JP2590890B2 - Resist removal method in chrome photolithography etching process - Google Patents
Resist removal method in chrome photolithography etching processInfo
- Publication number
- JP2590890B2 JP2590890B2 JP16517987A JP16517987A JP2590890B2 JP 2590890 B2 JP2590890 B2 JP 2590890B2 JP 16517987 A JP16517987 A JP 16517987A JP 16517987 A JP16517987 A JP 16517987A JP 2590890 B2 JP2590890 B2 JP 2590890B2
- Authority
- JP
- Japan
- Prior art keywords
- resist
- positive resist
- chrome
- reducing agent
- etching process
- 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 - Lifetime
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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
Description
【発明の詳細な説明】 産業上の利用分野 本発明はノボラック系ポジ型レジストを用いるクロー
ムフォトリソエッチングプロセスにおいて、セリウム
（IV）化合物系のエッチャント処理後のレジストの除去
方法に関する。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing a resist after a cerium (IV) compound-based etchant treatment in a chromium photolithography etching process using a novolak-based positive resist.
従来の技術及びその問題点 フォトマスク材料としてクローム膜を使用し、ノボラ
ック系ポジ型レジストを適用して、露光した後、クロー
ム膜のエッチングを行なう場合、従来エッチャント（エ
ッチング液）として硝酸セリウム第２アンモニウム〔Ce
（NH4）２（NO3）６〕の水溶液が用いられている。2. Description of the Related Art Conventional technology and its problems When a chrome film is used as a photomask material, a novolak-based positive resist is applied, and the chromium film is etched after exposure, cerium nitrate second is conventionally used as an etchant (etching solution). Ammonium (Ce
(NH 4 ) 2 (NO 3 ) 6 ].
この場合、その後のレジスト剥離の際にポジ型レジス
トの専用剥離液を使用してもレジストが完全に剥離でき
ず殘査物が基板に残りやすく、このことがデバイス製作
の歩留まり要化の大きな要因となっていた。In this case, the resist cannot be completely stripped even if a dedicated stripping solution for the positive resist is used during the subsequent stripping of the resist, and the residue tends to remain on the substrate, which is a major factor in the necessity of the device production yield. Had become.
従って、この発明の目的は前述したレジスト殘査物に
よるデバイス製作の歩留り悪化を解消し、クロームフォ
トリソエッチングプロセスにおいて完全にレジストを除
去できる方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method capable of completely removing a resist in a chrome photolithography etching process while eliminating the above-mentioned deterioration in device production yield due to resist residue.
問題点を解決するための手段 ポジ型レジストとしては、ノボラック系樹脂とナフト
キノンジアミドとの反応生成物である第４図に構造を示
すものが用いられているが、このようなノボラック系ポ
ジレストの未露光部（その構造は第４図の状態）は、最
後の工程で一般溶剤及び／またはアルカリ溶液により処
理して除去されるが、クロームのエッチャントであるセ
リウム（IV）化合物に接触すると表面が酸化され変質す
るため溶解性が極端に悪化する。Means for Solving the Problems As the positive resist, a resist having a structure shown in FIG. 4 which is a reaction product of a novolak resin and naphthoquinone diamide is used. The exposed part (the structure of which is shown in FIG. 4) is removed by treating it with a general solvent and / or an alkaline solution in the last step, but the surface is oxidized when it comes into contact with a cerium (IV) compound which is a chromium etchant. As a result, the solubility deteriorates extremely.
そこで本発明者等は （１）セリウム（IV）化合物によって酸化された構造
を、還元剤を作用させて未露光状態に戻すことによっ
て、剥離液による溶解作用を促進させ、前記の問題点を
解消し本発明を完成した。Then, the present inventors solve the above-mentioned problems by (1) promoting the dissolving action of the stripper by returning the structure oxidized by the cerium (IV) compound to a non-exposed state by the action of a reducing agent. Thus, the present invention has been completed.
すなわち、本発明は、ノボラック系ポジレジストを用
いたクローム膜の、セリウム（IV）化合物をエッチャン
トとするフォトリソエッチングプロセスにおけるレジス
ト除去方法において、未露光ポジレジスト層を剥離液で
剥離する剥離液処理工程前に、前記エッチャントにより
酸化された前記未露光ポジレジスト層を還元する還元剤
を前記未露光ポジレジスト層に作用させる工程を設けた
ことを特徴とするレジスト除去方法を提供する。That is, the present invention provides a method for removing a chromium film using a novolak-based positive resist in a photolithographic etching process using a cerium (IV) compound as an etchant, wherein a stripping solution treatment step of stripping an unexposed positive resist layer with a stripping solution. A method for removing a resist is provided, which comprises a step of causing a reducing agent, which reduces the unexposed positive resist layer oxidized by the etchant, to act on the unexposed positive resist layer.
