JPS63161449A - High contrast photoresist composition - Google Patents
High contrast photoresist compositionInfo
- Publication number
- JPS63161449A JPS63161449A JP31045286A JP31045286A JPS63161449A JP S63161449 A JPS63161449 A JP S63161449A JP 31045286 A JP31045286 A JP 31045286A JP 31045286 A JP31045286 A JP 31045286A JP S63161449 A JPS63161449 A JP S63161449A
- Authority
- JP
- Japan
- Prior art keywords
- naphthoquinone
- group
- diazide
- sulfonyl
- compd
- 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
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 9
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 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
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- XYJFAQCWRMHWFT-UHFFFAOYSA-N 2-sulfonylnaphthalene-1,4-dione Chemical class S(=O)(=O)=C1C(C2=CC=CC=C2C(C1)=O)=O XYJFAQCWRMHWFT-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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
- 239000004793 Polystyrene Substances 0.000 description 1
- 101150006306 Rhoq gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000000654 additive Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 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
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 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
- 150000005691 triesters Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、高コントラストなフォトレジスト組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to high contrast photoresist compositions.
〈従来の技術〉
半導体素子は、従来フォトエツチング法による微細加工
技術によって製造されている。近年、集積回路の高集積
化によってパターンの微細化が進み、このためレジスト
には微細パターンを精度よく形成することが望まれる。<Prior Art> Semiconductor elements are conventionally manufactured by microfabrication technology using photoetching. In recent years, patterns have become finer due to the increased integration of integrated circuits, and it is therefore desirable to form fine patterns on resists with high precision.
コントラストが高いほど種々の露光法によってパターニ
ングされたフォトレジストにおける幾何学的寸法が受け
る影響が小さくなる。つまり、コントラストが高いほど
微細パターンを精度よく形成することができる(特開昭
61−97652号公報)。The higher the contrast, the less the effect on the geometric dimensions in photoresists patterned by various exposure methods. In other words, the higher the contrast, the more accurately a fine pattern can be formed (Japanese Patent Application Laid-Open No. 61-97652).
一般に、アルミニウムやポリシリコンの段差の有る高反
射基板上においては微細パターンを精度よく形成するこ
とが困難であるが、高コントラストなレジストは高反射
基板上でも微細パターンの寸法制御性が良くなる。In general, it is difficult to form fine patterns with high accuracy on highly reflective substrates such as aluminum or polysilicon with steps, but a high contrast resist provides good dimensional control of fine patterns even on highly reflective substrates.
高反射基板上での微細パターンの寸法制御の改良法とし
てオイルイエロー等の吸光剤をフォトレジストに添加す
る方法が提案されている(特公昭51−37562号公
報)。As an improved method for controlling the dimensions of fine patterns on highly reflective substrates, a method has been proposed in which a light absorbing agent such as oil yellow is added to a photoresist (Japanese Patent Publication No. 37562/1982).
しかし、吸光剤を添加したフォトレジストは塗布膜を形
成し、プリベーク後保存中に吸光剤が析出したり、ブリ
ベータ時に昇華して濃度が下り、満足な効果が得られな
かったり、バラツキが生じるという欠点があった。However, photoresists containing light absorbing agents form a coating film, and the light absorbing agents precipitate during storage after prebaking, or sublimate during blubbling, resulting in a decrease in concentration, resulting in unsatisfactory effects and variations. There were drawbacks.
〈発明が解決しようとする問題点〉
本発明者らは上記従来技術の欠点を克服すべく鋭意検討
した結果、本発明を完成するに至った。<Problems to be Solved by the Invention> As a result of intensive studies to overcome the drawbacks of the above-mentioned prior art, the present inventors have completed the present invention.
本発明の目的は、高コントラストで、プリベーク条件変
化に対しても、高反射基板上で微細パターンの寸法制御
性の良いフォトレジスト組成物を提供することにある。An object of the present invention is to provide a photoresist composition with high contrast and good dimensional controllability of fine patterns on a highly reflective substrate even under changes in prebaking conditions.
