JPH0342461B2 - - Google Patents
Info
- Publication number
- JPH0342461B2 JPH0342461B2 JP1622583A JP1622583A JPH0342461B2 JP H0342461 B2 JPH0342461 B2 JP H0342461B2 JP 1622583 A JP1622583 A JP 1622583A JP 1622583 A JP1622583 A JP 1622583A JP H0342461 B2 JPH0342461 B2 JP H0342461B2
- Authority
- JP
- Japan
- Prior art keywords
- photoresist
- absorbing agent
- light absorbing
- hydrogen atom
- photosensitive composition
- 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.)
- Expired
Links
- 229920002120 photoresistant polymer Polymers 0.000 claims description 40
- 239000006096 absorbing agent Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 241000270708 Testudinidae Species 0.000 claims description 5
- 229920003986 novolac Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- -1 azo compound Chemical class 0.000 claims description 4
- 241000270666 Testudines Species 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001259 photo etching Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- WQMWHMMJVJNCAL-UHFFFAOYSA-N 2,4-dimethylpenta-1,4-dien-3-one Chemical compound CC(=C)C(=O)C(C)=C WQMWHMMJVJNCAL-UHFFFAOYSA-N 0.000 description 2
- AYKNBEUSHQHYSX-UHFFFAOYSA-N 4-[(4-ethoxyphenyl)diazenyl]-n,n-diethylaniline Chemical compound C1=CC(OCC)=CC=C1N=NC1=CC=C(N(CC)CC)C=C1 AYKNBEUSHQHYSX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NGPGYVQZGRJHFJ-BUHFOSPRSA-N 4-(4-nitrophenylazo)resorcinol Chemical compound OC1=CC(O)=CC=C1\N=N\C1=CC=C([N+]([O-])=O)C=C1 NGPGYVQZGRJHFJ-BUHFOSPRSA-N 0.000 description 1
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 1
- CQKQINNUKSBEQR-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]diazenyl]phenol Chemical compound CN(C)c1ccc(cc1)N=Nc1ccc(O)cc1 CQKQINNUKSBEQR-UHFFFAOYSA-N 0.000 description 1
- XUWHYFCWTFFFPS-UHFFFAOYSA-N 5-(dimethylamino)-2-phenyldiazenylphenol Chemical compound C1(=CC=CC=C1)N=NC1=C(C=C(C=C1)N(C)C)O XUWHYFCWTFFFPS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SJJISKLXUJVZOA-UHFFFAOYSA-N Solvent yellow 56 Chemical compound C1=CC(N(CC)CC)=CC=C1N=NC1=CC=CC=C1 SJJISKLXUJVZOA-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 1
- 230000037303 wrinkles Effects 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Description
【発明の詳細な説明】
本発明は、新規な吸光剤を含有して成る感光性
組成物に関し、特に半導体素子などの微細加工に
好適な感光性組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive composition containing a novel light absorbing agent, and particularly to a photosensitive composition suitable for microfabrication of semiconductor devices and the like.
トランジスター、IC、LSIなどの半導体素子
は、これまでホトエツチング法による微細加工技
術によつて製造されている。このホトエツチング
法は、シリコンウエハー上にホトレジスト層を形
成し、その上に所定のパターンを有するマスクを
重ねて露光し、現像して画像を形成させたのち、
エツチングにより、目的のパターンを形成し、こ
れを用いて選択拡散を行う方法である。そして、
通常このような工程を数回繰り返して選択拡散を
行つたのち、アルミニウム電極、配線処理を施し
て半導体の電子部品が作成される。 Semiconductor elements such as transistors, ICs, and LSIs have so far been manufactured using microfabrication technology using photoetching. This photoetching method involves forming a photoresist layer on a silicon wafer, overlaying a mask with a predetermined pattern on it, exposing it to light, and developing it to form an image.
In this method, a desired pattern is formed by etching and selective diffusion is performed using this pattern. and,
Normally, such steps are repeated several times to perform selective diffusion, and then aluminum electrodes and wiring are processed to produce a semiconductor electronic component.
