JPS6249355A - Stripping agent composition - Google Patents
Stripping agent compositionInfo
- Publication number
- JPS6249355A JPS6249355A JP17666285A JP17666285A JPS6249355A JP S6249355 A JPS6249355 A JP S6249355A JP 17666285 A JP17666285 A JP 17666285A JP 17666285 A JP17666285 A JP 17666285A JP S6249355 A JPS6249355 A JP S6249355A
- Authority
- JP
- Japan
- Prior art keywords
- agent composition
- stripping agent
- stripping
- photoresist film
- 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.)
- Granted
Links
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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は無機性基体上に形成されたフォトレジスト膜を
剥離するための剥離剤組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a stripping agent composition for stripping a photoresist film formed on an inorganic substrate.
（従来の技術）
半導体や集積回路は、無機性基体上にフォトレジストを
塗布し、露光させ、現像して、フォトレジスト膜を形成
し、次いで、エツチングや選択的拡散等の所要の微細加
工を施した後、上記フォトレジスト膜を基体から剥離除
去することによって製造される。(Prior art) Semiconductors and integrated circuits are manufactured by coating a photoresist on an inorganic substrate, exposing it to light, developing it to form a photoresist film, and then performing necessary microfabrication such as etching and selective diffusion. After applying the photoresist film, the photoresist film is peeled off and removed from the substrate.
一般に、上記フォトレジストには、露光によって可溶化
するポジ型と、露光によって不溶化するネガ型とがあり
、ポジ型としては、例えば、代表的にはフェノール・ホ
ルムアルデヒド樹脂と光増感剤とからなるフォトレジス
トが知られており、ネガ型としては、樹脂成分としてポ
リケイ皮酸ビニルや環化ゴムを含有するフォトレジスト
が知られている。In general, the above-mentioned photoresists are classified into positive type, which becomes solubilized by exposure to light, and negative type, which becomes insolubilized by exposure. Photoresists are known, and photoresists containing polyvinyl cinnamate or cyclized rubber as a resin component are known as negative-type photoresists.
このようにポジ型及びネガ型に応じて、無機性基体上に
フォトレジスト膜を形成し、微細加工を施した後にこの
フォトレジスト膜を剥離除去するための剥離剤組成物は
、従来、一般にフェノール又はその誘導体と、塩素系有
機溶剤を含有しており、この剥離剤組成物は、フォトレ
ジスト膜の剥離性にすぐれるのみならず、金属からなる
基体に対して実質的に腐食性がないために、従来、広く
使用されている。しかし、かかる剥離剤組成物は、フェ
ノール系化合物や塩素系有機溶剤を含有するために毒性
が指摘されており、また、その廃水処理にも問題を有す
る。Conventionally, a stripping agent composition for forming a photoresist film on an inorganic substrate and peeling off the photoresist film after microfabrication has been used, depending on the positive type or negative type, generally using phenol. or its derivative, and a chlorinated organic solvent, and this stripping agent composition not only has excellent stripping properties for photoresist films, but also has virtually no corrosivity to metal substrates. Traditionally, it has been widely used. However, such stripping agent compositions have been pointed out to be toxic because they contain phenolic compounds and chlorinated organic solvents, and also have problems in wastewater treatment.
このような問題を解決するために、既に特開昭５９−４
９５３８号公報には、ジメチルアセトアミド又はジメチ
ルホルムアミド、スルホラン及びジエチレングリコール
モノアルキルエーテルからなる非フエノール系、非塩素
系の剥離剤組成物が提案されている。In order to solve such problems, we have already developed
No. 9538 proposes a non-phenolic, non-chlorine stripping agent composition comprising dimethylacetamide or dimethylformamide, sulfolane and diethylene glycol monoalkyl ether.
しかし、近年においては、フォトレジスト膜形成後の基
体の加工精度を高めるために、現像後のフォトレジスト
膜のポストベーク温度が高められ、或いはプレベーク又
はボストベーク後に遠紫外線を照射して、フォトレジス
ト膜がより高度に硬化される傾向にあり、このようなフ
ォトレジスト膜に対しては、上記剥離剤組成物の剥離速
度は尚小さい。更に、ＬＳＩ、ＶＬＳ Ｉ等のように素
子の集積度が高まるにつれて、フォトレジスト膜形成後
の基体をプラズマエツチング、リアクティブ・イオン・
エツチング（ＲＩＥ処理）、イオン注入等の加工技術に
よって、一層微細且つ高度に加工することが一般化しつ
つあるが、このような加工の場合、処理される基体の近
傍のフォトレジスト膜は高温の熱履歴を受けて変質し、
上記の剥離剤組成物を含め、従来の剥離剤組成物によれ
ば、このように熱履歴を受けたフォトレジスト膜は容易
に且つ短時間に剥離されない。However, in recent years, in order to improve the processing accuracy of the substrate after photoresist film formation, the post-bake temperature of the photoresist film after development has been increased, or the photoresist film is irradiated with deep ultraviolet rays after pre-bake or post-bake. tends to be more highly cured, and the peeling rate of the above-mentioned stripping agent composition is still low for such photoresist films. Furthermore, as the degree of integration of devices such as LSI and VLSI increases, the substrate after photoresist film formation is subjected to plasma etching, reactive ion etching, etc.
Even finer and more sophisticated processing is becoming commonplace through processing techniques such as etching (RIE processing) and ion implantation, but in such processing, the photoresist film near the substrate being processed is exposed to high temperature heat. Changes due to history,
According to conventional stripping agent compositions, including the above-mentioned stripping agent compositions, a photoresist film that has been subjected to heat history in this way is not easily and quickly peeled off.
