JPS6088946A - Chromium mask washing method - Google Patents
Chromium mask washing methodInfo
- Publication number
- JPS6088946A JPS6088946A JP58197345A JP19734583A JPS6088946A JP S6088946 A JPS6088946 A JP S6088946A JP 58197345 A JP58197345 A JP 58197345A JP 19734583 A JP19734583 A JP 19734583A JP S6088946 A JPS6088946 A JP S6088946A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- film
- mask
- sulfuric acid
- oxide
- 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
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
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、半導体素子、IC,LSI等の半導体製造に
使用されるクロムマスクの洗浄方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for cleaning a chrome mask used in the manufacture of semiconductors such as semiconductor elements, ICs, and LSIs.
ここで、クロムマスクとは、ガラス基板上にクロム膜を
被覆したブランクや、前記クロム股上に酸化クロム膜を
積層したブランクや、前記ガラス基板と前記クロム膜の
間に酸化インジウム又は酸化スズ等の透明導電膜を介在
したブランク等を素材にして、前記クロム膜、又はこれ
ど前記酸化クロム膜を所定形状にパターン化したもので
あり、代表例どしては、クロム膜をパターン成形したク
ロムマスクが挙げられる。Here, the chrome mask refers to a blank in which a chromium film is coated on a glass substrate, a blank in which a chromium oxide film is laminated on the chrome crotch, or a blank in which indium oxide, tin oxide, etc. is deposited between the glass substrate and the chromium film. The chromium film or the chromium oxide film is patterned into a predetermined shape using a blank or the like with a transparent conductive film interposed therebetween.A typical example is a chrome mask in which a chromium film is patterned. can be mentioned.
このクロムマスクは、半導体素子等の製造工程中におい
て、ゴミが付着することがしばしば起こる。Dust often adheres to this chrome mask during the manufacturing process of semiconductor devices and the like.
従来、このような11着物の洗浄方法としでは、クロム
マスクを硫酸に浸漬する方法が提案されている。Conventionally, as a method for cleaning such kimonos, a method has been proposed in which a chrome mask is immersed in sulfuric acid.
この提案によれば、クロム13!の表面は空気中の酸素
にJ:って酸化されて、常に数rim程度の酸化クロム
層に覆われているため、そのままではクロムマスクを硫
酸中に浸漬しても、クロム族は溶出せずに、11着物を
洗浄することは可OLであるが、ゴミとしてアルミニウ
ム等の金属小片が混在()てクロム膜表面の酸化クロム
層上に付着した場合、次のような作用を起こして、クロ
ム膜が硫酸中で溶出する。1なわち、アルミニウム等の
金属小片は、その一部が硫酸中において陽イオンどなっ
て溶けると共に、その金属小片に残る電子か、金属小片
下の酸化クロム層中に移動j;ム敗していく。これは、
クロム膜表面上の酸化クロム層に電子が与えられた、換
言すれば、酸化クロム層が還元されたことになる。そし
て、表面の酸化クロム層が還元されて金属クロムとなり
、この金属クロムは硫酸に可溶であることから、結局、
金属クロムとなった酸化クロム層は硫酸中に溶出すると
共に、その下のクロム膜も溶出することになり、ついに
はクロム膜が欠落することになる。このようにクロム膜
の欠落したクロムマスクは、パターンに断線を引き起こ
したり、島状のクロム膜が無くなることから、半導体素
子等の製造に供することができなくなる。According to this proposal, Chrome 13! The surface of the mask is oxidized by oxygen in the air and is always covered with a layer of chromium oxide of several rims, so even if the chrome mask is immersed in sulfuric acid, the chromium group will not be eluted. 11 It is possible to wash the kimono, but if small pieces of metal such as aluminum are mixed in as dust and adhere to the chromium oxide layer on the surface of the chromium film, the following effects will occur and the chromium will be washed away. The membrane is eluted in sulfuric acid. 1. In other words, a part of a small piece of metal such as aluminum dissolves into cations in sulfuric acid, and the electrons remaining in the metal piece move into the chromium oxide layer beneath the metal piece. go. this is,
Electrons were given to the chromium oxide layer on the surface of the chromium film, in other words, the chromium oxide layer was reduced. Then, the chromium oxide layer on the surface is reduced to metallic chromium, and since this metallic chromium is soluble in sulfuric acid, eventually
The chromium oxide layer, which has become metallic chromium, is eluted into the sulfuric acid, and the chromium film underneath it is also eluted, resulting in the chromium film being missing. A chromium mask with a missing chromium film in this manner cannot be used for manufacturing semiconductor devices or the like because it causes disconnection in the pattern or the island-like chromium film is missing.