このような半導体素子の製造においては、選択
拡散を数回行えば、通常1μｍ以上の段差を生じ、
これにパツシベーシヨンを施せば段差はさらに大
きくなる。このような表面に、アルミニウム配線
を施す場合、シリコンウエハーの表面にアルミニ
ウムを蒸着し、これをホトエツチング法によりエ
ツチングする必要があるが、アルミニウムを表面
に蒸着した基板上にホトレジスト層を形成し、露
光を行なつた場合には一般にアルミニウム表面に
よるハレーシヨンが大きく、ネガ型又はポジ型の
ホトレジストあるいはデイープUVレジストを用
いると、表面の平担な部分ばかりでなく、前記の
段差部分において、基板面に垂直に入射してきた
光線がその段部の傾斜面で乱反射を起し、そのた
め数μｍの細い線幅のパターンを正確に再現する
ことが困難になるという欠点があつた。 In the manufacture of such semiconductor devices, if selective diffusion is performed several times, a step difference of 1 μm or more usually occurs;
If we apply passivation to this, the difference in level will become even larger. When applying aluminum wiring to such a surface, it is necessary to evaporate aluminum onto the surface of the silicon wafer and then etch it using a photoetching method. When this is done, halation due to the aluminum surface is generally large, and when negative or positive photoresists or deep UV resists are used, not only the flat parts of the surface but also the stepped parts mentioned above, there is a large halation due to the aluminum surface. The disadvantage is that the incident light beams are diffusely reflected on the sloped surface of the stepped portion, making it difficult to accurately reproduce a pattern with a narrow line width of several micrometers.
このハレーシヨンを防止し、微細な画像を正確
に再現する目的で、従来ホトレジストの研究が
種々行われ、これに、吸光性材料を添加する技術
が開発されている（特公昭51−37562号公報）。 In order to prevent this halation and accurately reproduce fine images, various researches have been conducted on photoresists, and a technology has been developed to add light-absorbing materials to them (Japanese Patent Publication No. 37562/1983). .
従来、ホトレジスト用吸光剤としては、有機染
料の一種であるオイルイエロー（商品名）や１−
アルコキシ−４−（4′−Ｎ，Ｎ−ジアルキルアミ
ノフエニルアゾ）ベンゼン誘導体などが採用され
てきた（特開昭55−36838号公報）。しかし、オイ
ルイエローは、通常80〜100℃の温度で行なわれ
るプレベーキングにおいて容易に昇華してホトレ
ジスト膜から揮散し、露光時のハレーシヨン防止
効果が著しくそこなわれる欠点があり、またプレ
ベーキングの処理条件に大きく影響されてバラツ
キが生ずるという欠点があつた。一方後者は、プ
レベーキング時の昇華揮散性に問題はないが、例
えばフエノール）ボラツク樹脂とｏ−キノンジア
ジド化合物より成るポジ型ホトレジストに配合し
た場合、感度が著しく低下するという欠点があつ
た。 Conventionally, light absorbers for photoresists include Oil Yellow (trade name), a type of organic dye, and 1-
Alkoxy-4-(4'-N,N-dialkylaminophenylazo)benzene derivatives have been employed (Japanese Patent Application Laid-open No. 36838/1983). However, oil yellow has the disadvantage that it easily sublimes and evaporates from the photoresist film during pre-baking, which is usually carried out at a temperature of 80 to 100°C, which significantly impairs the anti-halation effect during exposure. The drawback was that it was greatly influenced by conditions, resulting in variations. On the other hand, the latter has no problem with sublimation and volatility during pre-baking, but has the disadvantage that, when incorporated into a positive photoresist comprising, for example, a phenolic volcanic resin and an o-quinone diazide compound, the sensitivity is significantly lowered.
本発明者らは、このような従来の感光性樹脂組
成物のもつ欠点を克服し、どのようなホトレジス
トにおいても効果的に作用しうる吸光剤について
鋭意研究を重ねた結果、ある種のアゾ化合物系吸
光剤がこの目的を達成するのに効果的であること
を見出し、この知見に基づいて本発明を完成する
に至つた。 The present inventors have conducted extensive research on light absorbers that can overcome the drawbacks of conventional photosensitive resin compositions and act effectively in any photoresist, and as a result, have developed a certain azo compound. The inventors have discovered that a light absorbing agent is effective in achieving this objective, and have completed the present invention based on this knowledge.
すなわち、本発明は、
ホトレジストに、一般式
■■■ 亀の甲 ［0279］ ■■■
〔式中のR1は水素原子又は水酸基、R2は水素原
子、ニトロ基又はジ（低級アルキル）アミノ基で
ある〕
■■■ 亀の甲 ［0280］ ■■■
（式中のR3とR4の一方は水酸基であつて他方は
水素原子である）
又は
■■■ 亀の甲 ［0281］ ■■■
（式中のR5は
■■■ 亀の甲 ［0282］ ■■■
■■■ 亀の甲 ［0283］ ■■■
又は
■■■ 亀の甲 ［0284］ ■■■
である）
で表わされるアゾ化合物の中から選ばれた少なく
とも１種の吸光剤を配合したことを特徴とする感
光性組成物を提供するものである。 That is, the present invention provides a photoresist having the general formula ■■■ Tortoiseshell [0279] ■■■ [In the formula, R 1 is a hydrogen atom or a hydroxyl group, and R 2 is a hydrogen atom, a nitro group, or a di(lower alkyl) amino group] ] ■■■ Tortoise shell [0280] ■■■ (One of R 3 and R 4 in the formula is a hydroxyl group and the other is a hydrogen atom) or ■■■ Tortoise shell [0281] ■■■ (In the formula, one of R 3 and R 4 is a hydroxyl group and the other is a hydrogen atom) R 5 is at least one azo compound selected from among the azo compounds represented by The present invention provides a photosensitive composition characterized in that it contains a certain type of light absorbing agent.
