JPH03263048A - Method for peeling resist for photomask - Google Patents
Method for peeling resist for photomaskInfo
- Publication number
- JPH03263048A JPH03263048A JP2063259A JP6325990A JPH03263048A JP H03263048 A JPH03263048 A JP H03263048A JP 2063259 A JP2063259 A JP 2063259A JP 6325990 A JP6325990 A JP 6325990A JP H03263048 A JPH03263048 A JP H03263048A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- photomask
- film
- substrate
- irradiated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 7
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 6
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims abstract 2
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000011651 chromium Substances 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 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
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Landscapes
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔概要〕
フォトマスクの製造に関し、
クローム膜上のレジストを完全に除去することを目的と
し、
アクリル樹脂系ポジ型レジストを選択露光した後、ガラ
ス基板上のクローム膜を選択エツチングし、引き続いて
前記レジストを剥離してフォトマスクを形成する処理工
程において、該レジストに紫外線の照射を行った後にア
ルカリ溶液に浸漬し、加水分解させて除去することを特
徴としてフォトマスク用レジストの剥離方法を構成する
。[Detailed Description of the Invention] [Summary] Regarding the production of a photomask, the purpose is to completely remove the resist on the chrome film, and after selectively exposing the acrylic resin-based positive resist, the chrome film on the glass substrate is exposed. For photomasks, characterized in that in the process of selectively etching and subsequently peeling off the resist to form a photomask, the resist is irradiated with ultraviolet rays and then immersed in an alkaline solution to be hydrolyzed and removed. A resist stripping method is configured.
本発明はフォトマスク用レジストの剥離方法に関する。 The present invention relates to a method for removing a photomask resist.
半導体集積回路の製造には電子線を光源とし、被処理基
板上にフォトレジストを被覆し、選択露光を行って後に
現像してレジストパターンを作り、このレジストをマス
クとしてウェットエツチング或いはドライエツチングを
施し、被処理基板を選択エツチングして微細パターンを
形成する写真蝕刻技術（フォトリソグラフィ）が行われ
ている。In manufacturing semiconductor integrated circuits, an electron beam is used as a light source, a photoresist is coated on the substrate to be processed, selective exposure is performed, and then development is performed to create a resist pattern, and this resist is used as a mask for wet etching or dry etching. 2. Description of the Related Art Photolithography has been used to form fine patterns by selectively etching a substrate to be processed.
こ＼で、被処理基板上のフォトレジストを選択露光する
のに使用するフォトマスクについても製造方法は同様で
あって写真蝕刻技術が使用されている。The manufacturing method is the same for the photomask used to selectively expose the photoresist on the substrate to be processed, and photolithographic technology is used.
第１図はフォトマスクの製造工程の一例を示す断面図で
あって、石英ガラスからなり、厚さが約２．３１のガラ
ス基板１の上にスパッタ法を用いて、クローム（Ｃｒ）
からなる遮光膜２を６００〜１３００人の厚さに形成し
、この上にスピンコード法によりアクリル樹脂系のポジ
型のレジスト３を約５０００人の厚さに膜形成する。（
以上第１図Ａ）次に、電子線を光源として露光した後に
現像し、露光部を溶解させてレジストパターンを形成し
、遮光膜２を構成するＣｒ膜４を部分的に露出させる。FIG. 1 is a cross-sectional view showing an example of the manufacturing process of a photomask, in which chromium (Cr) is deposited on a glass substrate 1 made of quartz glass and having a thickness of about 2.3 mm using a sputtering method.
A light-shielding film 2 is formed to have a thickness of 600 to 1,300 wafers, and a positive resist 3 made of acrylic resin is formed thereon to a thickness of about 5,000 wafers by a spin code method. (
1A) Next, after exposure using an electron beam as a light source, development is performed to dissolve the exposed portion to form a resist pattern, thereby partially exposing the Cr film 4 constituting the light shielding film 2.