第１図（ａ）〜（ｆ）は、還元剤を使用する本発明の
方法を適用したクロームフォトリソエッチングプロセス
の説明図である。1 (a) to 1 (f) are explanatory views of a chrome photolithography etching process to which the method of the present invention using a reducing agent is applied.
通常の方法により、基板１にレジスト膜２を設け（第
１図（ａ））、その上にポジレジスト層３を形成し（第
１図（ｂ））、露光した後その部分を溶解し（第１図
（ｃ））、露光クローム膜をセリウム（IV）化合物含有
エッチャントにより除去する（第４図（ｄ））。By a usual method, a resist film 2 is provided on a substrate 1 (FIG. 1A), a positive resist layer 3 is formed thereon (FIG. 1B), and after exposure, the portion is dissolved ( (FIG. 1 (c)), the exposed chromium film is removed by a cerium (IV) compound-containing etchant (FIG. 4 (d)).
この後剥離液処理を行ない、その溶解作用でレジスト
を除去するが、セリウム化合物系エッチャントを使用し
た場合、未露光レジスト（構造中のベンジル位等）が酸
化を受けレジスト膜の表面層が第２図に示すごとく変質
しレジスト専用剥離液に対して不溶化する。そこで本発
明ではこの不溶化したレジストに還元剤を作用させるこ
とにより変質層を再び可溶構造にして専用剥離液にて容
易に溶解するようにした。Thereafter, a stripping solution treatment is performed, and the resist is removed by its dissolving action. However, when a cerium compound-based etchant is used, the unexposed resist (benzyl position in the structure, etc.) is oxidized and the surface layer of the resist film becomes the second As shown in the figure, the substance deteriorates and becomes insoluble in a resist-dedicated stripping solution. Therefore, in the present invention, the affected layer is made to have a soluble structure again by causing a reducing agent to act on the insolubilized resist so that the resist is easily dissolved by the exclusive stripper.
還元剤の作用は、基板を還元剤含有液中に浸漬処理す
ることにより行なわれる（第１図（ｅ））。The action of the reducing agent is performed by immersing the substrate in a reducing agent-containing liquid (FIG. 1 (e)).
還元剤としては、例えば、ホルムアルデヒド、ギ酸等
の水溶液が用いられる。浸漬条件（温度、時間等）は還
元剤の種類によって異なるが、上例の還元剤の場合には
常温下３〜５分間程度で充分である。As the reducing agent, for example, an aqueous solution of formaldehyde, formic acid or the like is used. The immersion conditions (temperature, time, etc.) vary depending on the type of the reducing agent, but in the case of the above-mentioned reducing agent, about 3 to 5 minutes at room temperature is sufficient.
この浸漬処理により、変質したレジスト表面酸化層が
還元される。By this immersion treatment, the altered resist surface oxide layer is reduced.
次いで、ポジ型レジスト専用剥離液で処理するとレジ
ストが容易に溶解し、完全なレジストの剥離が行なわ
れ、レジスト殘査物のないクロームパターンが形成され
る（第１図（ｆ））。Then, when the resist is treated with a stripper for exclusive use of a positive resist, the resist is easily dissolved, the resist is completely stripped, and a chrome pattern having no resist residue is formed (FIG. 1 (f)).
なお、本発明の方法に以下の方法を併用してもよい。 The following method may be used in combination with the method of the present invention.
レジストにノボラック系ポジレジスト、エッチャント
にセリウム（IV）化合物をそれぞれ用いるクローム膜の
フォトリソエッチングプロセスにおけるレジスト除去方
法において、剥離液処理工程前に、紫外光を未露光ポジ
レジスト層に照射する工程を設けたことを特徴とするレ
ジスト除去方法である。In a method of removing a resist in a lithographic etching process of a chromium film using a novolak-based positive resist as a resist and a cerium (IV) compound as an etchant, a step of irradiating an unexposed positive resist layer with ultraviolet light is provided before the stripping solution treatment step. A resist removing method.