上記の一般式（）、（）及び（）の中のフ
エニル基、ナフチル基は、所定の置換基に加え
て、さらに所望に応じ低級アルキル基、低級アル
コキシ基、ハロゲン原子及び水酸基の中から選ば
れた少くとも１種の置換基を有していてもよい。
このようなアゾ化合物の中で特に好適なものの例
を以下に示す。 In addition to the predetermined substituents, the phenyl group and naphthyl group in the above general formulas (), (), and () are selected from lower alkyl groups, lower alkoxy groups, halogen atoms, and hydroxyl groups as desired. may have at least one substituent.
Examples of particularly suitable azo compounds are shown below.
■■■ 亀の甲 ［0020］ ■■■
これらのアゾ化合物は、通常、単独で用いられ
るが所望ならば２種以上組み合わせて用いること
もできる。■■■ Turtle Shell [0020] ■■■ These azo compounds are usually used alone, but if desired, two or more types can be used in combination.
次に本発明組成物の基材として用いられるホト
レジストとしては、例えば高分子化合物とビスア
ジド化合物を主成分とするネガ型ホトレジスト、
フエノール、ノボラツク樹脂、クレゾールノボラ
ツク樹脂又はその両方と、少くとも１個のｏ−キ
ノンジアジド化合物を含むポジ型ホトレジスト、
あるいはポリメチルメタクリレート（PMMA）、
ポリメチルイソプロペニルケトン（PMIPK）又
はポリグリシジルメタクリレート（PGMA）等
の高分子物を主成分とするデイープUVレジスト
などをあげることができる。 Next, as the photoresist used as the base material of the composition of the present invention, for example, a negative photoresist containing a polymer compound and a bisazide compound as main components,
A positive photoresist comprising a phenol, a novolac resin, a cresol novolac resin, or both, and at least one o-quinonediazide compound;
or polymethyl methacrylate (PMMA),
Examples include deep UV resists whose main component is a polymer such as polymethyl isopropenyl ketone (PMIPK) or polyglycidyl methacrylate (PGMA).
前記ネガ型ホトレジストの例としては、
ONNR−20，ONNR−22（商品名、東京応化工
業(株)製）などがあり、ポジ型ホトレジストの例と
しては、OFPR−２、OFPR−77、OFPR−800
〔商品名、東京応化工業(株)製〕、AZ−1350、AZ−
1400〔商品名、シツプレー社製〕などがある。ま
たデイープUVレジストの例としてはODUR−
100、ODUR−1000、ODUR−1013〔商品名、東
京応化工業(株)製〕などを挙げることができる。 Examples of the negative photoresist include:
ONNR-20, ONNR-22 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), etc. Examples of positive photoresists include OFPR-2, OFPR-77, OFPR-800.
[Product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.], AZ-1350, AZ-
1400 [product name, manufactured by Situpre Co.], etc. Also, an example of deep UV resist is ODUR−
100, ODUR-1000, ODUR-1013 [trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.].
本発明の感光性組成物に含有させる前記吸光剤
の量は、上記ホトレジストの重量に基づき、0.1
〜20重量％の範囲、特に0.1〜15重量％の範囲で
添加するのが好ましい。添加量がこれより少ない
とハレーシヨン防止効果が発揮されないし、また
これよりも多くなると、ホトレジスト膜中に吸光
剤の結晶が析出し、不均一相を形成する傾向があ
るので好ましくない。 The amount of the light absorbing agent contained in the photosensitive composition of the present invention is 0.1 based on the weight of the photoresist.
Preferably, it is added in a range of ~20% by weight, particularly in a range of 0.1-15% by weight. If the amount added is less than this, the antihalation effect will not be exhibited, and if it is more than this, crystals of the light absorbing agent will tend to precipitate in the photoresist film and form a heterogeneous phase, which is not preferable.