（以上同図Ｂ）
次に、硝酸セリウム第２アンモニウム（（ＮＨ４”ｈＣ
ｅ （Ｎｏ ｓ） ｂ ）系の水溶液に浸漬することに
よ露出部のＣｒ膜を除去する。（以上同図Ｃ）
次に、アセトンやメチルエチルケトンのような有機溶剤
によりレジスト３を溶解、除去するか、或いはドライエ
ツチング装置を用い、酸素〔０□〕プラズマに曝すこと
により、レジスト３を灰化処理（Ａｓｈｉｎｇ）するこ
とにより、レジスト３を除去しフォトマスクが形成され
ていた。（仄二同図Ｄ）然し、溶剤を用いる方法では遮
光膜２の上のレジストが完全に除去できず、そのために
撥水性を示し、フォトマスクの洗浄後にシミが生じたり
、また、灰化処理は真空チャンバ内で放電を起こして行
うため、減圧操作の際にレジストの上に“ごみ”が残り
、レジストの残渣を生じるなどの問題があった。(The above is B in the same figure) Next, ceric ammonium nitrate ((NH4”hC
The exposed portion of the Cr film is removed by immersion in an aqueous solution of e (No s) b) system. (See Figure C) Next, the resist 3 is ashed by dissolving and removing it with an organic solvent such as acetone or methyl ethyl ketone, or by exposing it to oxygen [0□] plasma using a dry etching device. By ashing, the resist 3 was removed and a photomask was formed. (D of the same figure) However, with the method using a solvent, the resist on the light shielding film 2 cannot be completely removed, and therefore it exhibits water repellency, causing stains after cleaning the photomask, and the ashing process. Because this process is performed by generating an electric discharge in a vacuum chamber, there are problems such as "dust" remaining on the resist during the depressurization operation, resulting in resist residue.
先に記したように、フォトマスクの形成において、遮光
膜上にレジストが存在すると、縮小投影露光を行う際に
、レジストが削れて“ごみ”となり、欠陥を形成するの
で、完全に除去する必要がある。As mentioned earlier, when forming a photomask, if there is resist on the light-shielding film, the resist will be scraped off and become "dust" during reduction projection exposure, creating defects, so it is necessary to completely remove it. There is.
然し、溶剤を用いて除去する場合は遮光膜との界面にレ
ジストが残って撥水性を示し、“しみ”が生じたり、ま
た、灰化法では処理中に生ずる“ごみ”のためにレジス
トの残渣を生ずると云う問題がある。However, when removing using a solvent, the resist remains at the interface with the light-shielding film and exhibits water repellency, resulting in "stains", and when using the ashing method, the resist is damaged due to "dust" generated during processing. There is a problem that a residue is produced.
そのため、フォトマスクの清浄度を向上するために激し
く洗浄処理することが必要となるが、これにより微細な
マスクパターンが剥がれ、不良品となることが問題であ
った。Therefore, in order to improve the cleanliness of the photomask, it is necessary to carry out vigorous cleaning treatment, but this causes the problem of peeling off of the fine mask pattern, resulting in a defective product.
上記の課題はアクリル樹脂系ポジ型レジストを選択露光
した後、ガラス基板上のクローム膜を選択エツチングし
、引き続いてレジストを剥離してフォトマスクを形成す
る処理工程において、このレジストに紫外線の照射を行
った後にアルカリ溶液に浸漬し、加水分解させて除去す
ることを特徴としてフォトマスク用レジストの剥離方法
を構成することにより解決することができる。The above problem was solved by selectively exposing the acrylic resin-based positive resist to light, selectively etching the chrome film on the glass substrate, and subsequently peeling off the resist to form a photomask. This can be solved by configuring a photomask resist stripping method characterized by immersing the photomask resist in an alkaline solution and removing it by hydrolysis.
本発明は写真蝕刻技術によりフォトマスクを形成した後
に残っているレジストパターンを除去する方法として、
レジストパターンが存在する基板の全面に紫外線の照射
を行って低分子量化した後にアルカリ溶液に浸漬し、加
水分解させるものである。The present invention provides a method for removing a resist pattern remaining after forming a photomask by photolithography.
The entire surface of the substrate on which the resist pattern is present is irradiated with ultraviolet rays to lower the molecular weight, and then immersed in an alkaline solution to be hydrolyzed.
すなわち、ポジ型レジストを形成するアクリル樹脂の構
造式は次の（１）式で表されるが、−（ＣＨ２−Ｃａ２
− ・・・（１）ＣＯＯＨ
但し、ＸはＣ８４基またはＣＩ基、
Ｒはアルキル基またはハロゲン化
アルキル基、
これは、紫外線照射により低分子に分解すると共に、こ
の低分子の末端基や側鎖にカルボシル基（−ＣＯＯＨ）
や水酸基（−ＯＲ）が付着して次の何れかの構造となる
。That is, the structural formula of the acrylic resin forming the positive resist is expressed by the following formula (1), and -(CH2-Ca2
- ... (1) COOH However, X is a C84 group or a CI group, R is an alkyl group or a halogenated alkyl group, This is decomposed into low molecules by ultraviolet irradiation, and the end groups and side chains of these low molecules carbosyl group (-COOH)
or a hydroxyl group (-OR) is attached to form one of the following structures.
ＯＯＲ
Ｃ０ＯＲ
次に、苛性カリ（ＫＯＨ）や苛性ソーダ（ＮａＯＨ）の
アルカリ溶液に浸漬すると、アルカリ溶液はレジスト中
に浸透すると共に次の（４）式に示すように加水分解が
進行し、アルカリ金属塩が生ずることから、基板より剥
がれ易くなる。OOR C0OR Next, when the resist is immersed in an alkaline solution of caustic potash (KOH) or caustic soda (NaOH), the alkaline solution penetrates into the resist and hydrolysis proceeds as shown in the following equation (4), and the alkali metal salt is This makes it easier to peel off from the substrate.
Ｃ０ＯＲ→ −ＣＯＯＭ ＋ ＲＯＨ・・・（４）ＯＢ
但し、ｈはアルカリ金属
次に、水洗洗浄をすることによりレジストを除去するこ
とができる。C0OR→ -COOM + ROH (4) OB However, h is an alkali metal. Next, the resist can be removed by washing with water.
大きさが５インチ角で厚さが２．３ ｍの石英からなる
ガラス基板の上にスパッタ法によりＣｒを１０００人の
厚さに形成した後、ポジ型レジスト（商品名ＥＲＲ−９
．東し■）をスピンコード法により５０００人の厚さに
塗布し、以下、先に第１図で説明したと全く同じ方法で
レジストパターンを作り、Ｃｒ膜を選択エツチングした
後、低圧水銀ランプを用いて波長が１８０〜３６０ｎｍ
の紫外線を６００秒に亙ってガラス基板の全面に亙って
照射し、レジストを低分子化した。After forming Cr to a thickness of 1,000 mm by sputtering on a quartz glass substrate measuring 5 inches square and 2.3 m thick, a positive resist (product name: ERR-9) was applied.
．． A resist pattern was formed using the spin code method to a thickness of 5,000 mm, and the Cr film was selectively etched using a low-pressure mercury lamp. The wavelength is 180 to 360 nm.
The entire surface of the glass substrate was irradiated with ultraviolet rays for 600 seconds to reduce the molecular weight of the resist.
次に、５％のＮａＯＨ水溶液に１０分間浸漬した後、水
洗洗浄をすることにより清浄度の高いフォトマスクを得
ることができた。Next, after immersing in a 5% NaOH aqueous solution for 10 minutes, a highly clean photomask could be obtained by washing with water.
なお、この実施例においては紫外線レジストを用いたフ
ォトレジストについて記したが、電子線レジスト Ｘ線
レジストなどを用いた場合でも、それぞ′れのレジスト
に吸収をもつ光或いは粒子線を照射することにより同様
な効果を得ることができる。Although this example describes a photoresist using an ultraviolet resist, even when electron beam resist, X-ray resist, etc. are used, each resist can be irradiated with absorbing light or particle beams. A similar effect can be obtained.
