JP2004176115A - Liquid composition for etching metallic thin film consisting essentially of silver - Google Patents
Liquid composition for etching metallic thin film consisting essentially of silver Download PDFInfo
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- JP2004176115A JP2004176115A JP2002342750A JP2002342750A JP2004176115A JP 2004176115 A JP2004176115 A JP 2004176115A JP 2002342750 A JP2002342750 A JP 2002342750A JP 2002342750 A JP2002342750 A JP 2002342750A JP 2004176115 A JP2004176115 A JP 2004176115A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、フラットパネルディスプレイ等の製造に用いられる銀を主成分とする金属薄膜のエッチング液組成物に関する。
【０００２】
【従来の技術】
反射型および半透過型液晶ディスプレイ装置の反射板または反射電極材料として、従来、アルミニウム薄膜が使用されていたが、近年においてアルミニウムよりも高反射率、低抵抗の特性を有する銀を主成分とする金属薄膜が注目されている（特許文献１、２参照）。
【０００３】
銀は微細加工性が劣る、塩化物や硫化物等と反応しやすい等の欠点があるが、導電率や反射率が高い等の理由で、銀膜上に透明導電膜を形成して配線の低抵抗化を実現する目的に従来から使用されてきた。
銀薄膜のエッチング液として、ウエットプロセスでは（１）希硝酸、（２）アンモニア水＋過酸化水素が知られており、ドライプロセスではイオンエッチングが使用されてきた（非特許文献１、２）。
銀膜上にＩＴＯ等の透明導電膜を形成した場合の一括エッチング液としては（３）塩酸、（４）塩酸＋硝酸、（５）硫酸＋硝酸、（６）硫酸＋硝酸＋バッファーとしての有機酸等、（７）硫酸＋硝酸＋界面活性剤等、様々なエッチング液が使用されてきた（特許文献３〜６）。
【０００４】
一般に金属のエッチングにおいては、金属表面を酸化させる酸化剤と、酸化された金属表面を溶解させる酸とが用いられる。被エッチング物がＩＴＯのような酸化物の場合には適宜選択した酸のみでもエッチングが可能である旨開示されている（特許文献７）。
上述の銀−ＩＴＯ一括エッチング液は酸化剤として硝酸を含み、酸として塩酸等を含むことから、この記述に一致している。
フラットパネルディスプレイにはアルミニウムやクロム等の各種金属が使用されているが、それらのエッチング液も酸化剤と酸の組み合わせとなっている。例えばアルミニウムのエッチング液はりん酸、硝酸、酢酸および水で構成されており、その代表的な液組成は８５重量％りん酸、９９重量％酢酸、７０重量％硝酸、水について１６：１：２：１（容量比）である（非特許文献２）。またクロムのエッチング液は硝酸第二セリウムアンモニウム、過塩素酸および水で構成されており、その代表的な濃度は硝酸第二セリウムアンモニウムが１５重量％、過塩素酸が４重量％である。
従って、反射膜等に適する銀合金について、例えば銀に従来使用されてきたエッチング液やアルミニウムやクロムに汎用されるエッチング液が使用できる可能性があるが、近年の微細化が進んだパターンをエッチングするには種々の問題がある。
その一つはエッチングレートが高いことであり、従来の銀エッチング液はエッチングレートが高く、フラットパネルディスプレイのように微細化が進み、線幅が３〜５μｍとなった現在ではエッチング時間の僅かな差でパターン消失の危険すら生じることになる。また、エッチング時に気泡が多量に発生しエッチングムラが生じる等の問題があり、優れたパターンを形成することができない。
例えば、希釈したアルミニウムエッチング液である、りん酸：硝酸：酢酸：水＝４：１：４：４（容量比、重量％ではりん酸３５．４重量％、硝酸５．２重量％、酢酸２５．７重量％、残りが水）の液が銀合金のエッチング液して使用できることが開示されている（非特許文献３）が、実際にエッチング液として使用してみると、優れたエッチングパターンを形成することができない。