本発明で用いる吸光剤は、ネガ型ホトレジス
ト、ポジ型ホトレジスト及びデイープUVレジス
トのいずれの皮膜形成成分に対しても優れた相容
性を有し、またエチレングリコール、モノエチル
エーテルアセテート、エチレングリコールモノエ
チルエーテル、シクロヘキサ）ン等の多くの有機
溶剤に易溶性であるから、レジスト膜形成用液に
直接添加するか、あるいは該液に溶解する有機溶
剤の少量に溶解して添加することにより、容易に
均一な組成物を得ることができる。さらに、本発
明で用いる吸光剤は、高温下においても昇華性を
示さず、プレベーキングしたのちでもホトレジス
ト皮膜中に高い残存率で安定に存在するので、露
光の際のハレーシヨン防止効果が極めて大きく、
各種ホトレジストのパターン形成能を高めること
ができる。特に、従来プレベーキングによる感度
低下が大きいとされているフエノールノボラツク
樹脂とＯ−キノンジアジド化合物より成るポジ型
ホトレジストに前記一般式（）〜（）の吸光
剤を含有させるとき、その感度低下を極めて小さ
くすることができ、満足し得る特性をもつた実用
的ポジ型感光性組成物が提供される。 The light absorbing agent used in the present invention has excellent compatibility with film-forming components of negative photoresists, positive photoresists, and deep UV resists, and also has excellent compatibility with film-forming components of negative photoresists, positive photoresists, and deep UV resists. It is easily soluble in many organic solvents such as ethyl ether and cyclohexane, so it can be easily added to the resist film forming solution either directly or by dissolving it in a small amount of the organic solvent that dissolves in the solution. A uniform composition can be obtained. Furthermore, the light absorbing agent used in the present invention does not show sublimation even at high temperatures and remains stably in the photoresist film at a high residual rate even after pre-baking, so it has an extremely large anti-halation effect during exposure.
The pattern forming ability of various photoresists can be improved. In particular, when a positive photoresist made of a phenol novolac resin and an O-quinone diazide compound, which is conventionally known to cause a large sensitivity reduction due to prebaking, contains a light absorbing agent of the general formulas () to (), the sensitivity reduction is extremely severe. A practical positive-working photosensitive composition that can be made small and has satisfactory properties is provided.
このように、本発明の感光性組成物は、その塗
膜を例えば80〜100℃の温度でプレベーキングし
て溶剤を蒸散させた場合に、吸光剤が揮散したり
変化することなくレジスト膜中に安定に存在する
ので、完全に溶剤を除くことができ、またアルミ
ニウムなどの基板表面からのハレーシヨンを防止
して、再現性よく微細パターンを形成しうる極め
て望ましい高感度ホトレジスト膜を提供する。し
たがつて、本発明の組成物を用いるとき、溶剤の
残留により表面にしわなどを生ずることがなく、
基板に強固に接着したホトレジスト膜を容易に形
成させることができる。また、プレベーキング後
長時間放置、保存しても、ホトレジスト皮膜中に
結晶が析出し不均一相を形成することがないの
で、皮膜として保存することも可能であるためホ
トエツチング作業の操作の許容幅が広くなり、取
扱い処理が容易になる。さらに、品質の安定した
ものを多量生産できまた吸光剤添加による感度低
下がないので投影方式のマスクアライナーも使用
でき超微細の加工分野にも利用可能となる。 As described above, when the photosensitive composition of the present invention pre-bakes the coating film at a temperature of, for example, 80 to 100°C to evaporate the solvent, the light absorbing agent remains in the resist film without volatilization or change. The present invention provides an extremely desirable high-sensitivity photoresist film that can completely remove the solvent, prevent halation from the surface of a substrate such as aluminum, and form fine patterns with good reproducibility. Therefore, when using the composition of the present invention, wrinkles etc. do not occur on the surface due to residual solvent,
A photoresist film that firmly adheres to a substrate can be easily formed. In addition, even if left for a long time after prebaking, crystals will not precipitate in the photoresist film and form a heterogeneous phase, so it can be stored as a film, which reduces the allowable range of photoetching operations. The area becomes wider and handling becomes easier. Furthermore, since products of stable quality can be mass-produced and there is no decrease in sensitivity due to the addition of a light-absorbing agent, a projection-type mask aligner can also be used, and it can also be used in the field of ultra-fine processing.
次に、本発明を実施例を挙げてさらに詳細に説
明するが、本発明はこれらの実施例によつて、何
らの制限をも受けるものではない。 EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited in any way by these Examples.
実施例 １
フエノールノボラツク樹脂と、少なくとも１個
のＯ−キノンジアジド化合物を含むポジ型ホトレ
ジストOFPR−800（商品名、東京応化工業社製、
固形分含有量27重量％）に対し、その固形分の３
重量％の吸光剤４−ヒドロキシ−4′−ジメチルア
ミノアゾベンゼンを添加し、感光性組成物を調製
した。Example 1 Positive photoresist OFPR-800 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing a phenol novolac resin and at least one O-quinonediazide compound
Solid content: 27% by weight), its solid content is 3% by weight.
A photosensitive composition was prepared by adding the light absorbing agent 4-hydroxy-4'-dimethylaminoazobenzene in an amount of % by weight.
