JPS63210923A - Resin composition for pattern formation - Google Patents
Resin composition for pattern formationInfo
- Publication number
- JPS63210923A JPS63210923A JP4478387A JP4478387A JPS63210923A JP S63210923 A JPS63210923 A JP S63210923A JP 4478387 A JP4478387 A JP 4478387A JP 4478387 A JP4478387 A JP 4478387A JP S63210923 A JPS63210923 A JP S63210923A
- Authority
- JP
- Japan
- Prior art keywords
- pattern
- resin composition
- acid
- novolak resin
- molecular weight
- 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 abstract description 18
- 230000007261 regionalization Effects 0.000 title description 4
- 229920003986 novolac Polymers 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 14
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000001312 dry etching Methods 0.000 abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- -1 1,2-benzoquinone diazidosulfonic acid ester Chemical class 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical class [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WHGXZPQWZJUGEP-UHFFFAOYSA-N 2-prop-1-enylphenol Chemical compound CC=CC1=CC=CC=C1O WHGXZPQWZJUGEP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RLNPMMZDOVEXFF-UHFFFAOYSA-N S(O)(O)(=O)=O.[N-]=[N+]=[N-].[N-]=[N+]=[N-] Chemical compound S(O)(O)(=O)=O.[N-]=[N+]=[N-].[N-]=[N+]=[N-] RLNPMMZDOVEXFF-UHFFFAOYSA-N 0.000 description 1
- ALVGSDOIXRPZFH-UHFFFAOYSA-N [(1-diazonioimino-3,4-dioxonaphthalen-2-ylidene)hydrazinylidene]azanide Chemical compound C1=CC=C2C(=N[N+]#N)C(=NN=[N-])C(=O)C(=O)C2=C1 ALVGSDOIXRPZFH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229940100630 metacresol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical class [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はパターン形成用樹脂組成物に関し、詳しくはパ
ターン形成時に用いられるポジ型フォトレジスト樹脂組
成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a pattern-forming resin composition, and more particularly to a positive photoresist resin composition used in pattern formation.
従来、集積回路を作成するためのフォトレジストとして
は、環化イソプレンゴムにビスアジド化合物を配合した
ネガ型フォトレジストが知られて −いる、しかし、こ
のネガ型フォトレジストは解像度に限界があり集積回路
の高集積化に充分に対応できない欠点を有し、さらには
近年微細パターン形成のために行われているドライエツ
チング法において耐ドライエツチング性に欠ける欠点を
有する。Conventionally, as a photoresist for creating integrated circuits, a negative photoresist made of cyclized isoprene rubber mixed with a bisazide compound has been known. However, this negative photoresist has a limited resolution and cannot be used for integrated circuits. It has the disadvantage that it cannot sufficiently cope with high integration, and furthermore, it has a disadvantage that it lacks dry etching resistance in dry etching methods that have been used in recent years to form fine patterns.
一方、このネガ型フォトレジストに比ベポジ型フォトレ
ジストは、解像度が優れているため集積回路の高集積化
に充分に対応し得るものと期待されている。従来のポジ
型フォトレジストはアルカリ可溶性ノボラック樹脂に、
ナフトキノンジアジド系化合物を添加し°たものが大部
分であり、ナフトキノンジアジド系化合物が光照射によ
り分解してインデンカルボン酸となり露光部がアルカリ
可溶性になり、一方、未露光部では逆にアルカリ不溶性
を示す性質を利用している。On the other hand, since positive-type photoresists have superior resolution compared to negative-type photoresists, it is expected that they will be able to adequately respond to higher integration of integrated circuits. Conventional positive photoresists are made of alkali-soluble novolak resin.
Most of the products contain naphthoquinone diazide compounds, which decompose upon light irradiation and turn into indenecarboxylic acid, making the exposed areas alkali-soluble, while the unexposed areas conversely become alkali-insoluble. It takes advantage of the properties shown.