第３図（ａ）〜（ｅ）は紫外光を照射する本発明の方
法を適用するクロームフォトリソエッチングプロセスの
説明図である。3 (a) to 3 (e) are explanatory views of a chrome photolithography etching process to which the method of the present invention for irradiating ultraviolet light is applied.
還元剤を使用した第１図の方法と同様、常法により基
板１にクローム膜２を設け（第３図（ａ））、ポジレジ
スト層３を形成し（第３図（ｂ））、露光後その部分を
溶解してレジストのパターニングまで行なう（第３図
（ｃ））。Similar to the method of FIG. 1 using a reducing agent, a chromium film 2 is provided on a substrate 1 by a conventional method (FIG. 3A), a positive resist layer 3 is formed (FIG. 3B), and exposure is performed. Thereafter, the portion is dissolved and the patterning of the resist is performed (FIG. 3 (c)).
その後露出クローム膜をセリウム（IV）化合物含有エ
ッチャントにより除去し（第３図（ｄ））、次いでレジ
ストを剥離液により除去するのであるが、本発明による
紫外光の照射処理工程は、前記（ｃ）工程の直前及び／
または（ｄ）工程の直前の３通りの方法で実施される。Thereafter, the exposed chromium film is removed with an etchant containing a cerium (IV) compound (FIG. 3 (d)), and then the resist is removed with a stripping solution. ) Just before the process and / or
Alternatively, the method is performed by three methods immediately before the step (d).
方法１） クロームのセリウム（IV）によるウェットエ
ッチング前に、基板全面に対して紫外線光（300〜600mJ
/cm2）を照射し、未露光部レジストの感光基末端ジアジ
ドの光分解を起させる（第５図参照、第５図の構造から
Ｃ−Ｃ結合が開裂して可溶性のカルボン酸構造を生じ
る。）。その後クロームウェットエッチングを行なった
後（第３図（ｄ））、レジスト剥離液にてレジストを溶
解して完全除去する（第３図（ｅ））。Method 1) Before wet etching of chromium with cerium (IV), apply ultraviolet light (300 to 600 mJ)
/ cm 2 ) to cause photodecomposition of the photosensitive group terminal diazide of the unexposed portion of the resist (see FIG. 5, the CC bond is cleaved from the structure of FIG. 5 to produce a soluble carboxylic acid structure) .). Then, after performing chrome wet etching (FIG. 3 (d)), the resist is dissolved and completely removed with a resist stripper (FIG. 3 (e)).
方法２） クロームウェットエッチング後（第３図
（ｄ））、基板全面に対して紫外光（300〜600mJ/cm2）
を照射し、未露光部レジストの感光基を分解させ（第５
図）、その後剥離液処理してレジストを完全に除去する
（第３図（ｅ））。Method 2) After chrome wet etching (FIG. 3 (d)), ultraviolet light to the entire surface of the substrate (300~600mJ / cm 2)
To decompose the photosensitive group of the unexposed portion of the resist (No. 5
(FIG. 3) Then, the resist is completely removed by a stripping solution treatment (FIG. 3E).
方法３） クロームエッチング前（第３図（ｃ）の状
態）とエッチング後（第３図（ｄ）の状態）の計２回、
前記の１）及び２）の方法と同一条件で紫外光照射を行
ない、その後剥離液処理してレジストを完全に溶解、除
去する（第３図（ｅ））。Method 3) A total of two times before the chromium etching (the state in FIG. 3 (c)) and after the etching (the state in FIG. 3 (d))
Irradiation with ultraviolet light is performed under the same conditions as in the above methods 1) and 2), and thereafter, a resist is completely dissolved and removed by a stripping solution treatment (FIG. 3 (e)).
発明の効果 本発明は、ノボラック系ポジ型レジストを用いるクロ
ームフォトリソエッチングプロセスにおいてセリウム
（IV）系化合物でクロームをエッチングした時にレジス
トが変質し、その後レジスト除去を完全に行なえなくな
る問題を、還元剤処理を施すことによって解消したもの
である。Advantageous Effects of the Invention The present invention solves the problem that when chromium is etched with a cerium (IV) -based compound in a chrome photolithography etching process using a novolak-based positive resist, the resist deteriorates and the resist cannot be completely removed thereafter. This is solved by applying
本発明の方法を採用することによって、基板からレジ
ストが完全に除去されるのでデバイス製作の歩留りが向
上する。By employing the method of the present invention, the yield of device fabrication is improved because the resist is completely removed from the substrate.