本発明の目的は、上述したような欠点を除去し、クロム
膜の欠落の生じないフォトマスクの洗浄方法を提供する
ことである。An object of the present invention is to provide a photomask cleaning method that eliminates the above-mentioned drawbacks and does not cause chipping of the chromium film.
このような目的を達成するため、本発明者は、前述した
ようにクロム膜の欠落原因がクロム膜表面の酸化クロム
層を還元して金属クロムとなることに着目して、洗浄液
に酸化作用が持続する限り、酸化クロム層が還元されて
金属クロムになっても、すぐに酸化されて、再びクロム
膜表面が酸化クロム層に覆われ、クロム膜が洗浄液中に
溶出することのない現象を見い出し、本発明を完成する
に至った。本発明の要点は、硫酸に酸化剤を加えること
により、洗浄液に酸化作用を持続させたことにある。In order to achieve such an objective, the present inventor focused on the fact that the cause of chromium film loss is the reduction of the chromium oxide layer on the surface of the chromium film to become metallic chromium, as described above, and developed a cleaning solution that has an oxidizing effect. We discovered that as long as the chromium oxide layer is reduced to metallic chromium, it is immediately oxidized and the surface of the chromium film is covered with a chromium oxide layer again, so that the chromium film will not be eluted into the cleaning solution. , we have completed the present invention. The gist of the present invention is that by adding an oxidizing agent to sulfuric acid, the oxidizing effect is sustained in the cleaning liquid.
以下、本発明を図面を参照して説明づ−る。The present invention will be explained below with reference to the drawings.
アルミニウム等の金属小片がクロム膜表面の酸化クロム
層上に付着して硫酸溶液中にクロムマスクを浸漬したと
き、金属小片の一部が陽イオンとなって溶解した後に残
る電子が酸化クロム層に移動する現象は、硫酸溶液中に
2つの電極を置き、一方の電極に酸化クロム層で覆われ
たクロム膜を用いて、これに負電圧を印加することと同
一である。この知見に基づいて、本発明を第1図に示す
実験装置について説明する。同図において、恒温槽1は
電解槽3内の液温を約50℃に保持する水2が収容され
、この電解槽3内には、酸化剤として硝酸を加えた硫酸
硝酸混液4を収容して、この混液4中にクロムマスク5
を浸漬づる。このクロムマスク5は、周知のとおり、ガ
ラス基板6上にクロムl!7を所定形状にパターン化し
たもので、クロム膜7の表面には、空気中の酸素により
酸化クロム層8が被覆されている。そして、前述した酸
化クロム層8を陰極板とし、対向する銅板9を陽極板と
してそれぞれ直流電源10が接続されている。When small pieces of metal such as aluminum adhere to the chromium oxide layer on the surface of the chromium film and the chrome mask is immersed in a sulfuric acid solution, some of the metal pieces become cations and dissolve, and the remaining electrons are transferred to the chromium oxide layer. The phenomenon of movement is the same as placing two electrodes in a sulfuric acid solution, using a chromium film covered with a chromium oxide layer as one electrode, and applying a negative voltage to this electrode. Based on this knowledge, the present invention will be explained using an experimental apparatus shown in FIG. In the figure, a constant temperature bath 1 contains water 2 that maintains the temperature of the liquid in an electrolytic cell 3 at approximately 50°C, and a sulfuric acid/nitric acid mixture 4 containing nitric acid as an oxidizing agent is contained in the electrolytic cell 3. Then, add chrome mask 5 to this mixture 4.
Soak the vine. As is well known, this chrome mask 5 is made of chrome l! on a glass substrate 6. 7 is patterned into a predetermined shape, and the surface of the chromium film 7 is coated with a chromium oxide layer 8 by oxygen in the air. A DC power source 10 is connected to the chromium oxide layer 8 described above as a cathode plate and the opposing copper plate 9 as an anode plate.
