JPH1184687A - Resist removing agent composition and its use method - Google Patents

Resist removing agent composition and its use method

Info

Publication number
JPH1184687A
JPH1184687A JP25282697A JP25282697A JPH1184687A JP H1184687 A JPH1184687 A JP H1184687A JP 25282697 A JP25282697 A JP 25282697A JP 25282697 A JP25282697 A JP 25282697A JP H1184687 A JPH1184687 A JP H1184687A
Authority
JP
Japan
Prior art keywords
pgme
alkylamine
water
resist
alkylammonium hydroxide
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
Application number
JP25282697A
Other languages
Japanese (ja)
Inventor
Yoshitaka Nishijima
佳孝 西嶋
Takeshi Kotani
武 小谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NAGASE DENSHI KAGAKU KK
Original Assignee
NAGASE DENSHI KAGAKU KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NAGASE DENSHI KAGAKU KK filed Critical NAGASE DENSHI KAGAKU KK
Priority to JP25282697A priority Critical patent/JPH1184687A/en
Publication of JPH1184687A publication Critical patent/JPH1184687A/en
Pending legal-status Critical Current

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  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Weting (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

PROBLEM TO BE SOLVED: To remove a residual resist with high performance which is produced in a forming process of wirings in the production of a semiconductor element circuit or the like, by using at least either alkylamine or alkylammonium hydroxide, and water and propyleneglycol monomethylether(PGME) as the main component. SOLUTION: This removing agent compsn. for a residual resist consists of at least either alkylamine or alkylammonium hydroxide, and water and PGME as the main component. The agent is prepared, for example, by adding PGME to a removing agent essentially comprising water and at least either alkylamine or alkylammonium hydroxide. The add amt. of PGME is 5.0 to 70.0 wt.%, preferably 20.0 to 70.0 wt.%. If the amt. of PGME added is less than the lower limit, the removing performance for a residual resist decreases. If the amt. exceeds the upper limit, it means decrease in the concn. of other components, and this also causes decrease in the removing performance for a residual resist.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、半導体集積回路、
液晶パネルの半導体素子回路等の製造に用いられるフォ
トレジスト剥離剤組成物及びその使用方法、詳しくは、
半導体基板上又は液晶用ガラス基板上に配線を形成する
ときに生成するレジスト残渣の除去性能を向上させるフ
ォトレジスト剥離剤組成物及びその使用方法に関するも
のである。
[0001] The present invention relates to a semiconductor integrated circuit,
Photoresist stripper composition used in the manufacture of semiconductor element circuits and the like of liquid crystal panels and methods of using the same, in detail,
The present invention relates to a photoresist stripping composition that improves the performance of removing a resist residue generated when wiring is formed on a semiconductor substrate or a glass substrate for liquid crystal, and a method for using the same.

【0002】[0002]

【従来の技術】剥離剤組成物は、半導体集積回路、液晶
パネルの半導体素子回路等の製造に用いられるフォトレ
ジストを剥離する際に用いられる。半導体素子回路又は
付随する電極部の製造は、以下のように行われる。ま
ず、シリコン、ガラス等の基板上に金属膜をCVDやス
パッタ等の方法で積層させる。その上面にフォトレジス
トを膜付けし、それを露光、現像等の処理でパターン形
成する。パターン形成されたフォトレジストをマスクと
して金属膜をエッチングする。その後、不要となったフ
ォトレジストを剥離剤組成物を用いて剥離・除去する。
その操作を繰り返すことで素子の形成が行われる。
2. Description of the Related Art A stripping composition is used for stripping a photoresist used for manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like. The manufacture of the semiconductor element circuit or the associated electrode unit is performed as follows. First, a metal film is laminated on a substrate such as silicon or glass by a method such as CVD or sputtering. A photoresist is coated on the upper surface, and a pattern is formed on the photoresist by processes such as exposure and development. The metal film is etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist is stripped and removed using a stripping composition.
The element is formed by repeating the operation.