この組成物を、厚さ0.5μｍのアルミニウム層を
蒸着した1μｍ厚の段差構造のシリコンウエハー
に、膜厚1.3μｍとなるようにスピンコートを行な
い、温風循環乾燥機を用いて90℃で20分間プレベ
ーキングして、被膜を形成した。これにマスクを
介して200W超高圧水銀灯をもつキヤノンマスク
アライナーPLA−500（キヤノン(株)製）で、4.5秒
間露光し、現像液NMD−３（商品名、東京応化
工業(株)製）に液温25℃で１分間浸し、浸漬法で現
像した。形成されたレジストパターンはハレーシ
ヨンの影響による段線及び定在波の影響によるギ
ザギザはなく、0.5μｍの線幅まで解像された。 This composition was spin-coated to a film thickness of 1.3 μm on a silicon wafer with a 1 μm-thick step structure on which a 0.5 μm-thick aluminum layer had been vapor-deposited. A film was formed by pre-baking for a minute. This was exposed through a mask for 4.5 seconds using a Canon Mask Aligner PLA-500 (manufactured by Canon Inc.) equipped with a 200W ultra-high pressure mercury lamp, and then exposed to developer NMD-3 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). It was immersed for 1 minute at a solution temperature of 25°C and developed using the immersion method. The formed resist pattern had no dashed lines due to the effect of halation or jaggedness due to the effect of standing waves, and was resolved to a line width of 0.5 μm.
比較例１及び対照例
実施例１において、吸光剤４−ヒドロキシ−
4′−ジメチルアミノアゾベンゼンに代えて、従来
使用されている４−エトキシ−4′−ジエチルアミ
ノアゾベンゼンを吸光剤として同量添加した以外
は全く同様に操作してレジストパターン形成能を
しらべた（比較例１）。Comparative Example 1 and Control Example In Example 1, the light absorber 4-hydroxy-
The resist pattern forming ability was examined using exactly the same procedure except that the same amount of the conventionally used 4-ethoxy-4'-diethylaminoazobenzene was added as a light absorber instead of 4'-dimethylaminoazobenzene (Comparative Example) 1).
また、吸光剤を全く使用しないポジ型ホトレジ
ストOFPR−800を感光性組成物として、同様に
レジストパターン形成能をしらべた（対照例）。 In addition, the resist pattern forming ability was similarly examined using a photosensitive composition using a positive photoresist OFPR-800 that does not use any light absorbing agent (control example).
その結果、吸光剤を添加しないものは、適切な
画像形成に必要な露光時間（露光量）は3.6秒で
あり、感度の点では問題はなかつたが、段差下部
のレジスト像は、段差側面よりのハレーシヨンの
影響をうけて虫食い状の個所が多数見られ、微細
パターン部では断線していた。また定在波の影響
によりパターンがギザギザしており、線幅1μｍ
までしか解像されなかつた。 As a result, the exposure time (exposure amount) required to form an appropriate image was 3.6 seconds for the resist without the addition of a light absorber, and there was no problem in terms of sensitivity. There were many moth-eaten spots due to the effect of halation, and there were breaks in the fine pattern areas. In addition, the pattern is jagged due to the influence of standing waves, and the line width is 1 μm.
Only up to this point could be resolved.
一方、比較例１の組成物は、ハレーシヨン及び
定在波の影響は全く見られず、線幅0.5μｍまで解
像されていたが、露光量は9.5秒間を要し、スル
ープツトの低下の原因となつている。 On the other hand, with the composition of Comparative Example 1, no effects of halation or standing waves were observed, and the line width was resolved down to 0.5 μm, but the exposure amount required 9.5 seconds, which may be the cause of the decrease in throughput. It's summery.
実施例 ２
実施例１の吸光剤に代えて２，４−ジヒドロキ
シ−4′−ニトロアゾベンゼンを用いるほかは実施
例１と全く同様に操作した。その結果、レジスト
の露光時間は4.5秒間であり、また、ハレーシヨ
ンや定在波の影響は全く見られなかつた。Example 2 The same procedure as in Example 1 was repeated except that 2,4-dihydroxy-4'-nitroazobenzene was used in place of the light absorbing agent used in Example 1. As a result, the exposure time of the resist was 4.5 seconds, and no effects of halation or standing waves were observed.
実施例３〜６，比較例２
実施例１の吸光剤に代え、第１表に示す他の本
発明の吸光剤４種類をそれぞれ用いた４種の感光
性組成物及び比較のためにオイルイエローSS（４
−ジエチルアミノアゾベンゼン）を用いた組成物
を実施例１と同様にして調製し、また同様な操作
を実施して、各レジストパターン形成能をしらべ
た。Examples 3 to 6, Comparative Example 2 Four types of photosensitive compositions in which four types of light absorbers of the present invention shown in Table 1 were used in place of the light absorber of Example 1, and Oil Yellow for comparison. SS (4
-diethylaminoazobenzene) was prepared in the same manner as in Example 1, and the same operations were carried out to examine the ability of each resist pattern to form.