（発明の目的）
本発明は、かかる問題を解決するためになされたもので
あって、フェノール系化合物や塩素系有機溶剤を含有せ
ず、フォトレジスト膜の剥離速度が大きく、且つ、作業
性及び安全性にすぐれ、また、基体に対しても実質的に
腐食性をもたないと共に、上記のようにより高度に硬化
されたフォトレジスト膜や、基体の微細加工によって熱
履歴を受けたフォトレジスト膜をも容易に且つ速やかに
剥離し得、更に、剥離力が長期間にわたる使用によって
も保持される剥離剤組成物を提供することを目的とする
。(Objective of the Invention) The present invention was made to solve such problems, and it does not contain phenolic compounds or chlorinated organic solvents, has a high peeling rate of photoresist films, and has excellent workability and A photoresist film that is highly safe and virtually non-corrosive to the substrate, as well as a photoresist film that has been hardened to a higher degree as described above, or a photoresist film that has undergone thermal history due to microfabrication of the substrate. It is an object of the present invention to provide a release agent composition which can be easily and quickly removed from the skin, and which maintains its release force even after long-term use.
（発明の構成）
本発明は、無機性基体上に形成されたフォトレジスト膜
を剥離するための剥離剤組成物において、（ａ） 一
般式
％式％）
（但し、ｍは２又は３の数を示し、ｎは１．２又は３の
数を示す。）
で表わされるアルカノールアミン、又は一般式１式％）
（但し、Ｘは２又は３の数を示し、ｙは２．３又は４の
数を示す。）
で表わされるポリアルキレンポリアミンのエチシンオキ
サイド付加物１０〜５０重量％、゛（ｂ）一般式
％式％
（但し、Ｒ１及びＲ２はそれぞれ独立に炭素数１又は２
のアルキル基、又は相互に結合して形成する炭素数４又
は５の環状アルキレン基を示す。）
で表わされるスルホン化合物１〜２０重量％、及び
（Ｃ） 一般式
％式％）
（但し、Ｒは炭素数１〜５のアルキル基を示し、ｐは１
．２又は３の数を示す。）
で表わされるグリコールモノアルキルエーテル３０〜８
９重量％
とからなることを特徴とする。(Structure of the Invention) The present invention provides a stripping agent composition for stripping a photoresist film formed on an inorganic substrate. (wherein, X represents a number of 2 or 3, and y represents a number of 2.3 or 4.) 10 to 50% by weight of an ethysine oxide adduct of a polyalkylene polyamine represented by the formula % formula % (however, R1 and R2 each independently have 1 or 2 carbon atoms)
represents an alkyl group, or a cyclic alkylene group having 4 or 5 carbon atoms formed by bonding with each other. 1 to 20% by weight of a sulfone compound represented by
．． Indicates the number 2 or 3. ) Glycol monoalkyl ether 30-8
9% by weight.
本発明において、無機性基体とは、二酸化ケイ素、ケイ
素、サファイア、ケイ素被膜を有するケイ素、窒化ケイ
素、ガリウムーヒ素（ヒ化ガリウム）、ガリウム−ガド
リウム−ガーネット（ＧＧＧ）、酸化クロム被膜を有す
る二酸化ケイ素、ニッケル、クロム及びアルミニウムの
ような導電性金属被膜を有するこれら無機性基体を含む
。In the present invention, inorganic substrates include silicon dioxide, silicon, sapphire, silicon with a silicon coating, silicon nitride, gallium-arsenide (gallium arsenide), gallium-gadolium-garnet (GGG), and silicon dioxide with a chromium oxide coating. , nickel, chromium, and aluminum with conductive metal coatings.
本発明による剥離剤組成物は、特にポジ型フォトレジス
ト膜の’！ＩＩ離に好適であり、かかるポジ型フォトレ
ジストとしては、例えば、重合体成分としてフェノール
・ホルムアルデヒド樹脂を含有するフォトレジストを挙
げることができる。The stripper composition according to the present invention can be used especially for positive photoresist films. Examples of such positive photoresists that are suitable for II release include photoresists containing phenol-formaldehyde resin as a polymer component.
本発明による剥離剤組成物は、−ｉ式
％式％（）
（但し、ｍは２又は３の数を示し、ｎは１．２又は３の
数を示す。）
で表わされるアルカノールアミン、又は一般式１式％）
（但し、Ｘは２又は３の数を示し、ｙは２．３又は４の
数を示す。）
で表わされるポリアルキレンポリアミンのエチレンオキ
サイド付加物をＩＩ離剤組成物に基づいて１０〜５０重
Ｍ％、好ましくは２０〜４０重量％の範囲で含有する。The stripping agent composition according to the present invention is an alkanolamine represented by the formula % (where m represents a number of 2 or 3, and n represents a number of 1.2 or 3); The ethylene oxide adduct of the polyalkylene polyamine represented by the general formula 1 (%) (wherein, X represents the number 2 or 3, and y represents the number 2.3 or 4) is added to the II release agent composition. The content is in the range of 10 to 50% by weight, preferably 20 to 40% by weight.