また、特許文献１、２には、前述のほか、「水、硝酸セリウム、硝酸銀の添加によりエッチングレートが制御できる」旨記載されているが、その具体的組成および具体的な開示は何らなされていない。
クロムのエッチング液を銀合金のエッチング液に使用した場合については、エッチングレートが高すぎてムラが生じ、また水で希釈した場合にはエッチング液が不安定となって経時変化により析出物が発生するなど、使用することができない。
【０００５】
ここで優れたエッチングパターンとは、エッチングムラのないエッチングであり、エッチングされた金属の線幅のエッチング精度が高いこと、パターンエッジ形状がシャープな形状であること、また、パターンの形状がテーパーであること等を指す。パターンエッジ形状がシャープでなく凹凸形状になると反射ムラの問題が起き、パターンの形状にテーパー形状が得られないと、次工程の薄膜成膜におけるステップ・カバレッジが悪くなる。
銀合金のエッチング液として、りん酸、硝酸、酢酸、水の混酸ではエッチングレートが高すぎるため、該混酸にエチレングリコールまたはグリセリンを２０〜４０重量％加えたエッチング液が開示されているが（特許文献８）、水溶性有機成分量が多く、環境への負荷が大きい欠点がある。
このように、フラットパネルディスプレイ等の製造に用いられる銀を主成分とする金属薄膜に対して優れたエッチングパターンが形成できるエッチング液組成物について開示した例は従来なく、新しいエッチング液組成物が求められていた。
【０００６】
【特許文献１】
特開２００１−１９２７５２号公報
【特許文献２】
特開２００２−１４０９２９号公報
【特許文献３】
特開平７−１１４８４１号公報
【特許文献４】
特開平９−５９７８７号公報
【特許文献５】
特開平９−２０８２８７号公報
【特許文献６】
特開２０００−８１８４号公報
【特許文献７】
特開２００２−１２９３６１号公報
【特許文献８】
特開２００２−２３１７０６号公報
【非特許文献１】
「エレクトロニクスの精密微細加工」総合電子出版社、１９８０年発行、Ｐ８８
【非特許文献２】
「半導体工業における化学物質の取り扱いとその安全管理」株式会社フジテクノシステム社、１９８３年発行、Ｐ１２５
【非特許文献３】
（株）フルヤ金属［２００１年３月検索］、インターネット
＜ｈｔｔｐ：／／ｆｕｒｕｙａｍａｔｅｒｉａｌｓ．ｃｏ．ｊｐ＞
【０００７】
【発明が解決しようとする課題】
すなわち本発明の課題は、銀を主成分とする金属薄膜パターンを精度良くエッチング加工し、優れたパターン形状を形成し、かつ実用性に優れたエッチング液組成物を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく、鋭意、検討を重ねる中で、銀を主成分とする金属薄膜用エッチング液において、りん酸、硝酸、酢酸の組成比を最適化することにより、かかる課題を解決できることを見出し、さらに研究を進めた結果、本発明を完成するに至った。
すなわち、本発明は、銀を主成分とする金属薄膜をエッチングするエッチング液組成物であって、りん酸を４０〜５０重量％、硝酸を１．５〜３．５重量％、酢酸を２５〜４０重量％および水を配合してなる、前記エッチング液組成物に関する。
さらに、本発明は、金属薄膜が、銀（Ａｇ）、銀（Ａｇ）−パラジウム（Ｐｄ）合金、または銀（Ａｇ）−パラジウム（Ｐｄ）−銅（Ｃｕ）合金である、前記エッチング液組成物に関する。
また、本発明は、界面活性剤を含む、前記エッチング液組成物に関する
【０００９】
本発明のエッチング液組成物は、りん酸、硝酸、酢酸の組成比を最適化したことにより、銀を含む金属薄膜のエッチングをエッチング残渣を生じることなく十分に行うことができる。また、そのメカニズムは明確ではないが、本発明のエッチング液組成物は、腐食電位が高いことを特徴とし、エッチング活性の高さを維持しながらも、エッチング速度が抑えられたものであるため、サイドエッチングすることなく、優れたパターン形状が得られる。従って、本発明のエッチング液組成物は、銀を主成分とする、線幅３〜５μｍ程度の金属薄膜微細パターンであっても精度良くエッチング加工することができる。
【００１０】
【発明の実施の形態】
以下に本発明の実施の形態について詳述する。
本発明のエッチング液組成物は、りん酸の濃度が４０〜５０重量％、好ましくは４２〜４６重量％であり、硝酸の濃度が１．５重量％〜３．５重量％、好ましくは２．０重量％〜３．０重量％であり、酢酸の濃度が２５．０〜４０．０重量％、好ましくは３０．０〜３５．０重量％を含有してなるエッチング液組成物で、銀を主成分とする金属薄膜パターンを精度良くエッチング加工するものである。
【００１１】