く問題点を解決するための手段〉
本発明は、アルカリ可溶性樹脂に対し、ナフトキノン−
1,2−ジアジド−5−スルホニル基又はナフトキノン
−1,2−ジアジド−4−スルホニル基を2個以上有す
る化合物及び一般式(式中のD1ナフトキノン−1,2
−ジアジド−5−スルホニル基又はナフトキノン−1,
2−ジアジド−4−スルホニル基である。また、R1%
R,、R,はアルキル基、アリル基、アラルキル基、−
Q−CローQ 基又は水素原子である。)表わされる
化合物を配合することを特徴とする高コントラストなフ
ォトレジスト組成物である。Means for Solving the Problems> The present invention provides naphthoquinone-
Compounds having two or more 1,2-diazide-5-sulfonyl groups or naphthoquinone-1,2-diazide-4-sulfonyl groups and general formula (D1 naphthoquinone-1,2
-diazido-5-sulfonyl group or naphthoquinone-1,
It is a 2-diazide-4-sulfonyl group. Also, R1%
R,,R, is an alkyl group, an allyl group, an aralkyl group, -
It is a Q-C rhoQ group or a hydrogen atom. ) A high-contrast photoresist composition comprising the following compounds.
本発明の組成物の第1の感光成分として用いられる化合
物は、ナフトキノン−1,2−ジアジド−5−スルホニ
ル基又はナフトキノン−1,2−ジアジド−4−スルホ
ニル基を2個以上有する化合物であり、これらは水酸基
を2個以上有する化合物とナフトキノン−1,2−ジア
ジド−5−スルホニルクロリド又はナフトキノン−1,
2−ジアジド−4−スルホニルクロリドを弱アルカリの
存在下に縮合させることにより得られる。ここで水酸基
を2個以上有する化合物の例としては、ハイドロキノン
、レゾルシン、フロログルシン、2゜4−ジヒドロキシ
ベンゾフェノン、2.3.4−トリヒドロキシベンゾフ
ェノン、2,3,4゜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、没食子酸アルキルエステルなどがあげられ
る。The compound used as the first photosensitive component of the composition of the present invention is a compound having two or more naphthoquinone-1,2-diazido-5-sulfonyl groups or naphthoquinone-1,2-diazide-4-sulfonyl groups. , these are compounds having two or more hydroxyl groups and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,
It is obtained by condensing 2-diazide-4-sulfonyl chloride in the presence of a weak alkali. Examples of compounds having two or more hydroxyl groups include hydroquinone, resorcinol, phloroglucin, 2゜4-dihydroxybenzophenone, 2.3.4-trihydroxybenzophenone, 2,3,4゜4゜-tetrahydroxybenzophenone, Examples include 2°2°, 4.4°-tetrahydroxybenzophenone, and gallic acid alkyl ester.
第2の感光成分として用いられる化合物は分子内に1つ
の水酸基を有する芳香族化合物とナフトキノン−1,2
−ジアジド−5−スルホニルクロリド又はナフトキノン
−1,2−ジアジド−4−スルホニルクロリドを弱アル
カリの存在下に縮合させることにより得られる特達のモ
ノエステルである。分子内に1つの水酸基を有する芳香
族化合物としてはm−クレゾール、p−クレゾール、p
−ノニルフェノール、4−ヒドロキシベンゾフェノン、
p−tert−ブチルフェノール、2,4.6−トリー
tart−ブチルフェノール、3.5.6−亀
トリメチルフェノール、り戸嶌ルフェノール等があげら
れる。The compounds used as the second photosensitive component are aromatic compounds having one hydroxyl group in the molecule and naphthoquinone-1,2
It is a special monoester obtained by condensing -diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride in the presence of a weak alkali. Aromatic compounds having one hydroxyl group in the molecule include m-cresol, p-cresol, and p-cresol.
-nonylphenol, 4-hydroxybenzophenone,
Examples include p-tert-butylphenol, 2,4.6-tritart-butylphenol, 3.5.6-tortotrimethylphenol, Ritoshimaruphenol, and the like.
