JP4897148B2 - Etching solution for transparent conductive film - Google Patents
Etching solution for transparent conductive film Download PDFInfo
- Publication number
- JP4897148B2 JP4897148B2 JP2001094688A JP2001094688A JP4897148B2 JP 4897148 B2 JP4897148 B2 JP 4897148B2 JP 2001094688 A JP2001094688 A JP 2001094688A JP 2001094688 A JP2001094688 A JP 2001094688A JP 4897148 B2 JP4897148 B2 JP 4897148B2
- Authority
- JP
- Japan
- Prior art keywords
- halogen
- transparent conductive
- etching
- etching solution
- salt
- 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
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Weting (AREA)
Description
【技術分野】
【0001】
【発明の属する技術分野】
本発明は、液晶ディスプレイ(LCD)などに使用されるインジウム酸化物を含む透明導電性膜のエッチング液に関する。
【従来の技術】
【0002】
ITO(インジウム−錫酸化物)膜をはじめとする透明導電膜は、帯電防止膜、熱反射膜、光電変換素子や各種フラットパネルディスプレイの透明電極などの電子デバイス分野に広く用いられている。最近では、ノートPCや小型TV、携帯用情報端末などの普及とともに、液晶ディスプレイ(LCD)での需要が増加している。
【0003】
ITO等の透明導電膜は、フラットパネルディスプレイの分野においては、画素の表示電極として使用され、フォトリソグラフィーのエッチングにより作成される。このような透明導電膜は、金属層に対して酸化作用を有し、ハロゲンイオンを含有する酸性水溶液からなるエッチング液を用いることにより、微細な電極パターンを精度良く形成できる。
【0004】
特開平5−62966号公報では、蓚酸の飽和水溶液を用いる方法が提案されている。この方法では、結晶系透明電極でのエッチング速度が小さいために、非結晶系の透明電極膜に限定される。
【0005】
特開平10−91084号公報では、塩酸などのハロゲンイオンと酸化剤を含む酸性液によるエッチング処理したのち、ハロゲンアルカリ金属塩の液でスラッジを除去する処理方法が提案されている。この方法では、エッチング速度が小さいエッチングを行う第1段の処理とエッチング速度に関係しないハロゲンアルカリ金属塩液を用いた第2段の処理であるために、エッチング速度が小さい。
【発明が解決しようとする課題】
【0006】
本発明は、従来技術における上記の課題を解決し、結晶系透明電極膜の大きいエッチング速度を1段処理で得られるエッチング液を提供することにある。
【課題を解決するための手段】
【0007】
本発明者らは、ガラス基板、或いは、プラスチック基板上のインジウム酸化物を含む透明導電膜のパターニングにおいて鋭意研究を重ねた結果、ハロゲン酸及びハロゲン金属塩、さらには酸化剤を含有するエッチング液による1段階処理で大きなエッチング速度が得られ、且つ、装置材料の腐食の防止ができることを見出し本発明に到達した。すなわち、本発明は、ハロゲン酸およびハロゲン金属塩を含有する水溶液である透明導電膜のエッチング液、さらには酸化剤を含有する水溶液である透明導電膜のエッチング液に関するものである。
【発明の実施の形態】
【0008】
本発明の対象となる透明導電膜は、スパッタリング法、イオンプレーティング法、蒸着法などの方法でガラス基板、或いは、プラスチック基板上に100〜5000Åの厚みで成膜されたものが例示される。また、光透過率70%以上、比抵抗が1Ωcm以下の場合のものも例示される。薄膜には、酸化錫や酸化亜鉛など他の酸化物が添加される事もある。本発明のエッチング液は、特に、結晶タイプの透明電極に好都合である。
【0009】