上記アルカノールアミンとしては、例えば、モノエタノ
ールアミン、ジェタノールアミン、トリエタノールアミ
ン、モノプロパツールアミン、ジブロバノールアミン、
トリプロパツールアミン、又はこれらの混合物が用いら
れる。また、上記ポリアルキレンポリアミンのエチレン
オキサイド付加物としては、例えば、エチレンジアミン
、ジエチレントリアミン、トリエチレンテトラミン、テ
トラエチレンペンタミン、プロピレンジアミン等のエチ
レンオキサイド付加物、又はこらの混合物が用いられる
。上記したアルカノールアミン及びポリアルキレンポリ
アミンのエチレンオキサイド付加物のなかでは、特に、
モノエタノールアミンが好ましく用いられる。Examples of the alkanolamines include monoethanolamine, jetanolamine, triethanolamine, monopropanolamine, dibrobanolamine,
Tripropaturamine or mixtures thereof are used. Further, as the ethylene oxide adduct of the polyalkylene polyamine, for example, ethylene oxide adducts such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, propylene diamine, or mixtures thereof are used. Among the above-mentioned ethylene oxide adducts of alkanolamines and polyalkylenepolyamines, in particular,
Monoethanolamine is preferably used.
本発明による剥離剤組成物は、上記アルカノールアミン
又はポリアルキレンポリアミンのエチレンオキサイド付
加物と共に、一般式
１式％
（但し、Ｒ１及びＲ２はそれぞれ独立に炭素数１又は２
のアルキル基、又は相互に結合して形成する炭素数４又
は５の環状アルキレン基を示す、）゛で表わされるスル
ホン化合物を剥離剤組成物に基づいて１〜２０重量％、
好ましくは２〜１５重量％の範囲で含有する。かかるス
ルホン化合物の具体例としては、例えば、ジメチルスル
ホン、ジエチルスルホン、スルホラン（テトラヒドロチ
オフェン−１，１−ジオキシド）等を挙げることができ
るが、特に、スルホランが好ましく用いられる。The stripping agent composition according to the present invention, together with the ethylene oxide adduct of the alkanolamine or polyalkylene polyamine, has the general formula 1% (wherein R1 and R2 each independently have 1 or 2 carbon atoms).
1 to 20% by weight of a sulfone compound represented by ), which represents an alkyl group or a cyclic alkylene group having 4 or 5 carbon atoms formed by mutual bonding, based on the release agent composition;
It is preferably contained in a range of 2 to 15% by weight. Specific examples of such sulfone compounds include dimethylsulfone, diethylsulfone, sulfolane (tetrahydrothiophene-1,1-dioxide), and sulfolane is particularly preferably used.
更に、本発明による剥離剤組成物は、一般式１式％）
（但し、Ｒは炭素数１〜５のアルキル基を示し、ｐは１
２又は３の数を示す。）
で表わされるグリコールモノアルキルエーテルを剥離剤
組成物に基づいて３０〜８９ｉｆｆｔ％、好ましくは４
５〜７８重量％の範囲で含有する。かかるグリコールモ
ノアルキルエーテルとしては、例えば、エチレングリコ
ールモノエチルエーテル、エチレングリコールモツプチ
ルエーテル、ジエチレングリコールモノメチルエーテル
、ジエチレングリコールモノエチルエーテル、ジエチレ
ングリコールモノプロピルエーテル、ジエチレングリコ
ールモノブチルエーテル等を挙げることができるが、特
に、ジエチレングリコールモノブチルエーテルが好まし
く用いられる。Furthermore, the stripping agent composition according to the present invention has the general formula 1 (%) (wherein R represents an alkyl group having 1 to 5 carbon atoms, and p is 1
Indicates the number 2 or 3. ) based on the release agent composition, preferably 4 to 89 ifft%.
The content ranges from 5 to 78% by weight. Examples of such glycol monoalkyl ethers include ethylene glycol monoethyl ether, ethylene glycol motsubutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, etc., but in particular diethylene glycol Monobutyl ether is preferably used.
本発明による特に好ましい剥離剤組成物は、モノエタノ
ールアミン約３０重量％、スルホラン約１０重量％及び
ジエチレングリコールモノブチルエーテル約６０重量％
からなる。A particularly preferred stripping composition according to the invention is about 30% by weight monoethanolamine, about 10% by weight sulfolane and about 60% by weight diethylene glycol monobutyl ether.
Consisting of
本発明による剥離剤組成物は、通常、４０〜９０℃の温
度、好ましくは６０〜８０℃の温度にて、無機性基体上
のフォトレジスト膜に接触させた後、基体を水濯ぎし、
乾燥させるのみにて、フォトレジスト膜が完全に剥離さ
れた基体を得ることができる。しかし、必要に応じて、
基体を先ずメタノール、イソプロパツール等の低級アル
コールで洗浄し、次いで、水洗してもよい。The stripping agent composition according to the present invention is usually brought into contact with a photoresist film on an inorganic substrate at a temperature of 40 to 90°C, preferably 60 to 80°C, and then the substrate is rinsed with water.
Only by drying it is possible to obtain a substrate from which the photoresist film has been completely peeled off. However, if necessary,
The substrate may be first washed with a lower alcohol such as methanol or isopropanol, and then washed with water.
