JP4162652B2 - Sputtering target material - Google Patents

Sputtering target material Download PDF

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JP4162652B2
JP4162652B2 JP2004507551A JP2004507551A JP4162652B2 JP 4162652 B2 JP4162652 B2 JP 4162652B2 JP 2004507551 A JP2004507551 A JP 2004507551A JP 2004507551 A JP2004507551 A JP 2004507551A JP 4162652 B2 JP4162652 B2 JP 4162652B2
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mass
thin film
target material
sputtering target
based alloy
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JPWO2003100112A1 (en
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浩一 長谷川
信雄 石井
知美 朝木
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Ishifuku Metal Industry Co Ltd
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

Description

技術分野
本発明は、高い反射率を維持しながら、耐食性、特に耐硫化性を向上させた薄膜形成用スパッタリングターゲット材、およびこのスパッタリングターゲット材を用いて形成された薄膜に関する。
背景技術
ＣＤ（Ｃｏｍｐａｃｔ Ｄｉｓｃ）、ＤＶＤ（Ｄｉｇｉｔａｌ Ｖｅｒｓａｔｉｌｅ Ｄｉｓｃ）等の光学記録媒体に使用されている反射膜や、反射型ＳＴＮ（Ｓｕｐｅｒ Ｔｗｉｓｔ Ｎｅｍａｔｉｃ）液晶表示装置、有機ＥＬ（Ｅｌｅｃｔｒｏ ｌｕｍｉｎｅｓｃｅｎｃｅ）表示装置等に使用されている光反射性導電膜には、一般に、ＡｌやＡｌ合金が使用されている。
上記の光学記録媒体や液晶表示装置、有機ＥＬ表示装置などの用途に使用される光反射性薄膜は、一般に、所望とする性質をもつスパッタリングターゲット材を作製し、そのスパッタリングターゲット材を使用してＲＦ（高周波）スパッタリング法やＤＣ（直流）スパッタリング法等により成膜することにより製造されている。
上記の方法で製造されるＡｌやＡｌ合金からなる薄膜は、ある程度の反射率を有しかつ電気抵抗が低く、しかも、表層に不動態皮膜を形成するため、空気中においても安定した耐食性を有するが、ＡｌやＡｌ合金からなる薄膜の反射率は、例えば波長が７００ｎｍの光の場合８０％程度であり、高反射率が要求される用途に対しては充分に満足できるものではない。
そのため、高い反射率を有する薄膜が要求される、例えばＣＤやＤＶＤに代表される光ディスク媒体には、スパッタリングターゲット材として、ＡｌまたはＡｌ合金に代わりに、ＡｕやＡｇを使用して薄膜を形成することが提案されており、また、反射型ＳＴＮ液晶表示装置についても、薄膜材料として反射率の高いＡｇを使用することが提案されている。
しかしながら、Ａｕは高価であり、また、Ａｇは、Ａｌと比較して、耐食性、特に耐酸化性、耐硫化性に問題がある。例えば、Ａｇは硫黄と反応すると、Ａｇの硫化物を生成して黒色化し反射率が低下する。
そのため、例えば、特開平７−３３６３号公報には、Ａｇに少量のＭｇを添加して合金化することにより、耐食性を向上させることが提案されている。
しかしながら、これらのＡｇの合金化によっても、充分な耐食性は得られない。
また、次世代大容量光記録メディアでは、記憶容量の増加のために４０５ｎｍのような短波長のレーザー光を使用することが予定されており、そのような条件下での耐食性、耐熱性等が要求されている。
本発明の主たる目的は、高い反射率を維持しながら、耐食性、特に耐硫化性が改善されたＡｇ合金からなる薄膜形成用のスパッタリングターゲット材を提供することである。
発明の開示
本発明者らは、上記の目的を達成すべく鋭意検討を重ねた結果、今回、Ａｇに、特定少量のＩｎと、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分の少量とを添加して合金化すると、Ａｇがもつ高い反射率を維持しつつ、耐食性、特に耐硫化性および耐熱性が格段に向上したＡｇ基合金が得られること、そして該Ａｇ基合金成分に対し、さらにＡｕ、Ｐｔ及びＰｄから選ばれる少なくとも一種の他の金属成分の少量を添加して合金化すると、耐食性、特に耐硫化性がより一層向上することを見出し、本発明を完成するに至った。
かくして、本発明は、Ａｇに、Ｉｎを０．０１〜５．０ｍａｓｓ％と、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０．０１〜５．０ｍａｓｓ％含有せしめてなるＡｇ基合金より構成されていることを特徴とする高反射率を有する高耐食性薄膜形成用スパッタリングターゲット材を提供するものである。
本発明は、また、Ａｇに、Ｉｎを０．０１〜５．０ｍａｓｓ％と、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０．０１〜５．０ｍａｓｓ％と、Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種を０．０１〜０．１ｍａｓｓ％未満含有せしめてなるＡｇ基合金より構成されていることを特徴とする高反射率を有する高耐食性薄膜形成用スパッタリングターゲット材を提供するものである。