それらの結果を次表にまとめて示すとともに、
参考のために、前記実施例１，２及び比較例１の
データも併記した。表のデータから本発明に係る
吸光剤は、ポジ型ホトレジスト用として優れてい
ることがわかる。 The results are summarized in the table below, and
For reference, the data of Examples 1 and 2 and Comparative Example 1 are also listed. From the data in the table, it can be seen that the light absorbing agent according to the present invention is excellent for use in positive photoresists.
■■■ 亀の甲 ［0021］ ■■■
また、実施例１で用いた本発明に係る吸光剤４
−ヒドロキシ−4′−ジメチルアミノアゾベンゼン
（吸光剤Ａと称す）と比較例１で用いた従来使用
されている吸光剤４−エトキシ−4′−ジエチルア
ミノアゾベンゼン（吸光剤Ｂと称す）とのプレベ
ーキングにおける経時的ホトレジスト膜中残存率
を次のようにしてしらべた。■■■ Tortoise shell [0021] ■■■ In addition, the light absorbing agent 4 according to the present invention used in Example 1
- Prebaking of hydroxy-4'-dimethylaminoazobenzene (referred to as light absorber A) and the conventionally used light absorber 4-ethoxy-4'-diethylaminoazobenzene (referred to as light absorber B) used in Comparative Example 1 The residual rate in the photoresist film over time was investigated as follows.
ホトレジストとしてポジ型のOFPR−800を用
い、吸光剤Ａを添加配合した組成物を基板に塗布
して試料を作成し、同量の吸光剤Ｂを用いて全く
同様にして別の試料を作成した。次いで両試料を
80℃の温度でプレベーキングし、各ホトレジスト
膜中のそれぞれの吸光剤の量を経時的に定量し
た。 Using positive-type OFPR-800 as a photoresist, a sample was created by applying a composition containing light absorber A to the substrate, and another sample was created in exactly the same manner using the same amount of light absorber B. . Then both samples
Prebaking was performed at a temperature of 80°C, and the amount of each light absorber in each photoresist film was quantified over time.
添付図面は、各試料についてのプレベーキング
時間（分）と含有吸光剤のホトレジスト膜中残存
率（％）との関係を示すグラフで、吸光剤Ａが実
線、吸光剤Ｂが点線で示されている。 The attached drawing is a graph showing the relationship between the prebaking time (minutes) and the residual rate (%) of the contained light absorber in the photoresist film for each sample, with light absorber A shown as a solid line and light absorber B shown as a dotted line. There is.
この図から明らかなように、本発明に係る吸光
剤Ａは高い残存率を示すが、従来の吸光剤である
吸光剤Ｂは、プレベーキング時間が長いほど、そ
の昇華性のために被膜中の残存率が低下し、ハレ
ーシヨン防止効果が減退する。また、プレベーキ
ング温度が高いほど残存率が低下することも理解
できる。 As is clear from this figure, the light absorbent A according to the present invention exhibits a high residual rate, but the longer the pre-baking time, the more the light absorbent B, which is a conventional light absorber, becomes more concentrated in the film due to its sublimation property. The residual rate decreases and the antihalation effect decreases. It can also be understood that the higher the pre-baking temperature, the lower the survival rate.
実施例 ７
高分子化合物とビスアジド化合物よりなるネガ
型ホトレジストONNR−20（商品名、東京応化工
業(株)製、固形分含有量12％）に、その含有樹脂分
の３重量％の吸光剤
■■■ 亀の甲 ［0297］ ■■■
を添加して感光性組成物を調製した。Example 7 A negative photoresist ONNR-20 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd., solid content 12%) consisting of a polymer compound and a bisazide compound was added with a light absorbing agent of 3% by weight based on its resin content. ■■ Turtle shell [0297] ■■■ was added to prepare a photosensitive composition.
この組成物を、厚さ0.5μｍのアルミニウム層を
蒸着した厚さ1μｍの段差構造のシリコンウエハ
ーに、膜厚1.0μｍになるようにスピンコートし、
温風循環乾燥機を用いて100℃、30分間プレベー
キングを行い被膜形成を行つた。この被膜にマス
クを介して、キヤノンマスクアライナーPLA−
500（キヤノン(株)製）により８秒間露光し、次に
ONNR用現像液（商品名、東京応化工業(株)製）
及びONNR用リンス液（商品名、東京応化工業
(株)製）にそれぞれ１分間つづ浸漬してパターニン
グを行つた。形成されたパターンは、ハレーシヨ
ン及び定在波の影響はなく、3μｍのラインアン
ドスペースまで解像されていた。 This composition was spin-coated to a film thickness of 1.0 μm on a silicon wafer with a 1 μm-thick step structure on which a 0.5 μm-thick aluminum layer was vapor-deposited.