（発明の効果）
以上のように、本発明による剥離剤組成物は、所定のア
ルカノールアミン又はポリアルキレンポリアミンのエチ
レンオキサイド付加物、スルホン化合物及びグリコール
モノアルキルエーテルを含有し、フェノール類及び塩素
系有機溶剤を含有していので、安全性及び作業性にすぐ
れると共に、これら各成分の相乗効果によって、フォト
レジスト膜の剥離性に著しくすぐれ、従来の無機性基体
上のフォトレジスト膜は勿論、前記したように高温にて
ポストベークされたフォトレジスト膜、遠紫外線照射に
よって高度に硬化されたフォトレジスト膜のほか、基体
のプラズマエツチング、ＲＩＥ処理、イオン注入処理等
による高度加工によって熱履歴を受けて変質したフォト
レジスト膜をも、比較的低温での処理によって速やかに
且つ容易に剥離することができる。更に、基体及び金属
のいずれに対しても実質的に腐食性を有しない。(Effects of the Invention) As described above, the stripping agent composition according to the present invention contains an ethylene oxide adduct of a predetermined alkanolamine or polyalkylene polyamine, a sulfone compound, and a glycol monoalkyl ether, and contains phenols and a chlorinated organic Since it contains a solvent, it has excellent safety and workability, and due to the synergistic effect of these components, the removability of the photoresist film is extremely excellent, and it can be used not only for conventional photoresist films on inorganic substrates but also for the above-mentioned photoresist films. In addition to photoresist films post-baked at high temperatures, photoresist films highly hardened by deep ultraviolet irradiation, and photoresist films that undergo thermal history and undergo deterioration due to advanced processing such as plasma etching, RIE processing, and ion implantation processing of the substrate. Even a photoresist film that has been formed can be quickly and easily peeled off by processing at a relatively low temperature. Furthermore, it is substantially non-corrosive to both substrates and metals.
また、本発明の剥離剤組成物によれば、フォトレジスト
膜の剥離後のリンス工程において、芳香族炭化水素やハ
ロゲン化炭化水素のような溶剤を使用する必要がなく、
廃水処理も容易である。Furthermore, according to the stripper composition of the present invention, there is no need to use a solvent such as an aromatic hydrocarbon or a halogenated hydrocarbon in the rinsing step after stripping the photoresist film.
Wastewater treatment is also easy.
（実施例）
以下に実施例を挙げて本発明による剥離剤組成物を説明
する。(Example) The release agent composition according to the present invention will be explained below by giving examples.
実施例１
水蒸気酸化により表面に二酸化ケイ素膜を形成したシリ
コンウェハー上に、表に示す市販ポジ型フォトレジスト
をスピンナーにて厚み１．５μｍに塗布し、９５℃の温
度で３０分間プレベークレ、紫外線照射し、更に、１４
０℃又は１８０℃の温度で３０分間ポストベークしてフ
ォトレジスト膜を形成した。Example 1 On a silicon wafer with a silicon dioxide film formed on its surface by steam oxidation, a commercially available positive photoresist shown in the table was applied to a thickness of 1.5 μm using a spinner, prebaked at a temperature of 95° C. for 30 minutes, and irradiated with ultraviolet rays. And furthermore, 14
A photoresist film was formed by post-baking at a temperature of 0° C. or 180° C. for 30 minutes.
次に、これらフォトレジスト膜を本発明による剥離剤組
成物１に温度７５℃にて浸漬した後、メタノールで洗浄
し、この後、水濯ぎし、赤外線照射して乾燥させた後、
基体上の残存フォトレジストの有無を基体に単色光を照
射し、又は４００〜８００倍の光学顕微鏡にて観察する
ことにより、フォトレジストの剥離速度を求めた。結果
を表に示す。Next, these photoresist films were immersed in the stripper composition 1 according to the present invention at a temperature of 75°C, washed with methanol, rinsed with water, and dried by irradiation with infrared rays.
The peeling rate of the photoresist was determined by irradiating the substrate with monochromatic light or observing it with an optical microscope at a magnification of 400 to 800 times to determine the presence or absence of residual photoresist on the substrate. The results are shown in the table.
また、比較のために、次の剥離剤組成物２〜４を調製し
、上記と同様にして、フォトレジスト膜の剥離速度を求
めた。結果を併せて表に示す。For comparison, the following stripping agent compositions 2 to 4 were prepared, and the stripping speed of the photoresist film was determined in the same manner as above. The results are also shown in the table.
剥離剤組成物１
モノエタノールアミン ３０重世％スルホ
ラン １０重量％ジエチレングリ
コールモノブチル
エーテル ６０重量％剋離剋■戊
立１
モノエタノールアミン ３０重量％ジエチレ
ングリコールモノブチル
エーテル ７０重量％凱離徂則處
脱↓
ジメチルホルムアミド ６０重量％スルホラ
ン ３０重景気ジエチレングリ
コールモノブチル
エーテル １０重量％層１」すＩν
匪土
ジメチルアセトアミド ７０重量％スルホラ
ン ２０重量％ジエチレングリコ
ールモノブチル
エーテル １０重量％また、上記
剥離剤組成物ｌの７５℃におけるアルミニウムに対する
腐食速度は１人／分以下であった。Stripping agent composition 1 Monoethanolamine 30% by weight Sulfolane 10% by weight diethylene glycol monobutyl ether 60% by weight Stripping agent composition 1 Monoethanolamine 30% by weight Diethylene glycol monobutyl ether 70% by weight Dimethyl formamide 60% by weight Sulfolane 30% by weight Diethylene glycol monobutyl ether 10% by weight Layer 1'' Iv
Dimethylacetamide 70% by weight Sulfolane 20% by weight Diethylene glycol monobutyl ether 10% by weight Further, the corrosion rate of the above stripping agent composition 1 against aluminum at 75° C. was 1 person/min or less.
