 JP JP21536688A patent/JPH0263052A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100225207B1 (en) * | 1991-01-24 | 1999-10-15 | 마쯔모또 에이찌 | I-ray sensitive positive resist composition and pattern forming method using the same |
| EP0625568A1 (en) * | 1993-05-18 | 1994-11-23 | Sumitomo Chemical Company, Limited | Cleaning solution for apparatuses contacted with quinone diazide photosensitizers and cleaning method using the same |
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