【0003】従来、剥離剤組成物としては、有機アルカ
リ、無機アルカリ、有機酸、無機酸、極性溶剤等の単一
溶剤、これらの混合溶液、又はこれらの水溶液が用いら
れている。また、半導体素子回路等の製造工程における
配線形成時に生成するレジスト残渣を除去するために、
アルキルアミン及びアルキルアンモニウム水酸化物の少
なくともいずれかと、有機溶剤と、水とを主成分とする
レジスト剥離剤組成物も良く知られている。
Conventionally, a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, and a polar solvent, a mixed solution thereof, or an aqueous solution thereof has been used as a release agent composition. Further, in order to remove a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor element circuit or the like,
A resist stripping composition containing at least one of an alkylamine and an alkylammonium hydroxide, an organic solvent, and water is also well known.

【0004】[0004]

【発明が解決しようとする課題】現在、良く使用されて
いるモノエタノールアミン(MEA)と、極性有機溶剤
であるジメチルスルホキシド(DMSO)又はN−メチ
ルピロリドン(NMP)と、水とを主成分とするレジス
ト剥離剤組成物は、半導体素子回路等の製造工程におけ
る配線形成時に生成するレジスト残渣の除去性能が良く
ないという問題点を有している。
At present, monoethanolamine (MEA), which is often used at present, dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), which is a polar organic solvent, and water are the main components. However, such a resist stripping composition has a problem in that the resist residue formed at the time of forming a wiring in a manufacturing process of a semiconductor element circuit or the like is not effectively removed.

【0005】これらの点に鑑み、本発明者は種々の実験
を重ねた結果、MEA等のアルキルアミン又は/及びア
ルキルアンモニウム水酸化物と水とプロピレングリコー
ルモノメチルエーテル(PGME)とを主成分とするレ
ジスト剥離剤組成物が、配線形成時に生成するレジスト
残渣を高い性能で除去することを見出した。
In view of these points, the present inventors have conducted various experiments, and as a result, have found that the main components are alkylamine and / or alkylammonium hydroxide such as MEA, water and propylene glycol monomethyl ether (PGME). It has been found that the resist stripping composition removes a resist residue generated during wiring formation with high performance.

【0006】本発明は、上記の知見に基づいてなされた
もので、本発明の目的は、半導体素子回路等の製造工程
における配線形成時に生成するレジスト残渣を高性能で
除去するレジスト剥離剤組成物及びその使用方法を提供
することにある。
SUMMARY OF THE INVENTION The present invention has been made based on the above findings, and an object of the present invention is to provide a resist stripping composition for removing a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor device circuit or the like with high performance. And a method of using the same.

【0007】[0007]

【課題を解決するための手段】上記の目的を達成するた
めに、本発明のレジスト剥離剤組成物は、アルキルアミ
ン及びアルキルアンモニウム水酸化物の少なくともいず
れかと水とプロピレングリコールモノメチルエーテル
(PGME)とを主成分とするように構成されている。
本発明のレジスト剥離剤組成物は、例えば、アルキルア
ミン及びアルキルアンモニウム水酸化物の少なくともい
ずれかと水とを主成分とする剥離剤にPGMEを添加し
て調製される。しかし、調製方法はこの方法に限らず、
アルキルアミン及びアルキルアンモニウム水酸化物の少
なくともいずれか、水、及びPGME等を同時に混合し
てもよい。要は、剥離剤組成物中にPGMEが含まれる
ように調製すれば良く、添加順序は適宜選択される。
In order to achieve the above object, a resist stripping composition of the present invention comprises at least one of an alkylamine and an alkylammonium hydroxide, water, and propylene glycol monomethyl ether (PGME). Is a main component.
The resist stripping composition of the present invention is prepared, for example, by adding PGME to a stripping agent containing water and at least one of an alkylamine and an alkylammonium hydroxide. However, the preparation method is not limited to this method,
At least one of an alkylamine and an alkylammonium hydroxide, water, PGME and the like may be simultaneously mixed. The point is that the release agent composition may be prepared so as to contain PGME, and the order of addition is appropriately selected.