実施例２
実施例工と同じシリコンウェハー上にポジ型７オトレジ
ス）ＫＰＲ８２０，０ＦＰＲ８００（東京応化工業■製
）又はＡＺ１３５０ （シップレイ社製）を塗布し、プ
レベーク及びボストベークの工程を経て、厚み約１μｍ
のフォトレジスト膜を形成し、更に、このフォトレジス
ト膜に次の処理を施した。Example 2 Positive type 7 Otoregis) KPR820, 0FPR800 (manufactured by Tokyo Ohka Kogyo ■) or AZ1350 (manufactured by Shipley) was coated on the same silicon wafer as in the example work, and through the pre-bake and post-bake steps, the thickness was approximately 1 μm.
A photoresist film was formed, and the photoresist film was further subjected to the following treatment.
処理上 イオン注入処理
イオン源ヒ素イオン、イオン密度１０１３イオン／ｃｄ
、加速エネルギー１５０ＫｅＶにてイオン注入処理した
。Processing Ion implantation processing ion source arsenic ions, ion density 1013 ions/cd
, ion implantation was performed at an acceleration energy of 150 KeV.
実理２ ＲＩＥ処理
エツチングガスとして塩素、塩化ホウ素（ＢＣｊ！、）
又はテトラフルオロメタンを用いてＲＩＥ処理後、アフ
ター・コロ−ジョン処理した。Fact 2: Chlorine and boron chloride (BCj!) as etching gases for RIE processing
Alternatively, after RIE treatment using tetrafluoromethane, after-corrosion treatment was performed.
これらのフォトレジスト膜を前記剥離剤組成物■中に７
５〜８０℃の温度で１０分間浸漬したと°ころ、フォト
レジスト膜が完全に剥離されることが確認された。These photoresist films were placed in the stripping agent composition (7).
When the photoresist film was immersed for 10 minutes at a temperature of 5 to 80°C, it was confirmed that the photoresist film was completely peeled off.
特許出願人 長瀬産業株式会社
代理人 弁理士 牧 野 逸 部
手続補装置（自発）
昭和６１年 ９月１８日
昭和６０年特許願第１７６６６２号
９、発明の名称
剥離剤組成物
３、補正をする者
事件との関係 特許出願人
住 所 大阪市西区新町１丁目１番１７号名 称 長瀬
産業株式会社
４、代理人
住 所 大阪市西区新町１丁目８番３号５、補正命令の
日付 昭和 年 月 日、（発送日 昭和 年
月 日）６、補正により増加する発明の数
７、補正の対象′代理権を証明する書面及び明細書発明
の詳細な説明の欄−一
補正の内容
（１）明細書第１４頁第６行の「プレベークレ」を「プ
レベークし」と補正する。Patent Applicant Nagase Sangyo Co., Ltd. Agent Patent Attorney Ittsu Makino Dept. Procedural Support Device (Voluntary) September 18, 1985 Patent Application No. 176662 of 1985 9 Name of invention Stripping agent composition 3 Amended Patent applicant address: 1-1-17 Shinmachi, Nishi-ku, Osaka Name: Nagase Sangyo Co., Ltd. 4 Address of agent: 1-8-3-5 Shinmachi, Nishi-ku, Osaka City Date of amendment order: Showa year Month, day, (shipment date: Showa, month, day) 6, number of inventions increased by amendment 7, subject of amendment 'Document certifying power of representation and column for detailed explanation of specified invention - 1. Contents of amendment (1) "Pre-baked" on page 14, line 6 of the specification is corrected to "pre-baked."
（２）明細書第１４頁の表を次のように補正する。(2) The table on page 14 of the specification is amended as follows.
（３）明細書第１７頁第３行の次に以下を加入する。(3) Add the following to the third line of page 17 of the specification.
記
実施例３
実施例１と同じシリコンウェハー上にポジ型フォトレジ
ストＫＰＲ８２０又は０ＦＰＲ８００を塗布し、プレベ
ーク及び１５０℃で３０分間加熱するボストベークの工
程を経て、厚み約１．５μｍのフォトレジスト膜を形成
し、更に、このフォトレジスト膜に第２表に示すように
、所定のエツチングガスを用いてｓｏｙ、ｉｏ分の条件
下でＲＩＥ処理した。Example 3 A positive photoresist KPR820 or 0FPR800 was coated on the same silicon wafer as in Example 1, and a photoresist film with a thickness of about 1.5 μm was formed through a pre-baking and post-baking process of heating at 150° C. for 30 minutes. Furthermore, this photoresist film was subjected to RIE treatment using a predetermined etching gas under soy and io conditions as shown in Table 2.
次に、これらフォトレジスト膜を本発明による前記剥離
剤組成物２若しくは３、又は０−ジクロロベンゼン、パ
ークロロエチレン、フェノール及びアルキルベンゼンス
ルホン酸を主成分とする従来より知られている剥離剤Ｊ
−１００（長瀬産業■製）中に所定時間浸漬した後、所
定の後処理を施し、乾燥させた。この後、実施例１と同
様にして基体上のフォトレジスト膜の残存厚さを測定し
て、フォトレジスト膜の剥離速度を調べた。剥離１１Ｍ
１成物中への浸漬温度は、本発明による剥離剤 ′Ｉ成
物の場合は８５℃、Ｊ−１００の場合は１１０℃とした
。結果を第２表に示す。Next, these photoresist films are coated with the stripping agent composition 2 or 3 according to the present invention, or the conventional stripping agent J containing 0-dichlorobenzene, perchloroethylene, phenol, and alkylbenzene sulfonic acid as main components.