本発明の実施により、従来のように激しい洗浄を行うこ
となくレジストの剥離ができるので、微細なマスクパタ
ーンが剥がれると云う問題を解決することができる。By carrying out the present invention, it is possible to remove the resist without performing intensive cleaning as in the conventional method, and therefore it is possible to solve the problem of peeling off of fine mask patterns.
第１図はフォトマスクの製造工程を示す断面図である。
図において、
１はガラス基板、 ２は遮光膜、３はレジスト、
４はＣｒ膜、である。
（Ｂ）FIG. 1 is a cross-sectional view showing the manufacturing process of a photomask. In the figure, 1 is a glass substrate, 2 is a light shielding film, 3 is a resist,
4 is a Cr film. (B)
Claims (1)
ラス基板上のクローム膜を選択エッチングし、引き続い
て前記レジストを剥離してフォトマスクを形成する処理
工程において、該レジストに紫外線の照射を行った後に
アルカリ溶液に浸漬し、加水分解させて除去することを
特徴とするフォトマスク用レジストの剥離方法。After selectively exposing the acrylic resin-based positive resist to light, selectively etching the chrome film on the glass substrate, and subsequently peeling off the resist to form a photomask, after irradiating the resist with ultraviolet rays. A method for removing a resist for a photomask, characterized by immersing it in an alkaline solution and removing it by hydrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2063259A JPH03263048A (en) | 1990-03-14 | 1990-03-14 | Method for peeling resist for photomask |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2063259A JPH03263048A (en) | 1990-03-14 | 1990-03-14 | Method for peeling resist for photomask |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03263048A true JPH03263048A (en) | 1991-11-22 |
Family
ID=13224096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2063259A Pending JPH03263048A (en) | 1990-03-14 | 1990-03-14 | Method for peeling resist for photomask |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03263048A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969966A (en) * | 2014-05-15 | 2014-08-06 | 京东方科技集团股份有限公司 | Method for removing photoresist |
| JP2016075855A (en) * | 2014-10-08 | 2016-05-12 | 大日本印刷株式会社 | Production method of laminate and laminate |
| WO2019077924A1 (en) * | 2017-10-19 | 2019-04-25 | 富士フイルム株式会社 | Method for producing circuit board and method for producing touch panel |
| CN113176703A (en) * | 2021-03-26 | 2021-07-27 | 深圳市路维光电股份有限公司 | Mask stripping and photoresist removing method, manufacturing method and mask |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60151639A (en) * | 1984-01-18 | 1985-08-09 | Mitsubishi Electric Corp | Stripping-off method of photoresist |
| JPS6331591A (en) * | 1986-07-23 | 1988-02-10 | Sumitomo Heavy Ind Ltd | Treatment of photoresist waste liquid |
-
1990
- 1990-03-14 JP JP2063259A patent/JPH03263048A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60151639A (en) * | 1984-01-18 | 1985-08-09 | Mitsubishi Electric Corp | Stripping-off method of photoresist |
| JPS6331591A (en) * | 1986-07-23 | 1988-02-10 | Sumitomo Heavy Ind Ltd | Treatment of photoresist waste liquid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969966A (en) * | 2014-05-15 | 2014-08-06 | 京东方科技集团股份有限公司 | Method for removing photoresist |
| JP2016075855A (en) * | 2014-10-08 | 2016-05-12 | 大日本印刷株式会社 | Production method of laminate and laminate |
| WO2019077924A1 (en) * | 2017-10-19 | 2019-04-25 | 富士フイルム株式会社 | Method for producing circuit board and method for producing touch panel |
| JPWO2019077924A1 (en) * | 2017-10-19 | 2020-11-19 | 富士フイルム株式会社 | Circuit board manufacturing method and touch panel manufacturing method |
| CN113176703A (en) * | 2021-03-26 | 2021-07-27 | 深圳市路维光电股份有限公司 | Mask stripping and photoresist removing method, manufacturing method and mask |
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