【0008】上記のレジスト剥離剤組成物において、プ
ロピレングリコールモノメチルエーテル(PGME)の
添加量は5.0〜70.0重量%、望ましくは、20.
0〜70.0重量%である。PGMEの添加量が下限未
満の場合は、レジスト残渣除去性能が低下するという不
都合があり、一方、上限を超える場合は、他の成分濃度
が減少するため、レジスト残渣除去性能が低下するとい
う不都合がある。
In the above resist stripping composition, the amount of propylene glycol monomethyl ether (PGME) to be added is 5.0 to 70.0% by weight, preferably 20.
0 to 70.0% by weight. If the added amount of PGME is less than the lower limit, there is a disadvantage that the resist residue removing performance is reduced. On the other hand, if the added amount is more than the upper limit, the concentration of other components is reduced, and thus the resist residue removing performance is reduced. is there.

【0009】アルキルアミンとしては、モノメチルアミ
ン、モノエチルアミン、プロピルアミン、ブチルアミ
ン、2−エチルヘキシルアミン、2−エチルヘキシルオ
キシプロピルアミン、2−エトキシプロピルアミン、ジ
メチルアミン、ジエチルアミン、ジプロピルアミン、ジ
ブチルアミン、トリメチルアミン、トリエチルアミン、
トリプロピルアミン、トリブチルアミン、3−ジエチル
アミノプロピルアミン、ジ−2−エチルヘキシルアミ
ン、ジブチルアミノプロピルアミン、テトラメチルエチ
レンジアミン、トリ−n−オクチルアミン、t−ブチル
アミン、sec−ブチルアミン、メチルアミノプロピル
アミン、ジメチルアミノプロピルアミン、メチルイミノ
ビスプロピルアミン、3−メトキシプロピルアミン、ア
リルアミン、ジアリルアミン、トリアリルアミン、イソ
プロピルアミン、ジイソプロピルアミン、イミノプロピ
ルアミン、イミノビスプロピルアミン、モノエタノール
アミン(MEA)、N,N−ジメチルエタノールアミ
ン、N,N−ジエチルエタノールアミン、アミノエチル
エタノールアミン、N−メチル−N,N−ジエタノール
アミン、N,N−ジブチルエタノールアミン、N−メチ
ルエタノールアミン、3−アミノ−1−プロパノール等
を用いることができる。
Examples of the alkylamine include monomethylamine, monoethylamine, propylamine, butylamine, 2-ethylhexylamine, 2-ethylhexyloxypropylamine, 2-ethoxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine and trimethylamine. , Triethylamine,
Tripropylamine, tributylamine, 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, tetramethylethylenediamine, tri-n-octylamine, t-butylamine, sec-butylamine, methylaminopropylamine, dimethyl Aminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, iminopropylamine, iminobispropylamine, monoethanolamine (MEA), N, N-dimethyl Ethanolamine, N, N-diethylethanolamine, aminoethylethanolamine, N-methyl-N, N-diethanolamine, N, N-dibu Ethanolamine, N- methylethanolamine, it is possible to use 3-amino-1-propanol.

【0010】また、アルキルアンモニウム水酸化物とし
ては、テトラメチルアンモニウムハイドロオキサイドや
コリン等を用いることができる。
As the alkylammonium hydroxide, tetramethylammonium hydroxide, choline or the like can be used.

【0011】本発明のレジスト剥離剤組成物の使用方法
は、半導体基板上又は液晶用ガラス基板上に配線を形成
する場合に生成するレジスト残渣を、上記の本発明のレ
ジスト剥離剤組成物を用いて剥離・除去することを特徴
としている。
The method of using the resist stripping composition of the present invention is to remove the resist residue generated when wiring is formed on a semiconductor substrate or a glass substrate for liquid crystal by using the resist stripping composition of the present invention. It is characterized in that it is peeled off and removed.