A film was formed by pre-baking at 100°C for 30 minutes using a hot air circulation dryer. Canon Mask Aligner PLA-
500 (manufactured by Canon Inc.) for 8 seconds, then
ONNR developer (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.)
and ONNR rinsing liquid (product name, Tokyo Ohka Kogyo)
(manufactured by Co., Ltd.) for 1 minute each to perform patterning. The formed pattern was free from the effects of halation and standing waves, and was resolved down to lines and spaces of 3 μm.
比較例 ３
実施例７において、吸光剤を添加しないこと及
び露光量を５秒間にしたこと以外は実施例７と全
く同様にしてパターニングを行つた。このパター
ンの観察結果は4μｍのラインアンドスペースま
でしか解像されておらず、ギザギザが多発してい
た。Comparative Example 3 Patterning was carried out in exactly the same manner as in Example 7, except that no light absorbing agent was added and the exposure amount was set to 5 seconds. The observation result of this pattern was that it was only resolved down to lines and spaces of 4 μm, and there were many jagged edges.
実施例 ８
ポリメチルイソプロペニルケトン重合体に増感
剤を加えたデイープUVホトレジストODUR−
1013（商品名、東京応化工業(株)製、樹脂濃度10重
量％）に、樹脂量の５重量％の吸光剤
■■■ 亀の甲 ［0298］ ■■■
を添加して感光性組成物を調製した。Example 8 Deep UV photoresist ODUR- with sensitizer added to polymethyl isopropenyl ketone polymer
1013 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd., resin concentration 10% by weight), a photosensitive composition was prepared by adding the light absorbing agent ■■■ Tortoise Shell [0298] ■■■ in an amount of 5% by weight of the resin amount. did.
この組成物を、実施例１〜７と同様な段差のあ
るアルミニウム基板上に、膜厚1.0μｍに塗布し、
120℃の温風乾燥機で30分間プレベーキングを行
つた。この被膜にマスクを介して、コールドミラ
ー290を装着したデイープUV露光装置キヤノン
PLA−520（キヤノン(株)製）を用いて６秒間露光
した。ODUR現像液（商品名、東京応化工業(株)
製）で23℃、２分間浸漬法で現像を行い、
ODURリンス液（商品名、東京応化工業(株)製）
で23℃、１分間リンス処理を行つた。形成された
レジストパターンは、段差テーパー部からのハレ
ーシヨンによるカケ（虫喰い）や断線もなく、ま
た定在波の影響によるギザギザもなく、線幅0.5μ
ｍまで解像されていた。 This composition was applied to a film thickness of 1.0 μm on an aluminum substrate with steps similar to those in Examples 1 to 7,
Prebaking was performed for 30 minutes in a hot air dryer at 120°C. Canon's deep UV exposure system attached Cold Mirror 290 to this film through a mask.
Exposure was performed for 6 seconds using PLA-520 (manufactured by Canon Inc.). ODUR developer (product name, Tokyo Ohka Kogyo Co., Ltd.)
Developed using the immersion method at 23°C for 2 minutes at
ODUR rinse liquid (product name, manufactured by Tokyo Ohka Kogyo Co., Ltd.)
Rinse treatment was performed at 23°C for 1 minute. The formed resist pattern has no chips or breaks due to halation from the tapered step part, no jaggedness due to the influence of standing waves, and a line width of 0.5μ.
It was resolved up to m.
比較例 ４
実施例８において、吸光剤を添加しない以外
は、実施例８と全く同様にしてホトレジストパタ
ーンを形成させたところ、線幅1.0μｍで小さなギ
ザギザが多数発生し、解像力が低下していること
が認められた。Comparative Example 4 In Example 8, when a photoresist pattern was formed in exactly the same manner as in Example 8 except that no light absorbing agent was added, many small jags with a line width of 1.0 μm were generated, and the resolution was decreased. This was recognized.
図面は本発明と比較例との感光性組成物の塗膜
のプレベーキングにおけるベーキング時間と膜中
残存率を示すグラフである。
The drawing is a graph showing the baking time and residual rate in the film during pre-baking of the photosensitive compositions of the present invention and comparative examples.