しかしながら、ポジ型フォトレジストは■シリコンウェ
ハー等の基板に対する密着性に乏しい、■脆く割れやす
い、■感度が低い、■耐ドライエツチング性が不充分、
■耐熱性が不足等の問題があった。However, positive photoresists: ■ have poor adhesion to substrates such as silicon wafers, ■ are brittle and break easily, ■ have low sensitivity, and ■ have insufficient dry etching resistance.
■There were problems such as insufficient heat resistance.
特に、近年より高集積化が進むにつれ、耐ドライエツチ
ング性、パターン形成時のイオン注入時、リフトオフ方
式のような金属蒸着を施す際の耐熱性の向上が問題とな
っており、現状、限界とされている１２０−１３０℃よ
り高い温度、好ましくは１５０℃以上の温度での寸法安
定性が要求されていた。In particular, as higher integration has progressed in recent years, improvements in dry etching resistance, ion implantation during pattern formation, and heat resistance when performing metal vapor deposition such as lift-off methods have become issues, and currently there are limits to this. Dimensional stability at temperatures higher than the 120-130°C, preferably 150°C or higher, was required.
本発明者等は上記の点に鑑み鋭意研究した結果、高分子
量ノボラック樹脂と１．２−キノンジアジド系化合物を
含有する樹脂組成物を使用することにより従来のポジ型
フォトレジストにおける問題点を解決することができる
ことを見出し、本発明を完成するに至った。As a result of intensive research in view of the above points, the present inventors solved the problems in conventional positive photoresists by using a resin composition containing a high molecular weight novolak resin and a 1,2-quinonediazide compound. The present inventors have discovered that it is possible to do this, and have completed the present invention.
本発明で使用する高分子量ノボラック樹脂は、フェノー
ル類とホルムアルデヒドを塩酸、硝酸、硫酸、トルエン
スルホン酸、蓚酸等の酸性触媒の存在下に縮合させたも
のである。フェノール類としてはフェノール、クレゾー
ル、エチルフェノール、ブチルフェノール、ノニルフェ
ノール、プロペニルフェノール、ビニルフェノール、フ
ェニルフェノール、ナフトール等が挙げられる。好まし
くはオルトクレゾール、メタクレゾール又はバラクレゾ
ールであり、より好ましくはオルトクレゾール又はバラ
クレゾール又はオルトクレゾールとバラクレゾールの混
合物である。また、ホルムアルデヒドとしてはホルマリ
ン、トリオキサン、パラホルムアルデヒド等を使用する
ことができる。The high molecular weight novolak resin used in the present invention is a product obtained by condensing phenols and formaldehyde in the presence of an acidic catalyst such as hydrochloric acid, nitric acid, sulfuric acid, toluenesulfonic acid, or oxalic acid. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, nonylphenol, propenylphenol, vinylphenol, phenylphenol, naphthol, and the like. Preferably it is orthocresol, metacresol or vala-cresol, more preferably orthocresol or vala-cresol or a mixture of orthocresol and vala-cresol. Moreover, formalin, trioxane, paraformaldehyde, etc. can be used as formaldehyde.
このような原料を使用して高分子量ノボラック樹脂を製
造する方法としては、特開昭６０−２６０６１１号、同
６１−１２７１４号、同５７−１０６４４号および同５
８−１１５５１号公報等に記載されている公知の方法を
採用することができる。Methods for producing high molecular weight novolac resins using such raw materials include JP-A-60-260611, JP-A-61-12714, JP-A-57-10644 and JP-A-5.
A known method described in Publication No. 8-11551 and the like can be employed.