-100 (manufactured by Nagase Sangyo ■) for a predetermined period of time, and then subjected to a predetermined post-treatment and dried. Thereafter, the remaining thickness of the photoresist film on the substrate was measured in the same manner as in Example 1, and the peeling rate of the photoresist film was examined. Peeling 11M
The immersion temperature in the product J-100 was 85°C in the case of the release agent 'I product according to the invention and 110°C in the case of J-100. The results are shown in Table 2.
尚、上記後処理は、本発明による剥離剤組成物を用いた
場合は、常温にて超純水でリンスした後、赤外線にて加
熱乾燥させ、Ｊ−１００を用いた場合は、トリクレン中
で煮沸した後、常温でイソプロピルアルコール、次いで
超純水でリンスした後、赤外線にて加熱乾燥させた。The above post-treatment is performed by rinsing with ultrapure water at room temperature and then heating and drying with infrared rays when using the stripping agent composition according to the present invention, and by drying in trichlene when using J-100. After boiling, it was rinsed with isopropyl alcohol and then with ultrapure water at room temperature, and then dried by heating with infrared rays.
Claims (4)
離するための剥離剤組成物において、 （ａ）一般式 Ｈ＿３＿−＿ｎＮ（（ＣＨ＿２）＿ｍＯＨ）＿ｎ（但し
、ｍは２又は３の数を示し、ｎは１、２又は３の数を示
す。） で表わされるアルカノールアミン、又は一般式Ｈ＿２Ｎ
（（ＣＨ＿２）＿ｘＮＨ）＿ｙＨ （但し、ｘは２又は３の数を示し、ｙは２、３又は４の
数を示す。） で表わされるポリアルキレンポリアミンのエチレンオキ
サイド付加物１０〜５０重量％、 （ｂ）一般式 Ｒ＾１−ＳＯ＿２−Ｒ＾２ （但し、Ｒ＾１及びＲ＾２はそれぞれ独立に炭素数１又
は２のアルキル基、又は相互に結合して形成する炭素数
４又は５の環状アルキレン基を示す。） で表わされるスルホン化合物１〜２０重量％、及び （ｃ）一般式 ＨＯ−（Ｃ＿２Ｈ＿４Ｏ）＿ｐ−Ｒ （但し、Ｒは炭素数１〜５のアルキル基を示し、ｐは１
、２又は３の数を示す。） で表わされるグリコールモノアルキルエーテル３０〜８
９重量％ とからなる剥離剤組成物。(1) In a stripping agent composition for stripping a photoresist film formed on an inorganic substrate, (a) General formula H_3_-_nN((CH_2)_mOH)_n (where m is a number of 2 or 3) and n represents the number 1, 2 or 3), or an alkanolamine represented by the general formula H_2N
((CH_2)_xNH)_yH (where x represents a number of 2 or 3, and y represents a number of 2, 3 or 4) 10 to 50% by weight of an ethylene oxide adduct of a polyalkylene polyamine, (b) General formula R^1-SO_2-R^2 (However, R^1 and R^2 are each independently an alkyl group having 1 or 2 carbon atoms, or an alkyl group having 4 or 5 carbon atoms bonded to each other. 1 to 20% by weight of a sulfone compound represented by is 1
, indicates the number 2 or 3. ) Glycol monoalkyl ether 30-8
A release agent composition consisting of 9% by weight.
トリエタノールアミンであることを特徴とする特許請求
の範囲第１項記載の剥離剤組成物。(2) The stripping agent composition according to claim 1, wherein the alkanolamine compound is mono-, di-, and/or triethanolamine.
ンであることを特徴とする特許請求の範囲第１項記載の
剥離剤組成物。(3) The stripping agent composition according to claim 1, wherein the sulfone compound is dimethylsulfone or sulfolane.
リコールモノブチルエーテルであることを特徴とする特
許請求の範囲第１項記載の剥離剤組成物。(4) The stripping agent composition according to claim 1, wherein the glycol monoalkyl ether is diethylene glycol monobutyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60176662A JPH0612455B2 (en) | 1985-08-10 | 1985-08-10 | Release agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60176662A JPH0612455B2 (en) | 1985-08-10 | 1985-08-10 | Release agent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6249355A true JPS6249355A (en) | 1987-03-04 |
| JPH0612455B2 JPH0612455B2 (en) | 1994-02-16 |
Family
ID=16017506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60176662A Expired - Fee Related JPH0612455B2 (en) | 1985-08-10 | 1985-08-10 | Release agent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0612455B2 (en) |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0267540A2 (en) * | 1986-11-10 | 1988-05-18 | J.T. Baker Inc. | Stripping compositions and their use for stripping resists from substrates |
| EP0301756A2 (en) * | 1987-07-30 | 1989-02-01 | Ekc Technology, Inc. | Triamine positive photoresist stripping composition and prebaking process |
| JPS6442653A (en) * | 1987-08-10 | 1989-02-14 | Tokyo Ohka Kogyo Co Ltd | Peeling solution for positive type photoresist |
| JPS6481949A (en) * | 1987-09-25 | 1989-03-28 | Asahi Chemical Ind | Agent for peeling photoresist |
| JPS6481950A (en) * | 1987-09-25 | 1989-03-28 | Asahi Chemical Ind | Agent for peeling photoresist |
| JPS6488548A (en) * | 1987-09-30 | 1989-04-03 | Nagase Denshi Kagaku Kk | Toner composition |
| JPH04289866A (en) * | 1990-11-05 | 1992-10-14 | Ekc Technol Inc | Composition and method for removing anti-corrosive membrane from supporting body |
| JPH06266119A (en) * | 1992-07-09 | 1994-09-22 | Ekc Technol Inc | Cleaning agent containing nucleophilic amine compound provided with reduction and oxidation potential |