本発明は、また、Ａｇに、Ｉｎを０．０１〜５．０ｍａｓｓ％と、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０．０１〜５．０ｍａｓｓ％含有せしめてなるＡｇ基合金よりなる薄膜を提供するものである。
本発明は、さらにまた、Ａｇに、Ｉｎを０．０１〜５．０ｍａｓｓ％と、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０．０１〜５．０ｍａｓｓ％と、Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種を０．０１〜０．１ｍａｓｓ％未満含有せしめてなるＡｇ基合金よりなる薄膜を提供するものである。
以下、本発明についてさらに詳細に説明する。
発明の実施の形態
本発明のスパッタリングターゲット材は、一つの態様によれば、Ａｇをベースとし、これにＩｎと、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を添加して合金化してなるＡｇ合金からなるものである。
上記Ｉｎは、Ａｇに対し、０．０１〜５．０ｍａｓｓ％、好ましくは０．１〜１．５ｍａｓｓ％の範囲内の量で添加することができる。また、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分は、Ａｇに対し、合計で０．０１〜５．０ｍａｓｓ％、好ましくは０．１〜１．５ｍａｓｓ％の範囲内の量で添加することができる。
本発明のスパッタリングターゲット材は、別の態様によれば、Ａｇをベースとし、これにＩｎと、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分、及びさらにＡｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種の他の金属成分を添加し合金化してなるＡｇ基合金からなることもできる。
この後者の態様のＡｇ基合金において、Ｉｎは、Ａｇに対し、０．０１〜５．０ｍａｓｓ％、好ましくは０．１〜１．５ｍａｓｓ％の範囲内の量で添加することができる。また、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分は、Ａｇに対し、合計で０．０１〜５．０ｍａｓｓ％、好ましくは０．１〜１．５ｍａｓｓ％の範囲内の量で添加することができる。さらに、Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種の他の金属成分は、Ａｇに対し、合計で０．０１〜０．１ｍａｓｓ％未満、好ましくは０．０２〜０．０８ｍａｓｓ％の範囲内の量で添加することができる。
Ａｇ合金は、例えば、Ａｇに対し、ＩｎとＣｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分を上記の量で添加し、あるいはＡｇに対し、ＩｎとＣｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分とＡｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種の他の金属成分を上記の量で添加し、ガス炉、高周波溶解炉などの適当な金属溶解炉内で約１０００〜１２００℃の温度で溶融することにより製造することができる。溶解時の雰囲気は空気中で十分であるが、必要に応じ、不活性ガス雰囲気又は真空を使用してもよい。
原料として使用されるＡｇ；Ｉｎ；Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分ならびにＡｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種の他の金属成分としては、粒状、板状、塊状等の形態で市販されているものを使用することができるが、通常、純度が９９．９％以上、特に９９．９５％以上のものが好適である。
かくして、Ａｇ中に、Ｉｎと、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分、あるいはＩｎと、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種の金属成分と、Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種の他の金属成分を、前記の割合で含有するＡｇ基合金が得られる。このＡｇ基合金から構成されるスパッタリングターゲット材は、Ａｇが本来もつ高い反射率を維持しており、しかも、耐酸化性、耐硫化性などの耐食性が、従来のＡｇやＡｇ−Ｍｇ合金に比べて遥かに向上している。
したがって、本発明の上記Ａｇ基合金から構成されるスパッタリングターゲット材は、高反射率が要求されるＣＤやＤＶＤに代表される光ディスク媒体の反射膜用として、また、反射型ＳＴＮ液晶表示装置や有機ＥＬ表示装置などの光反射性薄膜用として有利に使用することができる。
また、ＣＤやＤＶＤに代表される光ディスク媒体および反射型ＳＴＮ液晶表示や有機ＥＬ表示装置に使用される反射膜に対しては、耐食性に加えて、使用条件下における耐高温高湿性や耐熱性も要求される。
耐高温高湿性及び耐熱性は、Ａｇ−Ｉｎ二元系Ａｇ基合金においてもＡｇに比較して或る程度向上するが、次世代大容量光記録メディア等に対しては、さらなる耐高温高湿性、耐熱性の改善が求められている。本発明のスパッタリングターゲット材から形成される薄膜はこの要求を満たすものであり、次世代大容量光記録メディア用の反射膜として特に有用である。
本発明のＡｇ基合金から構成されるスパッタリングターゲット材からの反射膜の形成は、それ自体既知のスパッタリング法、例えば、高周波（ＲＦ）スパッタリング法、直流（ＤＣ）スパッタリング法、マグネトロンスパッタリング法等により行なうことができる。