第１図（ａ）〜（ｆ）は還元剤を使用する本発明の方法
を適用したクロームフォトリソエッチングプロセスの説
明図、 第２図はセリウム（IV）化合物系エッチャント処理によ
るポジレジスト層の状態を示す断面図、 第３図（ａ）〜（ｅ）は紫外光を照射する本発明の方法
を適用したクロームフォトリソエッチングプロセスの説
明図、 第４図はノボラック系ポジレジストの構造式、 第５図は紫外光照射した直後のノボラック系ポジレジス
トの構造式である。 図中符号： １……基板;2……クローム膜;3……ポジレジスト;4……
未露光部ポジレジスト;5……還元剤含有液;6……ポジレ
ジスト変質層。1 (a) to 1 (f) are explanatory views of a chrome photolithography etching process to which a method of the present invention using a reducing agent is applied, and FIG. 2 is a view showing a state of a positive resist layer by a cerium (IV) compound-based etchant treatment. 3 (a) to 3 (e) are explanatory views of a chrome photolithography etching process to which the method of the present invention for irradiating ultraviolet light is applied, FIG. 4 is a structural formula of a novolak-based positive resist, FIG. Is a structural formula of a novolak-based positive resist immediately after irradiation with ultraviolet light. Symbols in the figure: 1 ... substrate; 2 ... chrome film; 3 ... positive resist; 4 ...
Unexposed part positive resist; 5 ... solution containing reducing agent; 6 ... Positive resist altered layer.
Claims (3)
ム膜の、セリウム（IV）化合物をエッチャントとするフ
ォトリソエッチングプロセスにおけるレジスト除去方法
において、未露光ポジレジスト層を剥離液で剥離する剥
離液処理工程前に、前記エッチャントにより酸化された
前記未露光ポジレジスト層を還元する還元剤を前記未露
光ポジレジスト層に作用させる工程を設けたことを特徴
とするレジスト除去方法。In a method of removing a chromium film using a novolak-based positive resist in a photolithography etching process using a cerium (IV) compound as an etchant, before a stripping solution treatment step of stripping an unexposed positive resist layer with a stripping solution. A method of applying a reducing agent that reduces the unexposed positive resist layer oxidized by the etchant to the unexposed positive resist layer.
項１に記載のレジスト除去方法。2. The method according to claim 1, wherein the reducing agent comprises an organic reducing agent.
液である請求項２に記載のレジスト除去方法。3. The method according to claim 2, wherein the reducing agent is an aqueous solution of formaldehyde or formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16517987A JP2590890B2 (en) | 1987-07-03 | 1987-07-03 | Resist removal method in chrome photolithography etching process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16517987A JP2590890B2 (en) | 1987-07-03 | 1987-07-03 | Resist removal method in chrome photolithography etching process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6410248A JPS6410248A (en) | 1989-01-13 |
| JP2590890B2 true JP2590890B2 (en) | 1997-03-12 |
Family
ID=15807351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16517987A Expired - Lifetime JP2590890B2 (en) | 1987-07-03 | 1987-07-03 | Resist removal method in chrome photolithography etching process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2590890B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6326130B1 (en) * | 1993-10-07 | 2001-12-04 | Mallinckrodt Baker, Inc. | Photoresist strippers containing reducing agents to reduce metal corrosion |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5550017B2 (en) * | 1972-09-08 | 1980-12-16 | ||
| JPS52143769A (en) * | 1976-05-26 | 1977-11-30 | Hitachi Ltd | Removing method of positive type photo resist |
| JPS6054776B2 (en) * | 1977-01-10 | 1985-12-02 | 株式会社日立製作所 | Manufacturing method for semiconductor devices |
| JPS5936257B2 (en) * | 1977-07-26 | 1984-09-03 | 東京応化工業株式会社 | How to remove resist material |
| JPS54153632A (en) * | 1978-05-24 | 1979-12-04 | Nec Corp | Developing device |
| JPS5559458A (en) * | 1978-10-30 | 1980-05-02 | Chiyou Lsi Gijutsu Kenkyu Kumiai | Processing method for electron beam resist |
| JPS60151639A (en) * | 1984-01-18 | 1985-08-09 | Mitsubishi Electric Corp | Stripping-off method of photoresist |
| JPS61138952A (en) * | 1984-12-11 | 1986-06-26 | Fujitsu Ltd | Method for peeling resist film |
-
1987
- 1987-07-03 JP JP16517987A patent/JP2590890B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6410248A (en) | 1989-01-13 |
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