そこで、混液4の硫酸と硝酸の各モル%をパラメータと
して、両電極間の印加電圧をOボルトカ1ら徐々に増大
しながら、クロム膜7の溶出開始電圧を測定した。その
結果を第1表に示す。Therefore, the elution start voltage of the chromium film 7 was measured while gradually increasing the voltage applied between the two electrodes from 1 O volt using each mole % of sulfuric acid and nitric acid in the mixed liquid 4 as parameters. The results are shown in Table 1.
第1表
この結果は、混液4に占める硝酸の比率が増大するに従
って、この混液4による酸化作用、が強くなり、クロム
膜7の表面の酸化クロム層8が還元されにくくなること
を示している。Table 1 The results show that as the proportion of nitric acid in the mixed liquid 4 increases, the oxidizing effect of this mixed liquid 4 becomes stronger, and the chromium oxide layer 8 on the surface of the chromium film 7 becomes less likely to be reduced. .
次に、2μm匹方0クロム膜7のパターン100個を形
成したクロムマスク5を用意して、このクロムマスク5
上にアルミニウム微粉を一様にふりかけたものを、硝酸
のモル%をパラメータにした硫酸硝酸混液4(液温:5
0℃)に浸漬して、クロム!l*7のパターンが何個欠
落するかを観測した。Next, prepare a chrome mask 5 on which 100 patterns of 2 μm 0 chromium film 7 are formed, and this chrome mask 5
A mixture of sulfuric acid and nitric acid with the mol% of nitric acid as a parameter (liquid temperature: 5
0℃) and chromium! We observed how many l*7 patterns were missing.
その結果を第2表に示す。The results are shown in Table 2.
この結果から、ごく少量の硝酸が含まれていても、クロ
ム膜7の欠落を防止することができ、5モル%以上の硝
酸を含む硫酸硝酸混液4にクロムマスク5を浸漬して洗
浄すれば、クロムIf! 7の欠落は生じないことが判
明した。From this result, even if a very small amount of nitric acid is contained, the chromium film 7 can be prevented from being chipped, and if the chromium mask 5 is cleaned by immersing it in a sulfuric acid/nitric acid mixture 4 containing 5 mol% or more of nitric acid. , Chrome If! It was found that the omission of 7 did not occur.
更に、5モル%以上の硝酸を含む硫酸硝酸混液について
、酸化作用の効力を持続する条件を調べた結果、1時間
に1.5モル%の割合で洗浄液に硝酸を追加すれば良い
ことが判明した。Furthermore, as a result of investigating the conditions for sustaining the oxidizing effect of a sulfuric acid/nitric acid mixture containing 5 mol% or more of nitric acid, it was found that nitric acid should be added to the cleaning solution at a rate of 1.5 mol% per hour. did.
また、硝酸を加えたことによるクロムマスクの特性の変
化については、光学濃度、表面反射率、膜厚及びパター
ン線幅のいずれも通常の洗浄時間(約10分〉では変化
しなかった。Regarding the changes in the properties of the chrome mask due to the addition of nitric acid, none of the optical density, surface reflectance, film thickness, and pattern line width changed during normal cleaning time (approximately 10 minutes).
以上のとおり、本発明によれば、硝酸をごく少量含む、
好ましくは5モル%以上含む硫酸硝酸混液を使用すれば
、クロムマスクの諸特性を何ら変えることなく、クロム
膜の欠落の生じない洗浄ができる。As described above, according to the present invention, the
If a sulfuric acid/nitric acid mixture containing preferably 5 mol % or more is used, cleaning can be performed without causing any loss of the chromium film without changing the properties of the chromium mask.