本発明に使用される被膜形成用物質として各種のアルカ
リ可溶性樹脂が用いられる。このアルカリ可溶性樹脂と
しては、例えばフェノール類とホルムアルデヒドから製
造されるノボラック樹脂、スチレン−無水マレイン酸コ
ポリマー、カルボキシル基を有するアクリル樹脂、ヒド
ロキシスチレンの重合体などをあげられる。好ましくは
m−クレゾール及び又はp−クレゾールとホルマリンよ
り合成されるクレゾールノボラック樹脂、m−及びp−
クレゾール及び3.5−キシレノールとホルマリンより
合成されるクレゾール系ノボラック樹脂等があげられ、
具体的には特開昭60−159846号公報で示され−
た方法があげられる。Various alkali-soluble resins are used as the film-forming substance used in the present invention. Examples of the alkali-soluble resin include novolac resins produced from phenols and formaldehyde, styrene-maleic anhydride copolymers, acrylic resins having carboxyl groups, and hydroxystyrene polymers. Preferably cresol novolak resins synthesized from m-cresol and/or p-cresol and formalin, m- and p-
Cresol-based novolac resins synthesized from cresol, 3,5-xylenol, and formalin, etc.
Specifically, it is shown in Japanese Patent Application Laid-open No. 159846/1984.
Here are some methods.
第1の感光成分と第2の感光成分の配合比は1:0゜5
〜1:3の範囲で用いるのが好ましい。The blending ratio of the first photosensitive component and the second photosensitive component is 1:0°5
It is preferable to use the ratio in the range of 1:3 to 1:3.
感光成分とアルカリ可溶性樹脂の配合比は1:1〜1:
6の範囲で用いるのが好ましい。The blending ratio of photosensitive component and alkali-soluble resin is 1:1 to 1:
It is preferable to use the range of 6.
第2の感光成分の比率が小さいとコントラストが低く、
高すぎると残膜率が低くなり好ましくない。またアルカ
リ可溶性樹脂が多すぎるとレジスト画像の忠実性が劣り
転写性が悪くなり、少なすぎるとレジスト膜の均一性が
悪く解像力も低下する。When the ratio of the second photosensitive component is small, the contrast is low;
If it is too high, the residual film rate will be low, which is not preferable. Furthermore, if the amount of the alkali-soluble resin is too large, the fidelity of the resist image will be poor and the transferability will be poor, and if it is too small, the uniformity of the resist film will be poor and the resolution will be reduced.
本発明の組成物は前記の感光成分とアルカリ可溶性樹脂
とを適当な溶媒に溶解して溶液で用いる。The composition of the present invention is used in the form of a solution by dissolving the photosensitive component and the alkali-soluble resin in a suitable solvent.
ここで用いる溶媒は、適当な乾燥速度で溶媒が蒸発した
後、均一で平滑な塗膜を与えるものがよい。The solvent used here is preferably one that provides a uniform and smooth coating film after the solvent evaporates at an appropriate drying rate.
そのようなものとして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、プロピレングリコールモノ
メチルエーテルアセテート、エチルセロソルブ、メチル
セロソルブ、シクロヘキサノン、インアミルケトン、メ
チルイソブチルケトン、酢酸ブチル、キシレン等があげ
られる。これらは単独で用いてもよいし、2種以上混合
して用いてもよい。Examples of such substances include ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl cellosolve, methyl cellosolve, cyclohexanone, inamyl ketone, methyl isobutyl ketone, butyl acetate, xylene, and the like. These may be used alone or in combination of two or more.
本発明の組成物は、さらに付加的な添加物として少量の
付加的な樹脂、可塑剤、染料などが添加されてもよい。The compositions of the present invention may also contain small amounts of additional resins, plasticizers, dyes, etc. as additional additives.
本発明の組成物の好適な使用方法についての一例を下記
に示す。An example of a preferred method of using the composition of the present invention is shown below.
シリコンウェハ、アルミニウム又はポリシリコン膜付ウ
ェハ等の基板に本発明の組成物をスピンコータ等で塗布
し、これをダイレクトコンタクトホットプレートでプリ
ベークすることによって親溶媒した塗布膜が得られる。The composition of the present invention is applied to a substrate such as a silicon wafer, aluminum or a wafer with a polysilicon film using a spin coater or the like, and then prebaked using a direct contact hot plate to obtain a solvent-friendly coating film.