りん酸および硝酸の濃度が上記範囲内であれば、エッチング速度が高すぎず、またサイドエッチングもなく精度良くエッチング加工することができる。エッチング速度が高い場合には、エッチング活性は良好であるが、エッチング反応時に気泡が発生し、エッチングムラの原因につながるため好ましくない。
また、りん酸および硝酸の濃度が上記範囲内であれば、エッチング残渣およびエッチングムラが発生しない。
【００１２】
また、酢酸の濃度が上記範囲内であれば、銀薄膜の腐食電位を高く維持することができ、エッチングが進行し、エッチング残渣やパターンエッジ形状の凹凸等の問題も発生しない。また、酢酸の濃度によっては凝固点が高い、引火性が生じる等の問題があるが、酢酸の濃度が上記範囲であればそれらの問題はなく、取扱い上、製造上、環境的、経済的にも好ましい。
本発明のエッチング液組成物は、腐食電位が高く、好ましくは、３８０ｍＶ（ｖｓＡｇ／ＡｇＣｌ）以上であることを特徴とする。腐食電位が高いことからもエッチング活性が高いことを示しているが、上述のように本発明のエッチング液組成物は、そのエッチング速度が低く抑えられたものである。従って、実用性に優れたエッチング特性が得られる。
また、本発明のエッチング液組成物のエッチングを行う温度は、好ましくは、２０〜４０℃である。低温ではエッチングレートが低すぎてエッチング所要時間が長過すぎる問題が生じ、また、高い温度ではエッチングレートが高すぎてサイドエッチング等の問題が生じる。
銀を主成分として用いる金属薄膜としては、銀（Ａｇ）、銀（Ａｇ）−パラジウム（Ｐｄ）合金、または銀（Ａｇ）−パラジウム（Ｐｄ）−銅（Ｃｕ）合金、銀（Ａｇ）−銅（Ｃｕ）−金（Ａｕ）合金、銀（Ａｇ）−ルテニウム（Ｒｕ）−金（Ａｕ）合金等が挙げられるが、好ましくは、銀（Ａｇ）、銀（Ａｇ）−パラジウム（Ｐｄ）合金、銀（Ａｇ）−パラジウム（Ｐｄ）−銅（Ｃｕ）合金、または銀（Ａｇ）−パラジウム（Ｐｄ）−ネオジウム（Ｎｄ）合金である。
また、本発明のエッチング液組成物には、エッチングを行なう面に対するぬれ性を改善するため、さらに界面活性剤を含んでもよい。界面活性剤は、アニオン系またはノニオン系が好ましい。
アニオン系界面活性剤としては、ふっ素系界面活性剤としてフタージェント１１０（株式会社ネオス）、ＥＦ−１０４（三菱マテリアル株式会社）、非ふっ素系界面活性剤としてパーソフトＳＦ−Ｔ（日本油脂株式会社）等があげられる。
また、ノニオン系界面活性剤としては、ふっ素系界面活性剤としてＥＦ−１２２Ａ（三菱マテリアル株式会社）、非ふっ素系界面活性剤としてフタージェント２５０（株式会社ネオス）等があげられる。
【００１３】
【実施例】
以下に、実施例と比較例を挙げて本発明を更に詳細に説明するが、本発明はこれら実施例により何ら限定されるものではない。
【００１４】
［実施例１〜１１］
１５００Åの膜厚のＡｇ合金（Ａｇ−Ｐｄ−Ｃｕ）膜上にレジストパターンを形成したガラス基板を準備し、表１（実施例１〜１１）のエッチング液に液温度３０℃、ジャストエッチング時間の１．２倍の時間で浸漬した。その後、水洗、乾燥後の基板について光学顕微鏡観察を行いエッチング後の残渣とサイドエッチング量について評価した。
ここで、エッチング液の調製には、８５重量％りん酸、９９重量％酢酸、７０重量％硝酸、水を用いており、組成は酸の重量と濃度から求めた。
結果を表１に示す。
【００１５】
［比較例１〜７］
実施例で用いたガラス基板を表１（比較例１〜７）のエッチング液に浸漬し、実施例と同様に処理を行った。結果を表１に併せて示す。
【００１６】
【表１】
比較例１は、従来のアルミニウムのエッチング液であるが、銀合金のエッチングに用いた場合、エッチングレートが高すぎるために、エッチングムラが生じて、優れたエッチングパターンを形成することができない。
【００１８】
［比較例８］
従来のクロムのエッチング液は、硝酸第二セリウムアンモニウム、過塩素酸および水で構成されており、これを用いて実験を行なった。
（１）代表的なクロムエッチング液を用いたエッチング
硝酸第二セリウムアンモニウムが１５重量％、過塩素酸が４重量％、残りが水のエッチング液を銀を主成分とする金属薄膜に用いた場合、エッチングレートが高すぎるため、優れたエッチングパターンを形成することができなかった。
（２）希釈したクロムエッチング液を用いたエッチング
エッチングレートを低くするため、３倍に希釈した前記エッチング液を用いるとエッチング残渣が発生しエッチングムラの問題が起きた。また、エッチング液は経時劣化が起こり、液中に析出物が発生した。
【００１９】
【発明の効果】