以下、本発明を実施例によりさらに具体的に説明するが、本発明の範囲はこれら実施例によって何ら限定されるものではない。
実施例
実施例１−１〜１−５及び比較例１−１〜１−３
Ａｇに所定の金属元素を加え、ガス炉内で約１０５０℃の温度に加熱して溶融した後、鋳型で鋳造し、加工し、表１に示す組成のスパッタリングターゲット材を作製した。
このスパッタリングターゲット材を用い、ＲＦスパッタリング法により、ガラス基板上に厚さが約１５０ｎｍの表１に示すと同じ組成の薄膜を形成せしめた。

Figure 0004162652
形成せしめた薄膜の反射率を測定した後、基板を０．０１％硫化ナトリウム（Ｎａ２Ｓ）水溶液中に１時間浸漬し、再度反射率を測定し、浸漬前後での反射率の変化率を下記式により算出した。その下記表２に結果を示す。
変化率（％）＝１００−（浸漬後の反射率／浸漬前の反射率×１００）
Figure 0004162652
表２から明らかなように、実施例１−１〜１−５の薄膜の反射率の変化は比較例１−１〜１−３の薄膜と比較して遥かに少なく、耐食性が向上していることがわかる。
実施例２−１〜２−４及び比較例２−１〜２−２
反射膜を液晶関係や有機ＥＬ、ＤＶＤ、ＤＶＤ−ＲＷやＤＶＤ−ＲＡＭ等に使用する場合、使用条件によっては２００℃以上の高温に曝される場合があるが、例えば、純銀の薄膜は２００℃以上に曝されると、膜の凝集等を起こし白く濁り反射率が落ちることがある。そのため、これらの用途では、熱に対する膜の安定性が求められる。特に、光記録メディアにおいて、レーザーの使用波長が４０５ｎｍの場合、短波長領域での耐熱性が要求される。
そこで、本発明のスパッタリングターゲット材から形成される薄膜の熱的安定性を調べるために、前記実施例と同様にして下記表３に示す組成のスパッタリングターゲット材を作製し、それを用いて前記実施例と同様にしてガラス基板上に膜さが約１５０ｎｍの下記表３に示す組成の薄膜を形成せしめ、その膜の熱的安定性を調べた。
Figure 0004162652
薄膜の熱的安定性を評価するため、形成せしめた薄膜の反射率を測定した後、その薄膜を大気中で２５０℃、１時間熱処理し、再度反射率を測定し、熱処理前後での反射率の変化率を下記式により算出した。その結果を下記表４に示す。
変化率（％）＝１００−（熱処理後の反射率／熱処理前の反射率×１００）
Figure 0004162652
表４の結果から、測定波長が７００ｎｍでは、各試料とも熱処理前後で反射率に殆ど変化が無いものの、測定波長が４００ｎｍの場合、実施例２−１〜２−４の薄膜は、比較例２−１及び２−２の薄膜と比較して、耐熱性が遥かに向上していることがわかる。
実施例３−１〜３−３及び比較例３−１
反射膜を液晶のような半透過・反射電極膜に使用する場合、反射膜に対しては、配線用のために、ウェットエッチングによるパターニング特性が求められる。
そこで、本発明のスパッタリングターゲット材から形成される薄膜のパターニング特性を調べるために、前記実施例と同様にして下記表５に示す組成のスパッタリングターゲット材を作製し、それから前記実施例と同様にして下記表５に示す組成の薄膜を形成せしめ、ウェットエッチングによるパターニングを行い、その特性を評価した。なお、ウェットエッチングには、燐酸＋硝酸＋酢酸＋水の混合溶液を使用した。その結果を下記表６に示す。
Figure 0004162652
Figure 0004162652
表６から明らかなように、実施例３−１〜３−３の薄膜では良好な結果が得られたが、比較例３−１の薄膜は、エッチング後、残渣物が一部溶け残り基板に付着していた。残渣物はＡｕであった。TECHNICAL FIELD The present invention relates to a sputtering target material for forming a thin film having improved corrosion resistance, particularly sulfidation resistance, while maintaining a high reflectance, and a thin film formed using this sputtering target material.
BACKGROUND ART Reflective films used in optical recording media such as CD (Compact Disc) and DVD (Digital Versatile Disc), reflective STN (Super Twist Nematic) liquid crystal display devices, organic EL (Electro luminescence) display devices, etc. In general, Al or an Al alloy is used for the light-reflective conductive film used.
The light-reflective thin film used for applications such as the above-mentioned optical recording media, liquid crystal display devices, and organic EL display devices is generally produced by producing a sputtering target material having desired properties and using the sputtering target material. It is manufactured by forming a film by an RF (high frequency) sputtering method, a DC (direct current) sputtering method, or the like.