本発明に使用されるハロゲン酸は、フッ酸、塩酸、臭化水素、ヨウ化水素が挙げられる。ハロゲン金属塩は、ナトリウム、カリウム等のアルカリ金属のフッ化物、塩化物、臭化物およびヨウ化物であるハロゲン塩、カルシウム、マグネシウム等のアルカリ土類金属のハロゲン塩、およびアルミニウムのハロゲン塩が挙げられる。特に、アルカリ土類金属は、ハロゲン酸に対する溶解度が大きいために、高濃度にできることによりエッチング速度を向上でき好ましい。これらのハロゲン金属塩は、2種以上用いることができる。このハロゲン酸およびハロゲン金属塩は、水またはアルコール類などの有機溶媒で希釈する。
【0010】
酸化剤は、エッチング速度を上昇させると共に、ハロゲン酸、ハロゲン金属塩による装置材料の腐食を大幅に低減させる為に使用する。具体的には、アルカリ金属やアルカリ土類金属の硝酸塩、亜硝酸塩、過酸化水素、過酸化有機物などであり、塩素酸カルシウム、硝酸ナトリウム、硝酸カルシウム、過酸化酢酸、過酸化水素が挙げられる。
【0011】
各成分の濃度は、ハロゲン酸が0.1〜6mol/L、好ましくは、1〜5mol/L、ハロゲン金属塩が0.01〜6mol/L、好ましくは、0.1〜5mol/L、更に、酸化剤が0.01〜2mol/Lである。さらに、好ましいエッチング速度を得るためには、エッチング液中のハロゲン濃度が1mol/L〜飽和濃度であり、且つ、ハロゲン金属塩のハロゲン量が、エッチング液中の全ハロゲン量の10〜90重量%である。
【0012】
エッチング温度は、所定のエッチング速度が得られる温度で使用し、一般的には、30〜70℃である。エッチング方法は、ディッピング法やスプレー法で実施されるが、特に限定されるものでない。また、酸素、塩素、酸化窒素、オゾンなどの気体状酸化剤を吹き込みながら、エッチングすることで装置材料の腐食を軽減し、装置の寿命を延ばすこともできる。
【0013】
エッチング液の使用法は、以下の順序で行われる。
1.薄膜上に感光材料を塗付する。
2.パターンが描かれたフォトマスクを通して、電磁波や電子線を感光材料に照射する。
3.感光材料を現像してレジストパターンを得る。
4.レジストで保護されていない部分の薄膜を本発明のエッチング液でエッチング・除去する。
【実施例】
【0014】
実施例により本発明を具体的に説明する。尚、濃度は、Mol/Lである。
【0015】
実施例1〜18、比較例1〜12
(1)成膜
厚みが1500Åの酸化インジウム(95%)+酸化錫(5%)の薄膜をガラス基板(厚み1mm)とポリエチレンフタレート基板(厚み0.25mm)上にスパッタリング法で薄膜を成膜した。
(2)膜特性
成膜した薄膜は、表1に示す光透過率、比抵抗であった。
【0016】
【表1】
【0017】
(3)レジストパターンの形成
表1の基板の薄膜面上にレジスト液をロールコーターで塗付し、100℃の温風で15分プレベークした。プレベーク後のレジストの厚みは、2μmであった。その後、パターンを描いたフォトマスクを通して、波長350〜450nmの光線をレジストに照射・露光した。その後、25℃の現像液に振動を与えながら浸漬・現像し、剥離剤で未露光部分のレジストを剥離後、水洗し、100℃で30分間乾燥した。
【0018】
(4)エッチング液
レジストパターニングされた基板の薄膜面のエッチングに使用した本発明の1段処理用水溶液である薬剤組成を表2の薬剤番号1〜7に示す。1段処理での比較例に用いる薬剤を薬剤番号8〜12、2段階処理での薬剤を番号13に示す。
【0019】
【表2】
【0020】
(5)エッチング
レジストパターニングされた基板の薄膜面に薬剤をスプレーし、表3に示す条件でエッチングした。エッチング所用時間は、エッチング後の表面抵抗がテスターで無限大になる時間をエッチング時間とした。
【0021】
【表3】
【0022】
(6)装置の金属材料の耐食性
装置に用いるTi合金材の丸棒(直径10mm×長さ5mm)を薬剤に25℃で7日間浸漬し、丸棒の重量減少量から薬剤の腐食性を確認した。その結果を表4に示す。
【0023】
【表4】
【発明の効果】
【0024】
本発明のエッチング液によりエッチング速度が向上し、良好なパターニングが得られる。そして、ハロゲン酸濃度の低減などが可能になり、ハロゲン酸の作業環境の汚染を緩和し、装置材料を腐食させないエッチングができる。【Technical field】
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an etching solution of the transparent conductive film containing a liquid crystal di spray lay (L C D) indium oxide used for such.