次いで縮小投影露光装置(ス′チッパ−)によって所要
のマスクパターンの描画されたレチクルを介して露光す
る。フンベクションオーブン等で必要に応じてアフター
ベークする。次に例えば1〜3%の水酸化テトラメチア
ンモニウム水溶液を使用し、露光した基板を自動現像機
で現像する。これによって露光によって可溶化した部分
が選択的に溶解除去されて、マスクパターンに忠実な画
像を得ることができる。Next, exposure is performed using a reduction projection exposure device (stripper) through a reticle on which a desired mask pattern has been drawn. After-bake in a function oven, etc. if necessary. Next, the exposed substrate is developed using an automatic developing machine using, for example, a 1 to 3% tetramethyammonium hydroxide aqueous solution. As a result, the portions solubilized by exposure are selectively dissolved and removed, making it possible to obtain an image faithful to the mask pattern.
第1図は、レジスト塗布膜の規格化膜厚と露光量の関係
を示し、図中で、曲線Eは残留している厚膜と露光量の
関係をとった一例である。FIG. 1 shows the relationship between the normalized film thickness of the resist coating film and the exposure amount, and in the figure, the curve E is an example of the relationship between the remaining thick film and the exposure amount.
膜数は感度とコントラストをこの曲線から測定した。一
般にガンマ(y)値が高いほど高コントラストであり、
レジスト/現像液系の性能が良い。The number of films was determined by measuring sensitivity and contrast from this curve. Generally, the higher the gamma (y) value, the higher the contrast;
The performance of the resist/developer system is good.
好ましいガンマ値は3以上である。ガンマ(γ)値は下
式で算出する。A preferable gamma value is 3 or more. The gamma (γ) value is calculated using the following formula.
本発明のフォトレジスト組成物は高コントラストであり
、プリベーク条件変化に対して高反射基板上で安定して
微細なパターンの寸法を正確に再現することができる。The photoresist composition of the present invention has high contrast and can stably and accurately reproduce the dimensions of a fine pattern on a highly reflective substrate even when prebaking conditions change.
〈実施例〉
以下、本発明を実施例及び比較例により具体的に説明す
るが、これによって本発明が制限されるものでない。<Examples> The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited thereto.
合成例1
2.3.4−)リヒドロキシベンゾフェノン38g(0
,17モル)とナフトキノン−1,2−ジアジド−5−
スルホニルクロリド55g (0,20モル)をジオキ
サン506gに溶解し、6%炭酸ナトリウム水溶液32
0gを撹拌下、25℃以下で3時間かけて滴下した。次
いで35%塩酸4gをイオン交換水1,500gで希釈
した希塩酸溶液を加えて反応物を析出させ、得られた析
出物をイオン交換水でよく洗浄し、水分除去後乾燥した
。Synthesis Example 1 2.3.4-) lyhydroxybenzophenone 38g (0
, 17 mol) and naphthoquinone-1,2-diazide-5-
Dissolve 55 g (0.20 mol) of sulfonyl chloride in 506 g of dioxane and add 32 g of 6% aqueous sodium carbonate solution.
0 g was added dropwise over 3 hours at 25° C. or below while stirring. Next, a dilute hydrochloric acid solution prepared by diluting 4 g of 35% hydrochloric acid with 1,500 g of ion-exchanged water was added to precipitate the reactant, and the resulting precipitate was thoroughly washed with ion-exchanged water, water was removed, and then dried.
この様にして得られた乾燥物をテトラヒドロフランに溶
解し、液体クロマトグラフで組成を決定した。トリエス
テル38.5%、ジエステル22.1%、モノエステル
28.2%、未反応物11.2%であった。The dried product thus obtained was dissolved in tetrahydrofuran, and its composition was determined by liquid chromatography. The contents were 38.5% triester, 22.1% diester, 28.2% monoester, and 11.2% unreacted materials.
合成例2
m−クレゾール 22g (0,20モル)を用いる以
外は・合成例1と同様にして反応生成物を得た。反応物
を分析したところ、エステル99%、未反応物1%であ
った。Synthesis Example 2 A reaction product was obtained in the same manner as Synthesis Example 1 except that 22 g (0.20 mol) of m-cresol was used. Analysis of the reaction product revealed that it contained 99% ester and 1% unreacted material.
合成例3
p−クレゾール22g (0,20モル)を用いる以外
は合成例1と同様にして反応生成物を得た。反応物を分
析したところ、エステル99%、未反応物1%であった
。Synthesis Example 3 A reaction product was obtained in the same manner as in Synthesis Example 1 except that 22 g (0.20 mol) of p-cresol was used. Analysis of the reaction product revealed that it contained 99% ester and 1% unreacted material.
合成例4
4−ヒドロキシベンゾフェノン40g (0,20モ
ル)を用いる以外は合成例1と同様にして反応生成物を
得た。反応物を分析したところ、エステル99%、未反
応物1%であった。Synthesis Example 4 A reaction product was obtained in the same manner as Synthesis Example 1 except that 40 g (0.20 mol) of 4-hydroxybenzophenone was used. Analysis of the reaction product revealed that it contained 99% ester and 1% unreacted material.
合成例5
p−ノニルフェノール44g (0,20モル)を用い
る以外は合成例1と同様にして反応生成物を得た。Synthesis Example 5 A reaction product was obtained in the same manner as in Synthesis Example 1 except that 44 g (0.20 mol) of p-nonylphenol was used.
反応物を分析したところ、エステル98%、未反応物2
%であった。Analysis of the reactants revealed 98% ester and 2 unreacted substances.
%Met.
実施例1〜4、比較例1〜3
クレゾールノボラック樹脂(分子量1.5万、ポリスチ
レン換算)10gに対して合成例1〜5の反応生成物を
それぞれ表1に示した量を添加し、エチレングリコール
モノエチルエーテルアセテート36gに溶解してフォト
レジスト組成物とした。これらレジスト組成物をアルミ
ニウム膜(M厚10.000人)付ウェハにスピンコー
ドして、プリベータをホットプレートで100℃1分間
行って膜厚1.28μmのレジスト膜を得た。ステッパ
ー(GCA社製 4800−DSW型)を用いて露光し
、コンベクションオーブン90℃、30分間アフターベ
ークした。2.38%の水酸化テトラメチルアンモニウ
ム水溶液で23℃、60秒の静止パドル現像し、水洗、
乾燥した。得られたパターンを走査型電子顕微鏡(SE
M)、光学顕微鏡(OM)で観察し又残膜厚を測定して
表−1の結果を得た。本発明のレジスト組成物は表1の
結果によって高コントラストでアルミニウム基板からの
ハレーションがよく防止されていることが認められる。Examples 1 to 4, Comparative Examples 1 to 3 The reaction products of Synthesis Examples 1 to 5 were added in the amounts shown in Table 1 to 10 g of cresol novolac resin (molecular weight 15,000, polystyrene equivalent), and ethylene A photoresist composition was prepared by dissolving in 36 g of glycol monoethyl ether acetate. These resist compositions were spin-coded onto a wafer with an aluminum film (M thickness: 10,000 mm), and prebater was performed on a hot plate at 100° C. for 1 minute to obtain a resist film with a thickness of 1.28 μm. It was exposed using a stepper (model 4800-DSW manufactured by GCA) and after-baked in a convection oven at 90° C. for 30 minutes. Stationary paddle development for 60 seconds at 23°C with a 2.38% tetramethylammonium hydroxide aqueous solution, washing with water,
Dry. The obtained pattern was subjected to scanning electron microscopy (SE
M) was observed with an optical microscope (OM) and the remaining film thickness was measured, and the results shown in Table 1 were obtained. The results shown in Table 1 show that the resist composition of the present invention has high contrast and well prevents halation from the aluminum substrate.
実施例5〜7、比較例4〜6
実施例1および比較例1のレジスト組成物をそれぞれ使
用してプリベーク温度を変更して表−2の結果を得た。Examples 5 to 7, Comparative Examples 4 to 6 Using the resist compositions of Example 1 and Comparative Example 1, the results shown in Table 2 were obtained by changing the prebake temperature.
本発明のレジスト組成物はプリベーク条件の変動による
性能変化が小さいことがわかる。It can be seen that the resist composition of the present invention shows little change in performance due to variations in prebaking conditions.
第1図は、レジスト塗布膜の規格化膜厚と露光量の関係
を示した図である。FIG. 1 is a diagram showing the relationship between the normalized film thickness of a resist coating film and the exposure amount.
Claims (2)
,2−ジアジド−5−スルホニル基又はナフトキノン−
1,2−ジアジド−4−スルホニル基を2個以上有する
化合物及び一般式 ▲数式、化学式、表等があります▼ (式中、Dはナフトキノン−1,2−ジアジド−5−ス
ルホニル基又はナフトキノン−1,2−ジアジド−4−
スルホニル基である。また、R_1、R_2、R_3は
アルキル基、アリル基、アラルキル基、▲数式、化学式
、表等があります▼基又は水素原子である。) で表わされる化合物を配合することを特徴とするフォト
レジスト組成物。(1) Naphthoquinone-1 for alkali-soluble resin
, 2-diazide-5-sulfonyl group or naphthoquinone-
Compounds having two or more 1,2-diazido-4-sulfonyl groups and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, D is naphthoquinone-1,2-diazide-5-sulfonyl group or naphthoquinone- 1,2-diazide-4-
It is a sulfonyl group. In addition, R_1, R_2, and R_3 are an alkyl group, an allyl group, an aralkyl group, a ▲ mathematical formula, a chemical formula, a table, etc. ▼ group, or a hydrogen atom. ) A photoresist composition comprising a compound represented by:
ル基又はナフトキノン−1,2−ジアジド−4−スルホ
ニル基を2個以上有する化合物と一般式 ▲数式、化学式、表等があります▼ (式中、Dはナフトキノン−1,2−ジアジド−5−ス
ルホニル基又はナフトキノン−1,2−ジアジド−4−
スルホニル基である。また、R_1、R_2、R_3は
アルキル基、アリル基、アラルキル基、▲数式、化学式
、表等があります▼基又は水素原子である。) で表わされる化合物の配合比が1:0.5〜1:3の範
囲である特許請求の範囲第1項記載のフォトレジスト組
成物。(2) Compounds having two or more naphthoquinone-1,2-diazide-5-sulfonyl groups or naphthoquinone-1,2-diazide-4-sulfonyl groups and general formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula , D is naphthoquinone-1,2-diazide-5-sulfonyl group or naphthoquinone-1,2-diazide-4-
It is a sulfonyl group. In addition, R_1, R_2, and R_3 are an alkyl group, an allyl group, an aralkyl group, a ▲ mathematical formula, a chemical formula, a table, etc. ▼ group, or a hydrogen atom. 2. The photoresist composition according to claim 1, wherein the compounding ratio of the compound represented by the following formula is in the range of 1:0.5 to 1:3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31045286A JPS63161449A (en) | 1986-12-24 | 1986-12-24 | High contrast photoresist composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31045286A JPS63161449A (en) | 1986-12-24 | 1986-12-24 | High contrast photoresist composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63161449A true JPS63161449A (en) | 1988-07-05 |
Family
ID=18005418
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31045286A Pending JPS63161449A (en) | 1986-12-24 | 1986-12-24 | High contrast photoresist composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63161449A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02287545A (en) * | 1989-04-28 | 1990-11-27 | Tokyo Ohka Kogyo Co Ltd | Positive type photosensitive composition |
JPH03242650A (en) * | 1990-02-20 | 1991-10-29 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
US6110963A (en) * | 1998-05-12 | 2000-08-29 | American Home Products Corporation | Aryl-oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia |
US6214877B1 (en) | 1998-05-12 | 2001-04-10 | John A. Butera | 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia |
US6221902B1 (en) | 1998-05-12 | 2001-04-24 | American Home Products Corporation | Biphenyl sulfonyl aryl carboxylic acids useful in the treatment of insulin resistance and hyperglycemia |
US6232322B1 (en) | 1998-05-12 | 2001-05-15 | American Home Products Corporation | Biphenyl oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia |
US6310081B1 (en) | 1999-05-10 | 2001-10-30 | American Home Products Corporation | Biphenyl sulfonyl aryl carboxylic acids useful in the treatment of insulin resistance and hyperglycemia |
US6451827B2 (en) | 1998-05-12 | 2002-09-17 | Wyeth | 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia |
US7141672B2 (en) | 1998-05-12 | 2006-11-28 | Wyeth | Oxazole-aryl-carboxylic acids useful in the treatment of insulin resistance and hyperglycemia |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5562444A (en) * | 1978-11-02 | 1980-05-10 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
JPS5784450A (en) * | 1980-11-13 | 1982-05-26 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
JPS58182632A (en) * | 1982-04-20 | 1983-10-25 | Japan Synthetic Rubber Co Ltd | Positive type photosensitive resin composition |
JPS62150245A (en) * | 1985-12-24 | 1987-07-04 | Japan Synthetic Rubber Co Ltd | Positive type radiation sensitive resin composition |
JPS62153950A (en) * | 1985-12-27 | 1987-07-08 | Japan Synthetic Rubber Co Ltd | Positive type radiation sensitive resin composition |
-
1986
- 1986-12-24 JP JP31045286A patent/JPS63161449A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5562444A (en) * | 1978-11-02 | 1980-05-10 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
JPS5784450A (en) * | 1980-11-13 | 1982-05-26 | Konishiroku Photo Ind Co Ltd | Photosensitive composition |
JPS58182632A (en) * | 1982-04-20 | 1983-10-25 | Japan Synthetic Rubber Co Ltd | Positive type photosensitive resin composition |
JPS62150245A (en) * | 1985-12-24 | 1987-07-04 | Japan Synthetic Rubber Co Ltd | Positive type radiation sensitive resin composition |
JPS62153950A (en) * | 1985-12-27 | 1987-07-08 | Japan Synthetic Rubber Co Ltd | Positive type radiation sensitive resin composition |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02287545A (en) * | 1989-04-28 | 1990-11-27 | Tokyo Ohka Kogyo Co Ltd | Positive type photosensitive composition |
JPH03242650A (en) * | 1990-02-20 | 1991-10-29 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
US6451827B2 (en) | 1998-05-12 | 2002-09-17 | Wyeth | 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia |
US6214877B1 (en) | 1998-05-12 | 2001-04-10 | John A. Butera | 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia |
US6221902B1 (en) | 1998-05-12 | 2001-04-24 | American Home Products Corporation | Biphenyl sulfonyl aryl carboxylic acids useful in the treatment of insulin resistance and hyperglycemia |
US6232322B1 (en) | 1998-05-12 | 2001-05-15 | American Home Products Corporation | Biphenyl oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia |
US6369072B2 (en) | 1998-05-12 | 2002-04-09 | American Home Products Corporation | Biphenyl oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia |
US6391897B2 (en) | 1998-05-12 | 2002-05-21 | American Home Products Corporation | Biphenyl oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia |
US6110963A (en) * | 1998-05-12 | 2000-08-29 | American Home Products Corporation | Aryl-oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia |
US6765021B2 (en) | 1998-05-12 | 2004-07-20 | Wyeth | 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia |
US7008636B2 (en) | 1998-05-12 | 2006-03-07 | Wyeth | 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia |
US7141672B2 (en) | 1998-05-12 | 2006-11-28 | Wyeth | Oxazole-aryl-carboxylic acids useful in the treatment of insulin resistance and hyperglycemia |
US6310081B1 (en) | 1999-05-10 | 2001-10-30 | American Home Products Corporation | Biphenyl sulfonyl aryl carboxylic acids useful in the treatment of insulin resistance and hyperglycemia |
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