高分子量ノボラック樹脂は好ましくは線状のノボラック
樹脂であり、より好ましくは線状のクレゾールノボラッ
ク樹脂である。またこの分子量は数平均分子量が１５０
０以上、好ましくは２０００以上、より好ましくは２５
００以上であればよく、一般的に用いられる溶剤に可溶
である範囲であれば格別上限を設ける必要はないが、好
ましくは３００００以下である。また、数平均分子量と
重量平均分子量の比（分散度）はｌＯ以下、好ましくは
５以下がよい０分子量が小さいと耐熱性が向上せず、ま
た分散度が大きいと耐熱性が向上せず、感度も低下する
。また、他のノボラック樹脂では、造膜性、シリコンウ
ェハーに対する密着性及び脆さの改良が行われず、また
耐ドライエツチング性及び耐熱性の向上が不充分となる
。The high molecular weight novolak resin is preferably a linear novolak resin, more preferably a linear cresol novolak resin. In addition, this molecular weight has a number average molecular weight of 150
0 or more, preferably 2000 or more, more preferably 25
00 or more, and there is no need to set a particular upper limit as long as it is soluble in commonly used solvents, but it is preferably 30,000 or less. In addition, the ratio of number average molecular weight to weight average molecular weight (dispersity) should be 1O or less, preferably 5 or less. If the molecular weight is small, the heat resistance will not improve, and if the dispersity is large, the heat resistance will not improve. Sensitivity also decreases. In addition, other novolak resins do not improve film-forming properties, adhesion to silicon wafers, or brittleness, and do not sufficiently improve dry etching resistance and heat resistance.
本発明で使用する１、２−キノンジアジド系化合物とし
ては、１．２−ベンゾキノンジアジドスルホン酸エステ
ル、１．２−ナフトキノンジ了シトスルホン酸エステル
、１．２−ナフトキノンジアジドスルホン酸アミド等の
従来公知の１．２−キノンジアジド系化合物を用いるこ
とができ、これらは１種又は２種以上の混合物でもよい
。The 1,2-quinonediazide-based compounds used in the present invention include conventionally known 1,2-benzoquinonediazide sulfonic acid esters, 1,2-naphthoquinonediazide sulfonic acid esters, and 1,2-naphthoquinonediazide sulfonic acid amides. 1.2-quinonediazide compounds can be used, and these may be used alone or in a mixture of two or more.
本発明パターン形成用樹脂組成物は、上述の高分子量ノ
ボラック樹脂と１．２−キノンジアジド系化合物とを含
有してなるものであり、高分子量ノボラック樹脂と１．
２−キノンジアジド系化合物の混合割合は特別限定を設
ける必要はないが、好ましくは８：ｌ〜１：２、より好
ましくは５：１〜１：１である。The pattern-forming resin composition of the present invention contains the above-mentioned high molecular weight novolak resin and a 1.2-quinonediazide-based compound.
The mixing ratio of the 2-quinonediazide compound is not particularly limited, but is preferably 8:1 to 1:2, more preferably 5:1 to 1:1.
本発明の樹脂組成物は高分子量ノボラック樹脂と１．２
−キノンジアジド系化合物を混合したものであってもよ
いが、通常はこの種の樹脂組成物に添加される溶媒、添
加剤等を含有する。また、パターン形成用樹脂組成物は
、通常は溶媒に溶解して用いられるが、この際に用いる
溶媒としては組成物に対して反応せず、充分な溶解度を
有し、良好な塗膜性を与える溶媒であれば特に限定され
るものではなく、例えばメチルセロソルブ、エチルセロ
ソルブ等のセロソルブ類、メチルセロソルブアセテート
等のセロソルブエステル類、ブチルアセテート等のエス
テル類等の溶媒、ジメチルホルムアルデヒド、ジメチル
スルホキシド等の極性溶媒が挙げられる。なお、一般に
ストリエーション防止のためには比較的揮発性の低い高
沸点溶媒が望ましい。The resin composition of the present invention includes a high molecular weight novolak resin and a
-Although it may be a mixture of quinonediazide compounds, it usually contains solvents, additives, etc. that are added to this type of resin composition. In addition, the pattern-forming resin composition is usually used after being dissolved in a solvent, but the solvent used at this time does not react with the composition, has sufficient solubility, and has good coating properties. There are no particular limitations on the solvent as long as it provides the solvent, such as cellosolves such as methyl cellosolve and ethyl cellosolve, cellosolve esters such as methyl cellosolve acetate, esters such as butyl acetate, dimethyl formaldehyde, dimethyl sulfoxide, etc. Examples include polar solvents. Note that, in order to prevent striation, a high boiling point solvent with relatively low volatility is generally desirable.