[Prior art]
[0002]
Transparent conductive films including ITO (indium-tin oxide) films are widely used in the field of electronic devices such as antistatic films, heat reflecting films, photoelectric conversion elements and transparent electrodes of various flat panel displays. In recent years, notebook PC and a small TV, along with the spread of portable information terminals, the demand for a liquid crystal Display Lee (LCD) has increased.
[0003]
A transparent conductive film such as ITO is used as a display electrode of a pixel in the field of flat panel display, and is formed by photolithography etching. Such a transparent conductive film has an oxidizing action on the metal layer, and a fine electrode pattern can be formed with high accuracy by using an etching solution made of an acidic aqueous solution containing halogen ions.
[0004]
Japanese Patent Application Laid-Open No. 5-62966 proposes a method using a saturated aqueous solution of succinic acid. This method is limited to the amorphous transparent electrode film because the etching rate of the crystalline transparent electrode is low.
[0005]
In JP-A 10-91084 and JP After etching treatment with an acidic solution containing halogen ions and an oxidizing agent such as hydrochloric acid, treatment how has been proposed to remove the sludge in the liquid halide alkali metal salts. This method has a low etching rate because it is a first-stage process that performs etching at a low etching rate and a second-stage process that uses a halogen alkali metal salt solution that is not related to the etching rate.
[Problems to be solved by the invention]
[0006]
An object of the present invention is to solve the above-mentioned problems in the prior art and to provide an etching solution capable of obtaining a large etching rate of a crystalline transparent electrode film by a one-step process.
[Means for Solving the Problems]
[0007]
The present inventors have glass substrate, or the result of intensive research in patterns over training of the transparent conductive film containing indium oxide on a plastic substrate, halogen acids and halogen metal salts, further contains an oxidizing agent etch The inventors have found that a large etching rate can be obtained by one-step treatment with a liquid and that corrosion of the device material can be prevented, and the present invention has been reached. That is, the present invention relates to an etching solution for a transparent conductive film which is an aqueous solution containing a halogen acid and a halogen metal salt, and further relates to an etching solution for a transparent conductive film which is an aqueous solution containing an oxidizing agent.
DETAILED DESCRIPTION OF THE INVENTION
[0008]
Subject to the transparent conductive film of the present invention, the scan package data ring method, ion plating computing method, a glass substrate by a method such as an evaporation method, or exemplified those deposited at a thickness of 100~5000Å on plastic substrates Is done. Moreover, the case where the light transmittance is 70% or more and the specific resistance is 1 Ωcm or less is also exemplified. Other oxides such as tin oxide and zinc oxide may be added to the thin film. The etching solution of the present invention is particularly advantageous for crystal-type transparent electrodes.
[0009]
Examples of the halogen acid used in the present invention include hydrofluoric acid, hydrochloric acid, hydrogen bromide, and hydrogen iodide. Halogen metal salts include alkali metal fluorides such as sodium and potassium, halogen salts which are chlorides, bromides and iodides, alkaline earth metal halogen salts such as calcium and magnesium, and aluminum halogen salts. In particular, an alkaline earth metal is preferable because it has a high solubility in a halogen acid, so that the etching rate can be improved by increasing the concentration. Two or more of these halogen metal salts can be used. The halogen acids and metal halide salt is diluted with an organic solvent, such as water or alcohol such.