| EP0723205A1 (en) * | 1995-01-10 | 1996-07-24 | Mitsubishi Gas Chemical Company, Inc. | Removing agent composition and method of removing photoresist using the same |
| US5633175A (en) * | 1991-12-19 | 1997-05-27 | Hitachi, Ltd. | Process for stripping photoresist while producing liquid crystal display device |
| US5911835A (en) * | 1990-11-05 | 1999-06-15 | Ekc Technology, Inc. | Method of removing etching residue |
| US6000411A (en) * | 1990-11-05 | 1999-12-14 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue and method of using |
| EP1035446A2 (en) | 1999-03-08 | 2000-09-13 | Mitsubishi Gas Chemical Company, Inc. | Resist stripping composition and process for stripping resist |
| US6140027A (en) * | 1998-12-31 | 2000-10-31 | Dongjin Semichem Co., Ltd. | Photoresist remover composition |
| US6218087B1 (en) | 1999-06-07 | 2001-04-17 | Tokyo Ohka Kogyo Co., Ltd. | Photoresist stripping liquid composition and a method of stripping photoresists using the same |
| US6242400B1 (en) | 1990-11-05 | 2001-06-05 | Ekc Technology, Inc. | Method of stripping resists from substrates using hydroxylamine and alkanolamine |
| US6399551B1 (en) | 1993-06-21 | 2002-06-04 | Ekc Technology, Inc. | Alkanolamine semiconductor process residue removal process |
| US6458517B2 (en) | 1999-03-31 | 2002-10-01 | Sharp Kabushiki Kaisha | Photoresist stripping composition and process for stripping photoresist |
| WO2002095502A1 (en) * | 2001-05-21 | 2002-11-28 | Dongjin Semichem Co., Ltd. | Resist remover composition |
| WO2002095501A1 (en) * | 2001-05-21 | 2002-11-28 | Dongjin Semichem Co., Ltd. | Resist remover composition |
| US6638694B2 (en) | 1999-02-25 | 2003-10-28 | Mitsubishi Gas Chemical Company, Inc | Resist stripping agent and process of producing semiconductor devices using the same |
| US6656895B2 (en) | 2000-12-27 | 2003-12-02 | Sumitomo Chemical Company, Limited | Remover composition |
| US6686322B1 (en) | 1998-11-12 | 2004-02-03 | Sharp Kabushiki Kaisha | Cleaning agent and cleaning process using the same |
| SG114566A1 (en) * | 2001-09-28 | 2005-09-28 | Mitsubishi Gas Chemical Co | Liquid composition for removing a photoresist |
| US7105474B2 (en) | 2002-08-23 | 2006-09-12 | Samsung Electronics Co., Ltd. | Organic stripping composition and method of etching oxide using the same |
| WO2007063767A1 (en) | 2005-12-01 | 2007-06-07 | Mitsubishi Gas Chemical Company, Inc. | Cleaning solution for semiconductor device or display device, and cleaning method |
| US7888300B2 (en) | 2008-03-19 | 2011-02-15 | Fujifilm Corporation | Cleaning liquid for semiconductor device and cleaning method |
| JP2012018982A (en) * | 2010-07-06 | 2012-01-26 | Tosoh Corp | Resist stripping agent and stripping method using the same |
| CN104635438A (en) * | 2013-11-12 | 2015-05-20 | 安集微电子科技(上海)有限公司 | Photoresist stripping liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5635424A (en) * | 1980-08-13 | 1981-04-08 | Toshiba Corp | Manufacture of semiconductor device |
| JPS5784456A (en) * | 1980-09-15 | 1982-05-26 | Shipley Co | Stripping composition and use thereof |
| JPS6026945A (en) * | 1983-07-25 | 1985-02-09 | ジエイ・テイ・ベ−カ−・ケミカル・カンパニ− | Stripping composition and stripping of resist |
-
1985
- 1985-08-10 JP JP60176662A patent/JPH0612455B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5635424A (en) * | 1980-08-13 | 1981-04-08 | Toshiba Corp | Manufacture of semiconductor device |
| JPS5784456A (en) * | 1980-09-15 | 1982-05-26 | Shipley Co | Stripping composition and use thereof |
| JPS6026945A (en) * | 1983-07-25 | 1985-02-09 | ジエイ・テイ・ベ−カ−・ケミカル・カンパニ− | Stripping composition and stripping of resist |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0267540A2 (en) * | 1986-11-10 | 1988-05-18 | J.T. Baker Inc. | Stripping compositions and their use for stripping resists from substrates |
| EP0301756A2 (en) * | 1987-07-30 | 1989-02-01 | Ekc Technology, Inc. | Triamine positive photoresist stripping composition and prebaking process |
| JPH01105949A (en) * | 1987-07-30 | 1989-04-24 | Ekc Technol Inc | Triamine positive photoresist tripping composition and prebaking |
| JPS6442653A (en) * | 1987-08-10 | 1989-02-14 | Tokyo Ohka Kogyo Co Ltd | Peeling solution for positive type photoresist |
| JPS6481949A (en) * | 1987-09-25 | 1989-03-28 | Asahi Chemical Ind | Agent for peeling photoresist |
| JPS6481950A (en) * | 1987-09-25 | 1989-03-28 | Asahi Chemical Ind | Agent for peeling photoresist |
| JPS6488548A (en) * | 1987-09-30 | 1989-04-03 | Nagase Denshi Kagaku Kk | Toner composition |