また本発明樹脂組成物には、必要に応じて現像性等の改
良のために界面活性剤、例えばポリオキシエチレンのモ
ノエーテル化物、モノエステル化物、ジエステル化物等
を添加してもよい。さらに必要に応じて、色素、顔料、
保存安定剤等を添加しても何らさしつかえない。Furthermore, a surfactant such as a monoether, monoester, diester, etc. of polyoxyethylene may be added to the resin composition of the present invention, if necessary, to improve developability and the like. In addition, dyes, pigments,
There is no harm in adding storage stabilizers or the like.
本発明パターン形成用樹脂組成物は、光照射により１，
２−キノンジアジド系化合物が光分解し、その光分解し
た部分を溶剤、つまり現像液に浸漬することによりパタ
ーンが形成される。The pattern-forming resin composition of the present invention can be irradiated with 1,
A pattern is formed by photodecomposing the 2-quinonediazide compound and immersing the photodecomposed portion in a solvent, that is, a developer.
上記現像液としては塩基性溶液であればいかなるもので
もよく、例えば水酸化ナトリウム、水酸化カリウム等の
無機塩基の水溶液、エチルアミン、ジエチルアミン、ジ
−ｎ−プロピルアミン等のアミン類の水溶液の他、テト
ラメチルアンモニウムハイドロオキサイド、トリメニル
ヒドロキシエチルアンモニウムハイドロオキサイドの水
溶液等が挙げられる。さらに上記現像液に必要に応じて
アルコール類、界面活性剤等を添加したものを用いるこ
とができる。The developing solution may be any basic solution, such as an aqueous solution of an inorganic base such as sodium hydroxide or potassium hydroxide, an aqueous solution of amines such as ethylamine, diethylamine, di-n-propylamine, etc. Examples include aqueous solutions of tetramethylammonium hydroxide and trimenylhydroxyethylammonium hydroxide. Furthermore, it is possible to use the above developer to which alcohols, surfactants, etc. are added, if necessary.
本発明樹脂組成物は、特に集積回路作成用レジストとし
て有用である他、プリント基板作成用レジストやオフセ
ット印刷、凸版印刷又は凹版印刷の版作成用感光性樹脂
、微細加工用レジスト等として用いることができる。The resin composition of the present invention is particularly useful as a resist for producing integrated circuits, and can also be used as a resist for producing printed circuit boards, a photosensitive resin for producing plates for offset printing, letterpress printing, or intaglio printing, a resist for microfabrication, etc. can.
次に、実施例を挙げて本発明を更に詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
数平均分子１２７００（単分散ポリスチレン換算ＧＰＣ
法）、分散度３．５、軟化点１８４℃（Ｂ＆Ｒ法） 、
ＯＲ当量１２７の線状高分子量タレゾールノボランク樹
脂（三菱油化■製： Ｌ−ＱＣＮ）１６．２５ｆｆｌ量
部と、ジアジドサルフエー・ト（Ｓ、Ｓ、Ｆｉｎｅｓ社
製： Ｎ Ｑ Ｄ Ｓ −Ｐｈｅｎｏｌ Ｎｏｖｏｌａ
ｋ Ｒｅ５ｉｎ Ｅｓｔｅｒ ２１８） ？、 ７５重
量部を溶剤（メチルセロソルブアセテート）７５重量部
に溶解し、孔径０．２μｍのフィルターで濾過して、本
発明パターン形成用樹脂組成物を得た。Example 1 Number average molecule 12700 (monodisperse polystyrene equivalent GPC
method), dispersity 3.5, softening point 184°C (B&R method),
16.25 ffl parts of linear high molecular weight Talesol Novolanc resin (manufactured by Mitsubishi Yuka Corporation: L-QCN) with an OR equivalent of 127 and diazide sulfate (S, S, manufactured by Fines Corporation: N Q D S -Phenol Novola
k Re5in Ester 218)? , was dissolved in 75 parts by weight of a solvent (methyl cellosolve acetate) and filtered through a filter with a pore size of 0.2 μm to obtain a pattern-forming resin composition of the present invention.