[0010]
The oxidizing agent is used to increase the etching rate and greatly reduce the corrosion of the device material by the halogen acid and the halogen metal salt. Specific examples include alkali metal and alkaline earth metal nitrates, nitrites, hydrogen peroxide, and organic peroxides, and examples include calcium chlorate, sodium nitrate, calcium nitrate, acetic acid peroxide, and hydrogen peroxide.
[0011]
Concentration of each component is 0.1-6 mol / L, preferably 1-5 mol / L for halogen acid, 0.01-6 mol / L for halogen metal salt, preferably 0.1-5 mol / L, The oxidizing agent is 0.01 to 2 mol / L. Furthermore, in order to obtain a preferable etching rate, the halogen concentration in the etching solution is 1 mol / L to a saturated concentration, and the halogen amount of the halogen metal salt is 10 to 90% by weight of the total halogen amount in the etching solution. It is.
[0012]
The etching temperature is used at a temperature at which a predetermined etching rate can be obtained, and is generally 30 to 70 ° C. Etching method is carried out in de-mappings method or spray method, not particularly limited. Further, the etching of the device material while blowing a gaseous oxidant such as oxygen, chlorine, nitrogen oxide, or ozone can reduce the corrosion of the device material and extend the life of the device.
[0013]
The usage of the etching solution is performed in the following order.
1. A photosensitive material is applied on the thin film.
2. Through a photomask patterns are drawn, irradiation with electromagnetic waves or electron beams to the photosensitive material.
3. Obtaining a resist pattern over emissions by developing the photosensitive material.
4). A portion of the thin film that is not protected by the resist is etched and removed with the etching solution of the present invention.
【Example】
[0014]
The present invention will be specifically described with reference to examples. The concentration is Mol / L.
[0015]
Examples 1-18, Comparative Examples 1-12
(1) indium oxide (95%) of the deposition thickness of 1500 Å + scan package data ring thin film on a polyethylene phthalate les over preparative substrate and a glass substrate (thickness 1 mm) (thickness 0.25 mm) of tin oxide (5%) A thin film was formed by this method.
(2) Film characteristics The formed thin film had the light transmittance and specific resistance shown in Table 1.
[0016]
[Table 1]
[0017]
(3) subjected apply a resist pattern over emissions resist solution on the thin film surface of the substrate forming table 1 in a roll coater, and 15 minutes Purebe over click at 100 ° C. hot air. The resist thickness after pre-baking was 2 μm. Thereafter, the resist was irradiated and exposed to light having a wavelength of 350 to 450 nm through a photomask on which a pattern was drawn. Thereafter, the film was immersed and developed while applying vibration to a 25 ° C. developer, and after removing the unexposed resist with a release agent, washed with water and dried at 100 ° C. for 30 minutes.
[0018]
(4) shows the pharmaceutical composition is a 1-stage process for an aqueous solution of the present invention used in the etching of the thin film surface of the etchant resist pattern over training has been substrate drug ID NO: 1 through 7 in Table 2. Drugs Nos. 8 to 12 are used for comparative examples in the first stage treatment, and No. 13 is a drug in the second stage treatment.
[0019]
[Table 2]
[0020]
(5) a drug and SPRAY on the thin film surface of the etching resist pattern Ningu been substrates were etched under the conditions shown in Table 3. Etching required time was the time at which the surface resistance after etching becomes infinite at the tester over the etching time.
[0021]
[Table 3]
[0022]
(6) Corrosion resistance of the metal material of the equipment Ti alloy material round bar (diameter 10mm x length 5mm) used in the equipment is immersed in the chemical for 7 days at 25 ° C, and the corrosiveness of the chemical is confirmed from the weight loss of the round bar did. The results are shown in Table 4.