Claims (1)
子、ニトロ基又はジ（低級アルキル）アミノ基で
ある〕 ■■■ 亀の甲 ［0274］ ■■■ （式中のR3とR4の一方は水酸基であつて他方は
水素原子である） 又は ■■■ 亀の甲 ［0275］ ■■■ （式中のR5は ■■■ 亀の甲 ［0276］ ■■■ ■■■ 亀の甲 ［0277］ ■■■ 又は■■■ 亀の甲 ［0278］ ■■■ である） で表わされるアゾ化合物の中から選ばれた少なく
とも１種の吸光剤を配合したことを特徴とする感
光性組成物。 ２ ホトレジストが、高分子化合物及びビスアジ
ド化合物を主成分とするネガ型ホトレジスト、ノ
ボラツク樹脂及び少なくとも１個のｏ−キノンア
ジド化合物を主成分とするポジ型ホトレジスト又
はデイープUVレジストである特許請求の範囲第
１項記載の感光性組成物。 ３ ホトレジストの重量当り0.1〜20重量％の吸
光剤を配合する特許請求の範囲第１項記載の感光
性組成物。[Claims] 1. In the photoresist, the general formula ■■■ Turtle shell [0273] ■■■ [In the formula, R 1 is a hydrogen atom or a hydroxyl group, and R 2 is a hydrogen atom, a nitro group, or a di(lower alkyl) amino group] ] ■■■ Tortoise shell [0274] ■■■ (One of R 3 and R 4 in the formula is a hydroxyl group and the other is a hydrogen atom) or ■■■ Turtle shell [0275] ■■■ (In the formula, one of R 3 and R 4 is a hydroxyl group and the other is a hydrogen atom) R 5 is at least an azo compound selected from among the azo compounds represented by A photosensitive composition characterized by containing one kind of light absorbing agent. 2. Claim 1, wherein the photoresist is a negative photoresist mainly composed of a polymer compound and a bisazide compound, a positive photoresist mainly composed of a novolac resin and at least one o-quinone azide compound, or a deep UV resist. The photosensitive composition described in . 3. The photosensitive composition according to claim 1, which contains a light absorbing agent in an amount of 0.1 to 20% by weight based on the weight of the photoresist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1622583A JPS59142538A (en) | 1983-02-04 | 1983-02-04 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1622583A JPS59142538A (en) | 1983-02-04 | 1983-02-04 | Photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59142538A JPS59142538A (en) | 1984-08-15 |
| JPH0342461B2 true JPH0342461B2 (en) | 1991-06-27 |
Family
ID=11910592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1622583A Granted JPS59142538A (en) | 1983-02-04 | 1983-02-04 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59142538A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61241759A (en) * | 1985-04-18 | 1986-10-28 | Toray Ind Inc | Lithographic plate requiring no water |
| JPH0743533B2 (en) * | 1985-05-13 | 1995-05-15 | 富士写真フイルム株式会社 | Positive photosensitive lithographic printing plate |
| JPH0766184B2 (en) * | 1985-06-04 | 1995-07-19 | 住友化学工業株式会社 | Positive photoresist composition |
| JP2614847B2 (en) * | 1986-06-16 | 1997-05-28 | 東京応化工業 株式会社 | Positive photosensitive composition |
| JPS63161443A (en) * | 1986-12-24 | 1988-07-05 | Sumitomo Chem Co Ltd | Photoresist composition |
| JPH0812422B2 (en) * | 1987-05-06 | 1996-02-07 | 三菱化学株式会社 | Positive photoresist composition |
| JP2563799B2 (en) * | 1987-06-03 | 1996-12-18 | 日本ゼオン株式会社 | Positive photoresist composition |
| JP2654947B2 (en) * | 1987-07-16 | 1997-09-17 | 日本ゼオン株式会社 | Positive photoresist composition |
| JP2640137B2 (en) * | 1989-02-28 | 1997-08-13 | 富士写真フイルム株式会社 | Positive photoresist composition |
| JP2619050B2 (en) * | 1989-03-27 | 1997-06-11 | 東京応化工業株式会社 | Positive photosensitive composition |
| JP2645587B2 (en) * | 1989-03-29 | 1997-08-25 | 富士写真フイルム株式会社 | Fine pattern forming material and fine pattern forming method |
| JPH02269348A (en) * | 1989-04-10 | 1990-11-02 | Sumitomo Chem Co Ltd | Photoresist composition |
| JPH0437851A (en) * | 1990-06-04 | 1992-02-07 | Mitsubishi Kasei Corp | Positive type photoresist composition |
| JP2989064B2 (en) * | 1991-12-16 | 1999-12-13 | 日本ゼオン株式会社 | Pattern forming method of metal deposition film |
| JP3510393B2 (en) | 1994-08-10 | 2004-03-29 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Flexographic printing plate obtained from a photocurable elastomer composition |
| JP2542800B2 (en) * | 1995-05-29 | 1996-10-09 | 東京応化工業株式会社 | Method of manufacturing resist pattern for semiconductor device |
| JP3506295B2 (en) | 1995-12-22 | 2004-03-15 | 富士写真フイルム株式会社 | Positive photosensitive lithographic printing plate |
| JP4553140B2 (en) | 2005-12-13 | 2010-09-29 | 信越化学工業株式会社 | Positive photoresist composition |
-
1983
- 1983-02-04 JP JP1622583A patent/JPS59142538A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59142538A (en) | 1984-08-15 |
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