得られた上記組成物をシラザン処理したシリコンウェハ
ー上に膜厚カ月、５μｍとなるようにスピンナー塗布し
、オーブンにて８０℃で２０分間ブリヘークした。次い
で、２５０Ｗ超高圧水銀灯を光源とするアライナ−によ
るテストパターンマスクの吸引密着露光を行い、しかる
後、テトラメチルアンモニウム水溶液に３０秒浸漬して
現像し、純水にて洗浄してレジストパターンを形成した
。The resulting composition was applied onto a silazane-treated silicon wafer using a spinner to a film thickness of 5 μm, and then baked in an oven at 80° C. for 20 minutes. Next, the test pattern mask was subjected to suction contact exposure using an aligner using a 250W ultra-high pressure mercury lamp as a light source, and then developed by immersing it in a tetramethylammonium aqueous solution for 30 seconds, and washing with pure water to form a resist pattern. did.
次いで、パターン形状の耐熱性評価のため１６０℃、２
００℃の温度でそれぞれ３０分間クリーンオープンにて
ポストベークした。Next, to evaluate the heat resistance of the pattern shape, it was heated at 160°C for 2
Each sample was post-baked in a clean open state at a temperature of 00°C for 30 minutes.
パターン形状の変化を走査型電子顕微鏡で観察し、耐熱
性、密着性を調べたところ、ポストベーク前、ポストベ
ーク後のいずれにおいてもシリコンウェハーに対する密
着性が良好で、ポストベーク後におけるパターン（ずれ
もおこさず、しかもパターンのライン及びスペース間隔
も変化が生じることがなかった。When we observed changes in pattern shape using a scanning electron microscope and examined heat resistance and adhesion, we found that the adhesion to the silicon wafer was good both before and after post-bake, and the pattern (misalignment) after post-bake was found to be good. Moreover, no change occurred in the line and space spacing of the pattern.
比較例１
ｐ−ヒドロキシベンズアルデヒドとオルトクレゾールの
反応により得られたｐ−ヒドロキシベンズアルデヒド−
オルトクレゾールノボラック樹脂（結晶性、融点２２７
℃、ＯＨ当量１０７．４）を実施例１の線状高分子量ク
レゾールノボラック樹脂の代わりに用いる他は、実施例
１と同様にしてパターン形成用樹脂組成物を調製し、そ
の後も実施例１と同様にレジストパターンを形成して同
様の方法にて耐熱性評価を行ったところ、現像時に未露
光部の溶出が起こり、鮮明なパターン形成は得られなか
った。Comparative Example 1 p-hydroxybenzaldehyde obtained by reaction of p-hydroxybenzaldehyde and orthocresol
Orthocresol novolac resin (crystalline, melting point 227
A pattern-forming resin composition was prepared in the same manner as in Example 1, except that C.C., OH equivalent: 107.4) was used in place of the linear high molecular weight cresol novolac resin in Example 1, and then the same procedure as in Example 1 was carried out. When a resist pattern was formed in the same manner and the heat resistance was evaluated using the same method, elution of unexposed areas occurred during development, and clear pattern formation could not be obtained.
比較例２
市販品であるノボラックキノンジアジド型のポジ型フォ
トレジスト組成物を用いてメーカー指示通りのパターン
形成を行い、実施例１と同様に耐熱評価を行ったが、１
６０℃ですでにパターンくずれをおこし、しかもライン
およびスペース間隔も狭くなり、一部融合していた。Comparative Example 2 A commercially available novolak quinone diazide type positive photoresist composition was used to form a pattern according to the manufacturer's instructions, and the heat resistance was evaluated in the same manner as in Example 1.