本発明のエッチング液組成物は、りん酸、硝酸、酢酸の組成比を最適化することにより、銀を主成分とする金属薄膜パターンをエッチング残渣もほとんどなく、精度良くエッチング加工し、優れたパターン形状を得ることができ、歩留まりの高い信頼性に優れたフラットパネルディスプレイ装置を製造できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an etchant composition for a metal thin film containing silver as a main component, which is used for manufacturing flat panel displays and the like.
[0002]
[Prior art]
Conventionally, aluminum thin films have been used as reflectors or reflective electrode materials for reflective and transflective liquid crystal display devices, but in recent years silver has a higher reflectivity and lower resistance than aluminum as a main component. Attention has been paid to metal thin films (see Patent Documents 1 and 2).
[0003]
Silver has drawbacks such as poor fine workability and easy reaction with chlorides and sulfides.However, due to high conductivity and reflectance, a transparent conductive film is formed on the silver film to form wiring. It has been used for the purpose of realizing low resistance.
As an etchant for a silver thin film, (1) diluted nitric acid and (2) aqueous ammonia + hydrogen peroxide are known in a wet process, and ion etching has been used in a dry process (Non-Patent Documents 1 and 2).
When a transparent conductive film such as ITO is formed on a silver film, the batch etching solution is (3) hydrochloric acid, (4) hydrochloric acid + nitric acid, (5) sulfuric acid + nitric acid, (6) sulfuric acid + nitric acid + organic as buffer. Various etching solutions such as acid and (7) sulfuric acid + nitric acid + surfactant have been used (Patent Documents 3 to 6).
[0004]
Generally, in metal etching, an oxidizing agent that oxidizes the metal surface and an acid that dissolves the oxidized metal surface are used. It is disclosed that when an object to be etched is an oxide such as ITO, etching can be performed using only an appropriately selected acid (Patent Document 7).
The above-described silver-ITO batch etching solution contains nitric acid as an oxidizing agent and hydrochloric acid as an acid, which is consistent with this description.