[0023]
[Table 4]
【Effect of the invention】
[0024]
Improves the etching rate by the etchant of the present invention, good pattern over training is obtained. Further, it becomes possible to reduce the concentration of the halogen acid, etc., to reduce the contamination of the working environment of the halogen acid, and to perform etching without corroding the device material.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001094688A JP4897148B2 (en) | 2001-03-29 | 2001-03-29 | Etching solution for transparent conductive film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001094688A JP4897148B2 (en) | 2001-03-29 | 2001-03-29 | Etching solution for transparent conductive film |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2002299326A JP2002299326A (en) | 2002-10-11 |
JP4897148B2 true JP4897148B2 (en) | 2012-03-14 |
Family
ID=18948847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001094688A Expired - Lifetime JP4897148B2 (en) | 2001-03-29 | 2001-03-29 | Etching solution for transparent conductive film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4897148B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI364072B (en) * | 2004-03-18 | 2012-05-11 | Dongjin Semichem Co Ltd | Etching composition |
JP5262478B2 (en) * | 2008-09-11 | 2013-08-14 | 東ソー株式会社 | Etching solution for transparent electrodes |
JP5788701B2 (en) * | 2011-04-11 | 2015-10-07 | 関東化学株式会社 | Etching composition for transparent conductive film |
KR101293628B1 (en) * | 2011-06-10 | 2013-08-13 | 솔브레인 주식회사 | Composition for wet etching of Crystallized ITO |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61145529A (en) * | 1984-12-19 | 1986-07-03 | Matsushita Electric Ind Co Ltd | Formation of transparent electrode pattern |
JPH02135619A (en) * | 1988-11-17 | 1990-05-24 | Asahi Glass Co Ltd | Wet etching method |
JPH0342829A (en) * | 1989-07-11 | 1991-02-25 | Citizen Watch Co Ltd | Etchant for transparent conductive film |
JP3711650B2 (en) * | 1996-09-12 | 2005-11-02 | 旭硝子株式会社 | Patterning method for transparent conductive film and substrate with transparent electrode |
-
2001
- 2001-03-29 JP JP2001094688A patent/JP4897148B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2002299326A (en) | 2002-10-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7329365B2 (en) | Etchant composition for indium oxide layer and etching method using the same | |
TWI411661B (en) | Etching solution for eletrically-conductive polymer use and method of patterning conductive polymer | |
JP2009231427A (en) | Etchant, method for etching transparent conductive film using etchant, substrate to be etched | |
EP0560442B1 (en) | Method of manufacturing an electrically conductive pattern of tin-doped indium oxide (ITO) on a substrate | |
JP4949416B2 (en) | Etching solution composition for ITO film and method for etching ITO film using the same | |
JP2002270051A (en) | Method of patterning conductive tin oxide film | |
JP4897148B2 (en) | Etching solution for transparent conductive film | |
JP6817655B2 (en) | Etching solution and its use | |
CN109797396B (en) | Silver film etching liquid composition, etching method using the same and metal pattern forming method | |
JP3611618B2 (en) | Method for patterning amorphous conductive film | |
KR20130084717A (en) | Etchant composition and method of manufacturing a display substrate using the etchant composition | |
JP4122971B2 (en) | Wet etchant composition | |
JP5020591B2 (en) | Etching solution for conductive polymer and method for patterning conductive polymer | |
JP2002367974A (en) | Etching agent composition for transparent conductive film | |
JP2002033304A (en) | Composition for etching | |
KR101744520B1 (en) | Etchant for the conductive film containing silver nanowire, transparent electrode and preparation method using the same | |
KR101406402B1 (en) | Manufacturing method of array substrate for liquid crystal display | |
JP5262477B2 (en) | Etching solution for transparent electrodes | |
JP2008047645A (en) | Etching liquid and etching method of transparent electrode | |
JP2002363776A (en) | Etching agent composition | |
JP3502365B2 (en) | Etching composition for transparent conductive film | |
JP2000150457A (en) | Method for etching transparent conductive film | |
KR20060062866A (en) | Etchant composition for indium zinc oxide layer and etching method using the same | |
JPH11269671A (en) | Method for patterning tin oxide thin film and etchant | |
KR20110079797A (en) | Etchant composition for indium zinc oxide layer and etching method using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040830 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20040830 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20040830 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20041021 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20041021 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20071025 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20071025 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071228 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091209 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091215 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100215 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100309 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100609 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100622 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20100813 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110929 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111102 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111222 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4897148 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150106 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |