JPH02245754A - Positive type resist composition - Google Patents
Positive type resist compositionInfo
- Publication number
- JPH02245754A JPH02245754A JP6716889A JP6716889A JPH02245754A JP H02245754 A JPH02245754 A JP H02245754A JP 6716889 A JP6716889 A JP 6716889A JP 6716889 A JP6716889 A JP 6716889A JP H02245754 A JPH02245754 A JP H02245754A
- Authority
- JP
- Japan
- Prior art keywords
- positive type
- type resist
- resist composition
- esters
- sulfonic acid
- 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 description 12
- 229920003986 novolac Polymers 0.000 claims abstract description 12
- -1 quinonediazide sulfonic acid esters Chemical class 0.000 claims description 17
- 150000002989 phenols Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- 150000004820 halides Chemical class 0.000 abstract 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UYBDKTYLTZZVEB-UHFFFAOYSA-N (2,3,4,5,6-pentahydroxyphenyl)-phenylmethanone Chemical compound OC1=C(O)C(O)=C(O)C(O)=C1C(=O)C1=CC=CC=C1 UYBDKTYLTZZVEB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical class OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 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、r値の高いレジスト組成物に関するものであ
る@
〈従来の技術及び発明の課題〉
キノンジアジド基を有する化合物とノボラック樹脂から
なる組成物は、800〜5 Q Q nmの光照射によ
りキノンジアジド基が分解してカルボキシル基を生ずる
ことにより、アルカリ不溶の状態からアルカリ可溶性に
なることを利用してポジ型レジストとして用いられろ。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a resist composition with a high r value @ <Prior Art and Problems of the Invention> A composition consisting of a compound having a quinonediazide group and a novolak resin The material can be used as a positive resist by utilizing the fact that the quinone diazide group decomposes to produce a carboxyl group upon irradiation with light of 800 to 5 Q Q nm, thereby changing from an alkali-insoluble state to an alkali-soluble state.
このポジ型レジストはネガ型レジストに比べ解像力が著
しく優れているという特長を有し、工CやLSIなどの
集積回路の製作に利用されている。This positive type resist has a feature that its resolution is significantly superior to that of a negative type resist, and is used in the production of integrated circuits such as electronic circuits and LSIs.
近年集積回路については高集積化に伴う微細化が進み、
今やサブミクロンのパターン形成が要求されるに至って
いる。その結果ポジ型レジストについてもより優れた解
像度(高いγ値)が求められろようになった。In recent years, integrated circuits have become increasingly finer due to higher integration.
Submicron pattern formation is now required. As a result, even better resolution (higher γ value) is required for positive resists.
しかるに、キノンジアジド化合物とノボラック樹脂から
なるレジスト材料において、従来からある材料の組合せ
ではr値の向上には限界があった。However, in a resist material made of a quinonediazide compound and a novolac resin, there is a limit to the improvement of the r value with conventional combinations of materials.
例えば、r値を向上させるには、キノンジアジド化合物
の量を増やすことが考えられる。For example, in order to improve the r value, it is possible to increase the amount of the quinonediazide compound.
ところが、キノンジアジド化合物の量を増やすことは、
感度の低下や現像残渣の増加といった重大な欠点がある
。However, increasing the amount of quinonediazide compound
There are serious drawbacks such as a decrease in sensitivity and an increase in development residue.
従って、r値の向上には制限があった。Therefore, there was a limit to the improvement of the r value.
本発明の目的は、r値の高いポジ型レジスト組成物を提
供することである。An object of the present invention is to provide a positive resist composition with a high r value.
本発明者は、特定の構造を有する多価フェノール化合物
のキノンジアジドスルエン酸エステルを用いれば著るし
くr値が向上することを見出し本発明を完成した。The present inventors have completed the present invention by discovering that the r value can be significantly improved by using a quinonediazide sulfate ester of a polyhydric phenol compound having a specific structure.
〈課題の解決手段〉
本発明は、ノボラック樹脂、および下記式で表わされる
フェノール化合物のキノンジアジドスルホン酸エステル
の1濡または2濡以上を含有するポジ型レジスト組成物
である。<Means for Solving the Problems> The present invention is a positive resist composition containing a novolac resin and one or two or more parts of a quinonediazide sulfonic acid ester of a phenol compound represented by the following formula.
上記のフェノール化合物のキノンジアジドスルホン酸エ
ステルの製造法としては公知の方法が用いられる。例え
ばナフトキノンジアジドスルホン酸ハロゲン化物や、ベ
ンゾキノンジアジドスルホン酸ハロゲン化物と上記のフ
ェノール化合物を、炭酸ソーダ等の弱アルカリの存在下
で縮合することにより得られる。テトラエステル体の含
量がこの反応により得られるエステル中の50重量%以
上となるような条件で反応することが好ましい。A known method can be used to produce the quinonediazide sulfonic acid ester of the above-mentioned phenol compound. For example, it can be obtained by condensing naphthoquinonediazide sulfonic acid halide or benzoquinonediazide sulfonic acid halide with the above-mentioned phenol compound in the presence of a weak alkali such as soda carbonate. It is preferable to carry out the reaction under conditions such that the content of the tetraester is 50% by weight or more in the ester obtained by this reaction.
本発明において、上述のキノンジアジドスルホン酸エス
テルは1覆類を用いてもよいし、2種類z上を用いても
よい。In the present invention, the above-mentioned quinonediazide sulfonic acid ester may be used in one type or in two types.
本発明の組成物には、他の多価フェノール化合物のキノ
ンジアジドスルホン酸エステルを加えてもよい。他の多
価フェノール化合物としては、ハイドロキノン、レゾル
シン、フロログリシン、2.4−ジヒドロキシベンゾフ
ェノン、2.8.4−トリヒドロキシベンゾフェノン、
2.8,8.4−テトラヒドロキシベンゾフェノン、2
.8,4.4’−テトラヒドロキシベンゾフェノン、2
.2’、4.4’−テトラヒドロキシベンゾフェノンな
どのテトラヒドロキシベンゾフェノン類、2,8.8’
、4’−ペンタヒドロキシベンゾフェノン、2 、8
、8’ 、 4 、5’−ペンタヒドロキシベンゾフェ
ノンなどのペンタヒドロキシベンゾフェノン類、没食子
酸アルキルエステル等が例示される。Quinonediazide sulfonic acid esters of other polyhydric phenol compounds may be added to the compositions of the present invention. Other polyhydric phenol compounds include hydroquinone, resorcinol, phloroglycin, 2.4-dihydroxybenzophenone, 2.8.4-trihydroxybenzophenone,
2.8,8.4-tetrahydroxybenzophenone, 2
.. 8,4.4'-tetrahydroxybenzophenone, 2
.. Tetrahydroxybenzophenones such as 2',4.4'-tetrahydroxybenzophenone, 2,8.8'
, 4'-pentahydroxybenzophenone, 2, 8
, 8', 4, 5'-pentahydroxybenzophenones such as pentahydroxybenzophenone, gallic acid alkyl esters, and the like.
本発明に用いられるノボラック樹脂は、フェノール類と
ホルムアルデヒドを付加縮合反応して得られるものであ
る。ノボラック樹脂の製造に用いられろフェノール類の
具体例としては、フェノール、クレゾール、キシレノー
ル、エチルフェノール、トリメチルフェノール、プロピ
ルフェノール、ブチルフェノール、ジヒドロキシベンゼ
ン、ナフトール類等を挙げることができる。これらフェ
ノール類は単独で、又は混合して使用することができる
。フェノール類と付加縮合反応させるホルムアルデヒド
としてはホルムアルデヒド水溶液(ホルマリン)やパラ
ホルムアルデヒドが用いられる。特に8796のホルマ
リンは工業的に量産されており好都合である。フェノー
ル類とホルムアルデヒドとの付加縮合反応は常法に従っ
て行われる。反応は通常60〜120°C,2〜80時
間で行なわれる。The novolak resin used in the present invention is obtained by addition-condensation reaction of phenols and formaldehyde. Specific examples of phenols used in the production of novolac resins include phenol, cresol, xylenol, ethylphenol, trimethylphenol, propylphenol, butylphenol, dihydroxybenzene, naphthols, and the like. These phenols can be used alone or in combination. As the formaldehyde to be subjected to an addition condensation reaction with phenols, an aqueous formaldehyde solution (formalin) or paraformaldehyde is used. In particular, formalin 8796 is industrially mass-produced and is convenient. The addition condensation reaction between phenols and formaldehyde is carried out according to a conventional method. The reaction is usually carried out at 60-120°C for 2-80 hours.
触媒としては有機酸或いは無機酸や二価金属塩等が用い
られる。具体例としては蓚酸、塩酸、硫酸、過塩素酸、
p−トルエンスルホン酸、トリクロル酢酸、リン酸、蟻
酸、酢酸亜鉛、酢酸マグネシウム等があげられる。As the catalyst, organic or inorganic acids, divalent metal salts, etc. are used. Specific examples include oxalic acid, hydrochloric acid, sulfuric acid, perchloric acid,
Examples include p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, formic acid, zinc acetate, and magnesium acetate.
また反応はバルクで1行なっても適当な溶剤を用いても
よい。Further, the reaction may be carried out in bulk or an appropriate solvent may be used.
本発明においてキノンジアジドスルホン酸エステル成分
の添加量は、レジスト組成物中の全固型分中に占める割
合が15〜60重量%の範囲であることが好ましい。In the present invention, the amount of the quinonediazide sulfonic acid ester component added is preferably in the range of 15 to 60% by weight in the total solid content of the resist composition.
レジスト液の調整は、キノンジアジドスルホン酸エステ
ルとノボラック樹脂を溶剤に混合溶解することにより行
なう。The resist solution is prepared by mixing and dissolving quinonediazide sulfonic acid ester and novolak resin in a solvent.
用いる溶剤は、適当な乾燥速度を有し、溶剤が蒸発して
均一で平滑な塗膜を与えるものがよい。The solvent used should preferably have an appropriate drying rate and evaporate to give a uniform and smooth coating film.
このような溶剤としては、エ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、工チルセロソルブ、メ
チルセロソルブ、プロピレングリコール、モノメチルエ
ーテルアセテート、酢酸ブチル、メチルイソブチルケト
ン、キシレン等があげられる。以上の方法で得られたレ
ジスト組成物は、さらに必要に応じて付加物として少量
の樹脂や染料等が添加されていてもよい。Examples of such solvents include ethyl cellosolve acetate, methyl cellosolve acetate, engineered methyl cellosolve, methyl cellosolve, propylene glycol, monomethyl ether acetate, butyl acetate, methyl isobutyl ketone, xylene, and the like. The resist composition obtained by the above method may further contain a small amount of a resin, a dye, etc. as an additive, if necessary.
〈発明の効果〉
本発明のポジ型レジスト組成物はr値の高いレジスト組
成物である。そして現像残渣の増加等の問題点もない。<Effects of the Invention> The positive resist composition of the present invention has a high r value. Further, there are no problems such as an increase in development residue.
〈実施例〉
次に実施例をあげて、本発明をさらに具体的に説明する
が、本発明はこれらの実施例によって何ら限定されるも
のではない。<Examples> Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples.
合成例1
内容積300 dの三ツロフラスコに、下式(1)で表
わされる化合物を5.20F、ナフトキノン−(1,2
)−ジアジド−(2)−5−スルホン酸クロリドを20
.91’、(反応モル比1:8.9)、ジオキサンを2
621仕込んだのち、攪拌して完溶させた。そののち、
攪拌しながら、フラスコを水浴に浸して、反応温度を2
0〜25℃にコントロールし、トリエチルア【ン8.6
8Pを滴下ロートを用いて80分間で滴下させた。その
のち、反応温度を20〜25°Cに保ちながら4時間攪
拌を続けた。Synthesis Example 1 A compound represented by the following formula (1) was placed in a Mitsuro flask with an internal volume of 300 d at 5.20F and naphthoquinone-(1,2
)-diazide-(2)-5-sulfonic acid chloride at 20
.. 91', (reaction molar ratio 1:8.9), dioxane 2
After adding 621, it was stirred to completely dissolve it. after that,
While stirring, immerse the flask in a water bath to bring the reaction temperature to 2.
Controlled at 0-25℃, triethylane 8.6
8P was added dropwise over 80 minutes using a dropping funnel. Thereafter, stirring was continued for 4 hours while maintaining the reaction temperature at 20-25°C.
反応後、イオン交換水にチャージしたのち、濾過、乾燥
させることによって、感放射線性成分Bを得た。After the reaction, the mixture was charged into ion-exchanged water, filtered, and dried to obtain radiation-sensitive component B.
合成例2
式(1)で表わされる化合物のかわ抄に2,8゜4.4
′−テトラヒドロキシベンゾフェノンを用いた以外は合
成例1と同様にして感放射線性成分を得た。得られた感
放射線性成分をCとする。Synthesis Example 2 2.8°4.4
A radiation-sensitive component was obtained in the same manner as in Synthesis Example 1 except that '-tetrahydroxybenzophenone was used. The obtained radiation-sensitive component is designated as C.
合成例8
式(1)で表わされる化合物のかわりに、2゜8.4−
トリヒドロキシベンゾフェノンをナフトキノン−(1,
2)−ジアジド−(2)−5−スルホン酸クロリドとの
モル比が1対2.8となるように用いた以外は、合成例
Iと同様にして感放射線性成分りを擾た。Synthesis Example 8 Instead of the compound represented by formula (1), 2°8.4-
Trihydroxybenzophenone is converted into naphthoquinone (1,
The radiation-sensitive component was stirred in the same manner as in Synthesis Example I, except that the molar ratio with 2)-diazide-(2)-5-sulfonic acid chloride was 1:2.8.
実施例及び比較例
合成例で得られた感放射線性成分をノボラック樹脂とと
もに、表1に示す組成で、エチルセロソルブアセテ−)
−48部に溶かし、レジスト液を調合した。調合したレ
ジスト液は0.2μmのテフロン製フィルターで一過す
ることにより、レジスト液を調整した。これを常法によ
って洗浄したシリコンウェハーに回転塗布機を用いて1
.8μ厚に塗布した。ついでこのシリコンウェハーを1
00℃のホットプレートで60秒間ベークした。ついで
このウェハーに486nm(P線)の露光波長を有する
縮小投影露光機(GC,A社DSW480ONA=0.
28)を用いて露光量を段階的に変化させて露光した。Examples and Comparative Examples The radiation-sensitive component obtained in the synthesis example was mixed with a novolac resin in the composition shown in Table 1 (ethyl cellosolve acetate).
-48 parts to prepare a resist solution. The prepared resist solution was passed through a 0.2 μm Teflon filter to prepare a resist solution. This was applied to a silicon wafer cleaned by a conventional method using a spin coating machine.
.. It was applied to a thickness of 8μ. Next, this silicon wafer
It was baked on a hot plate at 00°C for 60 seconds. Next, this wafer was exposed to a reduction projection exposure machine (GC, Company A DSW480ONA=0.
28), the exposure amount was changed stepwise.
これを住人化学製現像液5OPDで1分間現像すること
により、ポジ型パターンを得た。A positive pattern was obtained by developing this for 1 minute with a developer 5OPD manufactured by Sumitomo Chemical Co., Ltd.
ついで露光量の対数に対する、規格化膜厚(=残膜厚/
初期膜厚)をプロットし、その傾きθを求めianθを
r値とした。Next, the normalized film thickness (=residual film thickness/
(initial film thickness) was plotted, its slope θ was determined, and ian θ was taken as the r value.
結果を表1に示す。The results are shown in Table 1.
表−! *ノボラック樹脂 メタクレゾール/パラクレゾール; 7/8 クレゾール/ホルマリン=110.8 のモル比で、シェラ酸触媒を用い還流 下に反応させることにより得られた重 量平均分子量9800(ポリスチレン 換算)のノボラック樹脂。Table-! *Novolac resin Metacresol/paracresol; 7/8 Cresol/formalin = 110.8 Reflux using Shella acid catalyst at a molar ratio of The weight obtained by reacting Weight average molecular weight 9800 (polystyrene conversion) novolac resin.
(以下余白)(Margin below)
Claims (1)
化合物のキノンジアジドスルホン酸エステルの1種また
は2種以上を含有するポジ型レジスト組成物。 ▲数式、化学式、表等があります▼( I )[Scope of Claims] A positive resist composition containing a novolac resin and one or more quinonediazide sulfonic acid esters of phenol compounds represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6716889A JPH02245754A (en) | 1989-03-17 | 1989-03-17 | Positive type resist composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6716889A JPH02245754A (en) | 1989-03-17 | 1989-03-17 | Positive type resist composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02245754A true JPH02245754A (en) | 1990-10-01 |
Family
ID=13337096
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6716889A Pending JPH02245754A (en) | 1989-03-17 | 1989-03-17 | Positive type resist composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02245754A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57135947A (en) * | 1981-01-03 | 1982-08-21 | Hoechst Ag | Manufacture of photosensitive mixture and naphthoquinone deazidosulfonic ester |
JPS60121445A (en) * | 1983-12-06 | 1985-06-28 | Japan Synthetic Rubber Co Ltd | Positive type photosensitive resin composition |
JPS6446747A (en) * | 1987-08-14 | 1989-02-21 | Fuji Photo Film Co Ltd | Photoresist composition |
JPH01291243A (en) * | 1988-05-18 | 1989-11-22 | Tosoh Corp | Positive type photoresist material |
JPH01309052A (en) * | 1988-06-07 | 1989-12-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JPH02186351A (en) * | 1989-01-13 | 1990-07-20 | Tosoh Corp | Photosensitive agent for positive type photoresist |
-
1989
- 1989-03-17 JP JP6716889A patent/JPH02245754A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57135947A (en) * | 1981-01-03 | 1982-08-21 | Hoechst Ag | Manufacture of photosensitive mixture and naphthoquinone deazidosulfonic ester |
JPS60121445A (en) * | 1983-12-06 | 1985-06-28 | Japan Synthetic Rubber Co Ltd | Positive type photosensitive resin composition |
JPS6446747A (en) * | 1987-08-14 | 1989-02-21 | Fuji Photo Film Co Ltd | Photoresist composition |
JPH01291243A (en) * | 1988-05-18 | 1989-11-22 | Tosoh Corp | Positive type photoresist material |
JPH01309052A (en) * | 1988-06-07 | 1989-12-13 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
JPH02186351A (en) * | 1989-01-13 | 1990-07-20 | Tosoh Corp | Photosensitive agent for positive type photoresist |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2629356B2 (en) | Positive resist composition | |
JPH05232697A (en) | Positive resist composition | |
JP2636348B2 (en) | Composition for positive resist | |
JPH05323597A (en) | Positive resist composition | |
JPH02103543A (en) | Composition for positive type resist | |
JPH0450851A (en) | Positive type radiation sensitive resist composition | |
JP3070116B2 (en) | Polyhydric phenol compound and positive resist composition using the same | |
JP2814721B2 (en) | Positive radiation-sensitive resist composition | |
JPH08262712A (en) | Radiation sensitive resin composition | |
JPH01289947A (en) | Positive type resist composition | |
WO1992012205A1 (en) | Positive resist composition | |
JPH0534913A (en) | Positive type photoresist composition | |
JPH0219846A (en) | Positive type resist composition | |
JP2830348B2 (en) | Phenol compound and positive resist composition | |
JP2787943B2 (en) | Positive photoresist composition | |
JPH04284454A (en) | Positive photoresist composition | |
JPH02245754A (en) | Positive type resist composition | |
JP2629988B2 (en) | Positive resist composition | |
JPH022559A (en) | Composition for positive type resist | |
JPH06236030A (en) | Positive type resist composition | |
JP3235089B2 (en) | Positive resist composition for i-line and pattern forming method | |
JP2000066388A (en) | Radiation sensitive resin composition | |
JP4822384B2 (en) | Novel quinonediazide sulfonic acid ester compound, energy-sensitive linear agent for positive resist, and positive resist composition using the same | |
JPH04362645A (en) | Positive type resist composition | |
JP2000352823A (en) | Positive type radiation sensitive resist composition and production of resist pattern using the composition |