Various metals such as aluminum and chromium are used in flat panel displays, and their etching solutions are also combinations of oxidizing agents and acids. For example, an aluminum etchant is composed of phosphoric acid, nitric acid, acetic acid and water, and a typical liquid composition thereof is 16: 1: 2 for 85% by weight of phosphoric acid, 99% by weight of acetic acid, 70% by weight of nitric acid and water. : 1 (capacity ratio) (Non-Patent Document 2). The chromium etchant is composed of ceric ammonium nitrate, perchloric acid, and water, with typical concentrations of ceric ammonium nitrate of 15% by weight and perchloric acid of 4% by weight.
Therefore, for a silver alloy suitable for a reflection film or the like, for example, an etching solution conventionally used for silver or an etching solution commonly used for aluminum or chromium may be used, but a pattern that has recently been miniaturized is etched. There are various problems to do so.
One of them is that the etching rate is high, and the conventional silver etching solution has a high etching rate, and the fineness is advanced like a flat panel display, and the line width becomes 3 to 5 μm. The difference can even cause the risk of pattern loss. In addition, there is a problem that a large amount of air bubbles are generated at the time of etching and etching unevenness occurs, and an excellent pattern cannot be formed.
For example, phosphoric acid: nitric acid: acetic acid: water = 4: 1: 4: 4 (diluted aluminum etchant: 35.4% by weight of phosphoric acid, 5.2% by weight of nitric acid, 5.2% by weight of acetic acid, and 25% by weight of acetic acid) (Non-patent document 3) can be used as a silver alloy etchant, but when actually used as an etchant, an excellent etch pattern can be obtained. Cannot be formed.
In addition, Patent Documents 1 and 2 also describe that "the etching rate can be controlled by adding water, cerium nitrate, and silver nitrate" in addition to the above, but no specific composition and specific disclosure is made. Absent.
When the chromium etchant was used for the silver alloy etchant, the etching rate was too high, resulting in unevenness, and when diluted with water, the etchant became unstable and formed precipitates over time. Can not be used.
[0005]
Here, the excellent etching pattern is etching without etching unevenness, that the etching accuracy of the line width of the etched metal is high, the pattern edge shape is sharp, and the pattern shape is tapered. It means something. If the pattern edge shape is not sharp and has an uneven shape, a problem of reflection unevenness occurs. If a tapered shape is not obtained in the pattern shape, the step coverage in the next step of forming a thin film deteriorates.
As an etching solution for a silver alloy, a mixed acid of phosphoric acid, nitric acid, acetic acid, and water has an excessively high etching rate. Therefore, an etching solution in which ethylene glycol or glycerin is added to the mixed acid in an amount of 20 to 40% by weight is disclosed. Literature 8) has the disadvantage that the amount of water-soluble organic components is large and the burden on the environment is great.
As described above, there is no conventional example of an etchant composition capable of forming an excellent etching pattern on a metal thin film containing silver as a main component used in the manufacture of flat panel displays and the like. Had been.
[0006]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2001-192750 [Patent Document 2]
JP 2002-140929 A [Patent Document 3]
Japanese Patent Application Laid-Open No. 7-114481 [Patent Document 4]
JP-A-9-59787 [Patent Document 5]
Japanese Patent Application Laid-Open No. 9-208287 [Patent Document 6]
Japanese Patent Application Laid-Open No. 2000-8184 [Patent Document 7]
JP 2002-129361 A [Patent Document 8]
JP-A-2002-231706 [Non-Patent Document 1]
"Precision Microfabrication of Electronics" Sogo Denshi Publishing Co., 1980, p.88
[Non-patent document 2]
"Handling of Chemical Substances and Safety Management in the Semiconductor Industry" Fuji Techno System Co., Ltd., 1983, P125
[Non-Patent Document 3]
Furuya Metal Co., Ltd. [searched March 2001], Internet <http: // furuyamamaterials. co. jp>
[0007]
[Problems to be solved by the invention]
That is, an object of the present invention is to provide an etching solution composition which is capable of etching a metal thin film pattern containing silver as a main component with high precision to form an excellent pattern shape and is excellent in practical use.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, the present inventors have intensively studied and, by optimizing the composition ratio of phosphoric acid, nitric acid, and acetic acid in an etching solution for a metal thin film containing silver as a main component, As a result of finding out that such a problem can be solved and further researching, the present invention has been completed.
That is, the present invention relates to an etchant composition for etching a metal thin film containing silver as a main component, comprising 40 to 50% by weight of phosphoric acid, 1.5 to 3.5% by weight of nitric acid, and 25 to 50% by weight of acetic acid. The present invention relates to the etching solution composition, which comprises 40% by weight and water.
Furthermore, the present invention provides the etching solution composition, wherein the metal thin film is silver (Ag), a silver (Ag) -palladium (Pd) alloy, or a silver (Ag) -palladium (Pd) -copper (Cu) alloy. About.
Further, the present invention relates to the etching solution composition containing a surfactant.
By optimizing the composition ratio of phosphoric acid, nitric acid, and acetic acid, the etching composition of the present invention can sufficiently etch a metal thin film containing silver without generating an etching residue. Further, although the mechanism is not clear, the etching solution composition of the present invention is characterized by a high corrosion potential, while maintaining a high etching activity, while suppressing the etching rate, An excellent pattern shape can be obtained without side etching. Therefore, the etching solution composition of the present invention can be accurately etched even with a metal thin film fine pattern having a line width of about 3 to 5 μm containing silver as a main component.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
The etching solution composition of the present invention has a phosphoric acid concentration of 40 to 50% by weight, preferably 42 to 46% by weight, and a nitric acid concentration of 1.5 to 3.5% by weight, preferably 2. 0% to 3.0% by weight and an acetic acid concentration of 25.0 to 40.0% by weight, preferably 30.0 to 35.0% by weight. The metal thin film pattern as a main component is etched with high precision.
[0011]
When the concentrations of phosphoric acid and nitric acid are within the above ranges, the etching rate is not too high, and the etching can be accurately performed without side etching. When the etching rate is high, the etching activity is good, but air bubbles are generated at the time of the etching reaction, which leads to uneven etching, which is not preferable.
If the concentrations of phosphoric acid and nitric acid are within the above ranges, etching residues and etching unevenness do not occur.
[0012]
When the concentration of acetic acid is within the above range, the corrosion potential of the silver thin film can be kept high, and the etching proceeds, and problems such as etching residues and irregularities in the pattern edge shape do not occur. In addition, depending on the concentration of acetic acid, there are problems such as a high freezing point and flammability.However, if the concentration of acetic acid is within the above range, there are no such problems, and handling, manufacturing, environmentally, and economically are also difficult. preferable.
The etching solution composition of the present invention has a high corrosion potential, and is preferably 380 mV (vsAg / AgCl) or more. Although the high corrosion potential indicates that the etching activity is high, the etching solution composition of the present invention has a low etching rate as described above. Therefore, etching characteristics excellent in practicality can be obtained.
The temperature at which the etching solution composition of the present invention is etched is preferably 20 to 40 ° C. At low temperatures, the etching rate is too low and the required time for etching is too long. At high temperatures, the etching rate is too high and problems such as side etching occur.
Examples of the metal thin film using silver as a main component include silver (Ag), silver (Ag) -palladium (Pd) alloy, silver (Ag) -palladium (Pd) -copper (Cu) alloy, and silver (Ag) -copper. (Cu) -gold (Au) alloy, silver (Ag) -ruthenium (Ru) -gold (Au) alloy, etc., but preferably silver (Ag), silver (Ag) -palladium (Pd) alloy, It is a silver (Ag) -palladium (Pd) -copper (Cu) alloy or a silver (Ag) -palladium (Pd) -neodymium (Nd) alloy.
Further, the etching solution composition of the present invention may further contain a surfactant in order to improve the wettability on the surface to be etched. The surfactant is preferably anionic or nonionic.
Examples of the anionic surfactants include Futagent 110 (Neos Corporation) and EF-104 (Mitsubishi Materials Corporation) as fluorosurfactants, and Persoft SF-T (Nippon Oil & Fats Co., Ltd.) as non-fluorinated surfactants. ) And the like.
Examples of the nonionic surfactant include EF-122A (Mitsubishi Materials Corporation) as a fluorine-based surfactant, and Phantagent 250 (Neos Corporation) as a non-fluorinated surfactant.
[0013]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
[0014]
[Examples 1 to 11]
A glass substrate in which a resist pattern was formed on an Ag alloy (Ag-Pd-Cu) film having a thickness of 1500 ° was prepared, and the etching solution of Table 1 (Examples 1 to 11) was subjected to a solution temperature of 30 ° C. and a just etching time. It was immersed for 1.2 times. Thereafter, the substrate after washing with water and drying was observed under an optical microscope, and the residue after etching and the amount of side etching were evaluated.
Here, 85% by weight of phosphoric acid, 99% by weight of acetic acid, 70% by weight of nitric acid, and water were used for preparing the etching solution, and the composition was determined from the weight and concentration of the acid.
Table 1 shows the results.
[0015]
[Comparative Examples 1 to 7]
The glass substrates used in the examples were immersed in the etching solutions shown in Table 1 (Comparative Examples 1 to 7), and were treated in the same manner as in the examples. The results are shown in Table 1.
[0016]
[Table 1]
Comparative Example 1 is a conventional aluminum etchant, but when used for etching a silver alloy, the etching rate is too high, so that etching unevenness occurs and an excellent etching pattern cannot be formed.
[0018]
[Comparative Example 8]
The conventional chromium etchant was composed of ceric ammonium nitrate, perchloric acid and water, and experiments were performed using this.
(1) Etching using a typical chromium etching solution In the case of using an etching solution of 15% by weight of ceric ammonium nitrate, 4% by weight of perchloric acid, and the remaining water as a metal thin film mainly containing silver In addition, since the etching rate was too high, an excellent etching pattern could not be formed.
(2) Etching Using Diluted Chromium Etching Solution In order to lower the etching rate, if the etching solution diluted three times is used, an etching residue is generated, causing a problem of uneven etching. Further, the etching solution deteriorated with time, and a precipitate was generated in the solution.
[0019]
【The invention's effect】
By optimizing the composition ratio of phosphoric acid, nitric acid, and acetic acid, the etching solution composition of the present invention has a metal thin film pattern containing silver as a main component with almost no etching residue, and is etched with high accuracy. A shape can be obtained, and a flat panel display device with high yield and excellent reliability can be manufactured.
Claims (2)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002342750A JP4478383B2 (en) | 2002-11-26 | 2002-11-26 | Etching solution composition for metal thin film mainly composed of silver |
| TW092129410A TWI278535B (en) | 2002-11-26 | 2003-10-23 | Etchant compositions for metal thin films having as the major component silver |
| CNB2003101180446A CN100347344C (en) | 2002-11-26 | 2003-11-24 | Etching solution composition for metal foil using silver as main composition |
| KR1020030084114A KR101017390B1 (en) | 2002-11-26 | 2003-11-25 | Etchant compositions for metal thin films having as the major component silver |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002342750A JP4478383B2 (en) | 2002-11-26 | 2002-11-26 | Etching solution composition for metal thin film mainly composed of silver |
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| JP2004176115A true JP2004176115A (en) | 2004-06-24 |
| JP4478383B2 JP4478383B2 (en) | 2010-06-09 |
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| JP2002342750A Expired - Lifetime JP4478383B2 (en) | 2002-11-26 | 2002-11-26 | Etching solution composition for metal thin film mainly composed of silver |
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| Country | Link |
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| JP (1) | JP4478383B2 (en) |
| KR (1) | KR101017390B1 (en) |
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2002
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- 2003-11-24 CN CNB2003101180446A patent/CN100347344C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI278535B (en) | 2007-04-11 |
| CN100347344C (en) | 2007-11-07 |
| TW200408729A (en) | 2004-06-01 |
| CN1502722A (en) | 2004-06-09 |
| KR101017390B1 (en) | 2011-02-28 |
| JP4478383B2 (en) | 2010-06-09 |
| KR20040047634A (en) | 2004-06-05 |
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