| US6110881A (en) * | 1990-11-05 | 2000-08-29 | Ekc Technology, Inc. | Cleaning solutions including nucleophilic amine compound having reduction and oxidation potentials |
| JPH04289866A (en) * | 1990-11-05 | 1992-10-14 | Ekc Technol Inc | Composition and method for removing anti-corrosive membrane from supporting body |
| US5672577A (en) * | 1990-11-05 | 1997-09-30 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue with hydroxylamine, alkanolamine, and chelating agent |
| US5902780A (en) * | 1990-11-05 | 1999-05-11 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue and method of using |
| US5911835A (en) * | 1990-11-05 | 1999-06-15 | Ekc Technology, Inc. | Method of removing etching residue |
| US6000411A (en) * | 1990-11-05 | 1999-12-14 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue and method of using |
| US6242400B1 (en) | 1990-11-05 | 2001-06-05 | Ekc Technology, Inc. | Method of stripping resists from substrates using hydroxylamine and alkanolamine |
| US6564812B2 (en) | 1990-11-05 | 2003-05-20 | Ekc Technology, Inc. | Alkanolamine semiconductor process residue removal composition and process |
| US6140287A (en) * | 1990-11-05 | 2000-10-31 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue and method of using |
| US6319885B1 (en) | 1990-11-05 | 2001-11-20 | Ekc Technologies, Inc. | Cleaning solutions including nucleophilic amine compound having reduction and oxidation potentials |
| US5633175A (en) * | 1991-12-19 | 1997-05-27 | Hitachi, Ltd. | Process for stripping photoresist while producing liquid crystal display device |
| JPH06266119A (en) * | 1992-07-09 | 1994-09-22 | Ekc Technol Inc | Cleaning agent containing nucleophilic amine compound provided with reduction and oxidation potential |
| US6399551B1 (en) | 1993-06-21 | 2002-06-04 | Ekc Technology, Inc. | Alkanolamine semiconductor process residue removal process |
| EP0723205A1 (en) * | 1995-01-10 | 1996-07-24 | Mitsubishi Gas Chemical Company, Inc. | Removing agent composition and method of removing photoresist using the same |
| US6686322B1 (en) | 1998-11-12 | 2004-02-03 | Sharp Kabushiki Kaisha | Cleaning agent and cleaning process using the same |
| US6140027A (en) * | 1998-12-31 | 2000-10-31 | Dongjin Semichem Co., Ltd. | Photoresist remover composition |
| US6638694B2 (en) | 1999-02-25 | 2003-10-28 | Mitsubishi Gas Chemical Company, Inc | Resist stripping agent and process of producing semiconductor devices using the same |
| US6323169B1 (en) | 1999-03-08 | 2001-11-27 | Mitsubishi Gas Chemical Company, Inc. | Resist stripping composition and process for stripping resist |
| EP1035446A2 (en) | 1999-03-08 | 2000-09-13 | Mitsubishi Gas Chemical Company, Inc. | Resist stripping composition and process for stripping resist |
| US6458517B2 (en) | 1999-03-31 | 2002-10-01 | Sharp Kabushiki Kaisha | Photoresist stripping composition and process for stripping photoresist |
| US6218087B1 (en) | 1999-06-07 | 2001-04-17 | Tokyo Ohka Kogyo Co., Ltd. | Photoresist stripping liquid composition and a method of stripping photoresists using the same |
| US6656895B2 (en) | 2000-12-27 | 2003-12-02 | Sumitomo Chemical Company, Limited | Remover composition |
| WO2002095502A1 (en) * | 2001-05-21 | 2002-11-28 | Dongjin Semichem Co., Ltd. | Resist remover composition |
| WO2002095501A1 (en) * | 2001-05-21 | 2002-11-28 | Dongjin Semichem Co., Ltd. | Resist remover composition |
| SG114566A1 (en) * | 2001-09-28 | 2005-09-28 | Mitsubishi Gas Chemical Co | Liquid composition for removing a photoresist |
| US7105474B2 (en) | 2002-08-23 | 2006-09-12 | Samsung Electronics Co., Ltd. | Organic stripping composition and method of etching oxide using the same |
| WO2007063767A1 (en) | 2005-12-01 | 2007-06-07 | Mitsubishi Gas Chemical Company, Inc. | Cleaning solution for semiconductor device or display device, and cleaning method |
| US7998914B2 (en) | 2005-12-01 | 2011-08-16 | Mitsubishi Gas Chemical Company, Inc. | Cleaning solution for semiconductor device or display device, and cleaning method |
| US7888300B2 (en) | 2008-03-19 | 2011-02-15 | Fujifilm Corporation | Cleaning liquid for semiconductor device and cleaning method |
| JP2012018982A (en) * | 2010-07-06 | 2012-01-26 | Tosoh Corp | Resist stripping agent and stripping method using the same |
| CN104635438A (en) * | 2013-11-12 | 2015-05-20 | 安集微电子科技(上海)有限公司 | Photoresist stripping liquid |
| CN104635438B (en) * | 2013-11-12 | 2020-06-09 | 安集微电子科技（上海）股份有限公司 | Photoresist stripping liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0612455B2 (en) | 1994-02-16 |
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