なお、上記実施例では酸化剤として硝酸を使用したが、
本発明はこれに限定されず、過酸化水素水、過マンカン
酸、硝酸カリウム又はオゾン等を酸化剤として使用して
も、上記実施例と同様な効果を奏する。また、クロムマ
スクとして実施例で挙げたクロム膜のみの狭義のクロム
マスクの他に、クロム膜上に酸化クロムを積層したもの
やくこの場合、クロム膜の膜厚端面の欠落を防止する。In addition, in the above example, nitric acid was used as the oxidizing agent, but
The present invention is not limited thereto, and even if hydrogen peroxide, permancanic acid, potassium nitrate, ozone, or the like is used as the oxidizing agent, the same effects as in the above embodiments can be obtained. Further, in addition to the chromium mask in the narrow sense of only a chromium film mentioned in the embodiment, a chromium mask in which chromium oxide is laminated on a chromium film is used to prevent chipping of the thick end face of the chromium film.
〉、ガラス基板とクロム膜の間に透明導電llシ)を介
在したものに対しても、上記実施例と同様な効果を秦す
ることから、本発明のクロムマスクは、遮光性マスクと
してクロム膜を形成したしのであれば、どのような形態
のものであってもよい。〉The same effect as in the above embodiment can be obtained even when a transparent conductive film is interposed between the glass substrate and the chromium film. Therefore, the chromium mask of the present invention uses a chromium film as a light-shielding mask. It may take any form as long as it is formed.
第1図は本発明を説明するための実験装置を示す概略図
である。
1・・・恒温槽、2・・・水、3・・・電解山、4・・
・硫酸硝酸混液、5・・・クロムマスク、6・・・ガラ
ス基板、7・・・クロム膜、8・・・酸化クロム層、9
・・・銅板、10・・・直流電源
第1図 。
0
)FIG. 1 is a schematic diagram showing an experimental apparatus for explaining the present invention. 1... Constant temperature bath, 2... Water, 3... Electrolytic mountain, 4...
・Sulfuric acid/nitric acid mixture, 5...Chromium mask, 6...Glass substrate, 7...Chromium film, 8...Chromium oxide layer, 9
...Copper plate, 10...DC power supply Figure 1. 0)
Claims (2)
ムマスクを前記洗浄液に浸漬することを特徴とするクロ
ムマスクの洗浄方法。(1) A method for cleaning a chrome mask, which comprises using a solution prepared by adding an oxidizing agent to sulfuric acid as a cleaning liquid, and immersing a chrome mask in the cleaning liquid.
を特徴とする特許請求の範囲第1項記載のクロムマスク
の洗浄方法。(2) The method for cleaning a chrome mask according to claim 1, characterized in that nitric acid as the oxidizing agent is 5 mol % or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58197345A JPS6088946A (en) | 1983-10-21 | 1983-10-21 | Chromium mask washing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58197345A JPS6088946A (en) | 1983-10-21 | 1983-10-21 | Chromium mask washing method |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6088946A true JPS6088946A (en) | 1985-05-18 |
Family
ID=16372928
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58197345A Pending JPS6088946A (en) | 1983-10-21 | 1983-10-21 | Chromium mask washing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6088946A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009251243A (en) * | 2008-04-04 | 2009-10-29 | Shin Etsu Chem Co Ltd | Method of removing pellicle adhesive residue |
US20110124535A1 (en) * | 2008-05-15 | 2011-05-26 | Taiho Kogyo Co., Ltd. | Method for producing sliding member, sliding member, and substrate material of sliding member |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5924849A (en) * | 1982-08-02 | 1984-02-08 | Hitachi Ltd | Cleaning method of photomask |
JPS6053954A (en) * | 1983-09-05 | 1985-03-28 | Oki Electric Ind Co Ltd | Method for washing photomask |
-
1983
- 1983-10-21 JP JP58197345A patent/JPS6088946A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5924849A (en) * | 1982-08-02 | 1984-02-08 | Hitachi Ltd | Cleaning method of photomask |
JPS6053954A (en) * | 1983-09-05 | 1985-03-28 | Oki Electric Ind Co Ltd | Method for washing photomask |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009251243A (en) * | 2008-04-04 | 2009-10-29 | Shin Etsu Chem Co Ltd | Method of removing pellicle adhesive residue |
US20110124535A1 (en) * | 2008-05-15 | 2011-05-26 | Taiho Kogyo Co., Ltd. | Method for producing sliding member, sliding member, and substrate material of sliding member |
US9683603B2 (en) * | 2008-05-15 | 2017-06-20 | Taiho Kogyo Co., Ltd. | Method for producing sliding member, sliding member, and substrate material of sliding member |
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