【0012】[0012]

【実施例】以下に実施例及び比較例を示し、本発明の特
徴とするところをより一層明確にする。 実施例1〜7、比較例1〜9 シリコン酸化膜上にAl−Cuをスパッタ法により膜付
けした基板を、パターニングされたレジストをマスクと
してCl2 とBCl3 を用いてドライエッチングし、続
いて酸素と水を用いてアッシングした時に配線側壁又は
上部に生成するレジスト残渣を剥離対象物とした。この
剥離対象物を下記の剥離条件で処理した。すなわち、こ
の剥離対象物を表1に示す組成に調製された剥離剤組成
物中に60℃で10分間浸漬した後、イソプロパノール
中に24℃で5分間浸漬し、さらにイソプロパノール中
に24℃で5分間浸漬し、その後、純水中に24℃で5
分間浸漬し、最後に純水をエアーガンで吹き飛ばした。
走査電子顕微鏡(SEM)にて残渣除去の程度を観察
し、残渣除去性を比較した。結果を表1に示す。表1に
おいて、◎印は「残渣なし」、○印は「ほぼ残渣な
し」、△印は「処理前より残渣は除去できているが残渣
は残っている」、×印は「処理前の残渣の状態と同じ」
を示している。
EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention. Examples 1 to 7 and Comparative Examples 1 to 9 A substrate in which Al—Cu was formed on a silicon oxide film by a sputtering method was dry-etched using Cl 2 and BCl 3 using a patterned resist as a mask. A resist residue generated on the side wall or upper part of the wiring when ashing was performed using oxygen and water was used as an object to be stripped. The object to be peeled was processed under the following peeling conditions. That is, the object to be peeled was immersed in the release agent composition prepared in the composition shown in Table 1 at 60 ° C. for 10 minutes, immersed in isopropanol at 24 ° C. for 5 minutes, and further immersed in isopropanol at 24 ° C. for 5 minutes. Immersion in pure water at 24 ° C for 5 minutes
After immersion for a minute, pure water was blown off with an air gun.
The degree of residue removal was observed with a scanning electron microscope (SEM), and the residue removal properties were compared. Table 1 shows the results. In Table 1, ◎ indicates “no residue”, ○ indicates “no residue”, Δ indicates “residue has been removed but residue remains before treatment”, and “x” indicates residue before treatment. The same as
Is shown.

【0013】[0013]

【表1】 [Table 1]

【0014】表1において、TMAHはテトラメチルア
ンモニウムハイドロオキサイドを示し、PGMEはプロ
ピレングリコールモノメチルエーテルを示し、DMSO
はジメチルスルホキシドを示し、NMPはN−メチルピ
ロリドンを示し、防食剤はアミン系の防食剤で、一例と
して、一般式化1で表わされるN,N−ビス(2−ヒド
ロキシエチル)シクロヘキシルアミンが用いられる。
In Table 1, TMAH indicates tetramethylammonium hydroxide, PGME indicates propylene glycol monomethyl ether, and DMSO
Represents dimethylsulfoxide, NMP represents N-methylpyrrolidone, and the anticorrosive is an amine anticorrosive, for example, N, N-bis (2-hydroxyethyl) cyclohexylamine represented by the general formula 1 is used. Can be

【0015】[0015]

【化1】 Embedded image

【0016】カテコール(1,2−ジヒドロキシベンゼ
ン)も防食剤として添加されている。また、ヒドロキシ
ルアミンは残渣除去性能を向上させるために添加されて
いる。表1から、PGMEを含まない剥離剤組成物(比
較例1〜5)は残渣除去性が劣るが、PGMEを含む剥
離剤組成物は、残渣除去性能が向上していることがわか
る。
Catechol (1,2-dihydroxybenzene) has also been added as an anticorrosive. In addition, hydroxylamine is added to improve the residue removal performance. From Table 1, it can be seen that the release agent compositions containing no PGME (Comparative Examples 1 to 5) have poor residue removal properties, whereas the release agent compositions containing PGME have improved residue removal performance.