At 60° C., the pattern had already collapsed, and the line and space intervals had become narrower, with some fusion.
以上説明したように、本発明パターン形成用樹脂組成物
は高分子量ノボランク樹脂を用いることにより造膜性が
向上し、シリコンウェハーに対する密着性および脆さが
改良され、また耐熱性および耐ドライエツチング性が著
しく向上するという優れた効果がある。As explained above, the pattern-forming resin composition of the present invention has improved film-forming properties by using a high molecular weight novolank resin, improved adhesion and brittleness to silicon wafers, and improved heat resistance and dry etching resistance. It has the excellent effect of significantly improving
Claims (3)
ド系化合物を含有することを特徴とするパターン形成用
樹脂組成物。(1) A pattern-forming resin composition containing a high molecular weight novolak resin and a 1,2-quinonediazide compound.
ク樹脂である特許請求の範囲第１項記載のパターン形成
用樹脂組成物。(2) The pattern-forming resin composition according to claim 1, wherein the high molecular weight novolak resin is a linear high molecular weight novolak resin.
び／又はパラクレゾールと、ホルムアルデヒドとより形
成された線状クレゾールノボラック樹脂である特許請求
の範囲第１項記載のパターン形成用樹脂組成物。(3) The pattern-forming resin composition according to claim 1, wherein the high molecular weight novolac resin is a linear cresol novolac resin formed from ortho-cresol and/or para-cresol and formaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4478387A JPS63210923A (en) | 1987-02-27 | 1987-02-27 | Resin composition for pattern formation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4478387A JPS63210923A (en) | 1987-02-27 | 1987-02-27 | Resin composition for pattern formation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63210923A true JPS63210923A (en) | 1988-09-01 |
Family
ID=12701003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4478387A Pending JPS63210923A (en) | 1987-02-27 | 1987-02-27 | Resin composition for pattern formation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210923A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03208055A (en) * | 1990-01-11 | 1991-09-11 | Tokyo Ohka Kogyo Co Ltd | Positive type photoresist composition |
| JPH03208054A (en) * | 1990-01-11 | 1991-09-11 | Tokyo Ohka Kogyo Co Ltd | Novel positive type photoresist composition |
| EP0561079A1 (en) * | 1992-03-16 | 1993-09-22 | Pioneer Electronic Corporation | Photoresist for optical disc and method of preparing optical disc utilizing photoresist |
| EP0902326A3 (en) * | 1997-07-25 | 1999-09-29 | Tokyo Ohka Kogyo Co., Ltd. | Novolak resin precursor, novolak resin and positive photoresist composition containing the novolak resin |
| JP2001296654A (en) * | 2000-04-14 | 2001-10-26 | Koyo Kagaku Kogyo Kk | Positive-type photoresist composition |
-
1987
- 1987-02-27 JP JP4478387A patent/JPS63210923A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03208055A (en) * | 1990-01-11 | 1991-09-11 | Tokyo Ohka Kogyo Co Ltd | Positive type photoresist composition |
| JPH03208054A (en) * | 1990-01-11 | 1991-09-11 | Tokyo Ohka Kogyo Co Ltd | Novel positive type photoresist composition |
| EP0561079A1 (en) * | 1992-03-16 | 1993-09-22 | Pioneer Electronic Corporation | Photoresist for optical disc and method of preparing optical disc utilizing photoresist |
| EP0902326A3 (en) * | 1997-07-25 | 1999-09-29 | Tokyo Ohka Kogyo Co., Ltd. | Novolak resin precursor, novolak resin and positive photoresist composition containing the novolak resin |
| JP2001296654A (en) * | 2000-04-14 | 2001-10-26 | Koyo Kagaku Kogyo Kk | Positive-type photoresist composition |
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