【0017】つぎに、本発明の剥離剤組成物の使用方法
の一例について説明する。半導体基板上又は液晶用ガラ
ス基板上に金属薄膜をCVDやスパッタ等により形成さ
せる。その上面にフォトレジストを膜付けした後、露
光、現像等の処理でパターン形成する。パターン形成さ
れたフォトレジストをマスクとして金属薄膜をエッチン
グする。その後、不要となったフォトレジストを本発明
の剥離剤組成物を用いて剥離・除去して配線等が形成さ
れた半導体素子が製造される。
Next, an example of a method for using the release agent composition of the present invention will be described. A metal thin film is formed on a semiconductor substrate or a glass substrate for liquid crystal by CVD, sputtering, or the like. After a photoresist is applied on the upper surface, a pattern is formed by processes such as exposure and development. The metal thin film is etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist is stripped and removed using the stripping agent composition of the present invention to manufacture a semiconductor element on which wiring and the like are formed.

【0018】[0018]

【発明の効果】本発明は上記のように構成されているの
で、つぎのような効果を奏する。 (1) 剥離剤にプロピレングリコールモノメチルエー
テル(PGME)を含ませることで、半導体素子回路等
の製造工程における配線形成時に生成するレジスト残渣
を高性能で除去することができる。
As described above, the present invention has the following effects. (1) By including propylene glycol monomethyl ether (PGME) in the stripping agent, a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor element circuit or the like can be removed with high performance.

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 アルキルアミン及びアルキルアンモニウ
ム水酸化物の少なくともいずれかと水とプロピレングリ
コールモノメチルエーテルとを主成分とすることを特徴
とするレジスト剥離剤組成物。
1. A resist stripping composition comprising at least one of an alkylamine and an alkylammonium hydroxide, water and propylene glycol monomethyl ether as main components.
【請求項2】 プロピレングリコールモノメチルエーテ
ルの添加量が5.0〜70.0重量%である請求項1記
載のレジスト剥離剤組成物。
2. The resist stripping composition according to claim 1, wherein the amount of propylene glycol monomethyl ether is 5.0 to 70.0% by weight.
【請求項3】 半導体基板上又は液晶用ガラス基板上に
配線を形成する場合に生成するレジスト残渣を、請求項
1又は2記載のレジスト剥離剤組成物を用いて剥離・除
去することを特徴とするレジスト剥離剤組成物の使用方
法。
3. A resist stripping agent formed by forming a wiring on a semiconductor substrate or a liquid crystal glass substrate by using the resist stripping composition according to claim 1 or 2. To use the resist stripping composition.
JP25282697A 1997-09-02 1997-09-02 Resist removing agent composition and its use method Pending JPH1184687A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP25282697A JPH1184687A (en) 1997-09-02 1997-09-02 Resist removing agent composition and its use method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP25282697A JPH1184687A (en) 1997-09-02 1997-09-02 Resist removing agent composition and its use method

Publications (1)

Publication Number Publication Date
JPH1184687A true JPH1184687A (en) 1999-03-26

Family

ID=17242753

Family Applications (1)

Application Number Title Priority Date Filing Date
JP25282697A Pending JPH1184687A (en) 1997-09-02 1997-09-02 Resist removing agent composition and its use method

Country Status (1)

Country Link
JP (1) JPH1184687A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001356496A (en) * 2000-06-15 2001-12-26 Nagase Kasei Kogyo Kk Photoresist remover composition and method for using the same
WO2003038529A1 (en) * 2001-11-02 2003-05-08 Mitsubishi Gas Chemical Company, Inc. Method for releasing resist
US7994062B2 (en) 2009-10-30 2011-08-09 Sachem, Inc. Selective silicon etch process
US9217929B2 (en) * 2004-07-22 2015-12-22 Air Products And Chemicals, Inc. Composition for removing photoresist and/or etching residue from a substrate and use thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001356496A (en) * 2000-06-15 2001-12-26 Nagase Kasei Kogyo Kk Photoresist remover composition and method for using the same
WO2003038529A1 (en) * 2001-11-02 2003-05-08 Mitsubishi Gas Chemical Company, Inc. Method for releasing resist
CN100338530C (en) * 2001-11-02 2007-09-19 三菱瓦斯化学株式会社 Method for releasing resist
US9217929B2 (en) * 2004-07-22 2015-12-22 Air Products And Chemicals, Inc. Composition for removing photoresist and/or etching residue from a substrate and use thereof
US7994062B2 (en) 2009-10-30 2011-08-09 Sachem, Inc. Selective silicon etch process

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