The thin film made of Al or Al alloy produced by the above method has a certain degree of reflectivity, low electrical resistance, and forms a passive film on the surface layer, so that it has stable corrosion resistance even in the air. However, the reflectance of a thin film made of Al or an Al alloy is, for example, about 80% in the case of light having a wavelength of 700 nm, and is not sufficiently satisfactory for applications requiring high reflectance.
Therefore, a thin film having a high reflectance is required. For example, an optical disk medium represented by CD or DVD is formed by using Au or Ag as a sputtering target material instead of Al or Al alloy. It is also proposed to use Ag having a high reflectivity as a thin film material for the reflective STN liquid crystal display device.
However, Au is expensive, and Ag has a problem in corrosion resistance, particularly oxidation resistance and sulfidation resistance, as compared with Al. For example, when Ag reacts with sulfur, it produces Ag sulfide, which is blackened and the reflectance decreases.
Therefore, for example, Japanese Patent Laid-Open No. 7-3363 proposes to improve the corrosion resistance by adding a small amount of Mg to Ag and alloying.
However, sufficient corrosion resistance cannot be obtained even by alloying these Ags.
In addition, next-generation large-capacity optical recording media are planned to use laser light with a short wavelength such as 405 nm in order to increase the storage capacity. Corrosion resistance, heat resistance, etc. under such conditions are expected. It is requested.
A main object of the present invention is to provide a sputtering target material for forming a thin film made of an Ag alloy having improved corrosion resistance, particularly sulfidation resistance, while maintaining high reflectance.
DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve the above-mentioned object, the present inventors have now confirmed that Ag contains a specific small amount of In and a small amount of at least one metal component selected from Cu, Ni and Co. When an alloy is added to form an alloy, an Ag-based alloy with significantly improved corrosion resistance, particularly sulfidation resistance and heat resistance can be obtained while maintaining the high reflectivity of Ag. Furthermore, when a small amount of at least one other metal component selected from Au, Pt and Pd is added to form an alloy, the corrosion resistance, particularly the sulfidation resistance is further improved, and the present invention has been completed.
Thus, the present invention is composed of an Ag-based alloy comprising 0.01 to 5.0 mass% of In and 0.01 to 5.0 mass% of at least one selected from Cu, Ni and Co in Ag. The present invention provides a sputtering target material for forming a highly corrosion-resistant thin film having a high reflectivity.
In the present invention, Ag is selected from 0.01 to 5.0 mass% of In, 0.01 to 5.0 mass% of at least one selected from Cu, Ni and Co, and Au, Pd and Pt. The present invention provides a sputtering target material for forming a highly corrosion-resistant thin film having a high reflectance, characterized in that it is made of an Ag-based alloy containing at least one kind in an amount of less than 0.01 to 0.1 mass%.
The present invention also provides a thin film made of an Ag-based alloy containing 0.01 to 5.0 mass% of In and 0.01 to 5.0 mass% of at least one selected from Cu, Ni and Co in Ag. Is to provide.
In the present invention, moreover, Ag is selected from 0.01 to 5.0 mass%, at least one selected from Cu, Ni and Co from 0.01 to 5.0 mass%, and selected from Au, Pd and Pt. The present invention provides a thin film made of an Ag-based alloy containing at least one of the above components in an amount of less than 0.01 to 0.1 mass%.
Hereinafter, the present invention will be described in more detail.
BEST MODE FOR CARRYING OUT THE INVENTION According to one aspect, a sputtering target material of the present invention is based on Ag, and is an Ag alloy formed by alloying at least one selected from In, Cu, Ni and Co with In. It consists of
The In can be added in an amount within a range of 0.01 to 5.0 mass%, preferably 0.1 to 1.5 mass% with respect to Ag. In addition, at least one metal component selected from Cu, Ni and Co is added in a total amount of 0.01 to 5.0 mass%, preferably 0.1 to 1.5 mass% with respect to Ag. be able to.
According to another aspect, the sputtering target material of the present invention is based on Ag, and includes at least one metal component selected from In, Cu, Ni, and Co, and at least selected from Au, Pd, and Pt. It can also be made of an Ag-based alloy obtained by alloying with another kind of metal component.
In the Ag-based alloy of the latter embodiment, In can be added in an amount in the range of 0.01 to 5.0 mass%, preferably 0.1 to 1.5 mass% with respect to Ag. In addition, at least one metal component selected from Cu, Ni and Co is added in a total amount of 0.01 to 5.0 mass%, preferably 0.1 to 1.5 mass% with respect to Ag. be able to. Further, at least one other metal component selected from Au, Pd and Pt is a total amount of 0.01 to less than 0.1 mass%, preferably 0.02 to 0.08 mass% with respect to Ag. Can be added.
In the Ag alloy, for example, at least one metal component selected from In, Cu, Ni, and Co is added to Ag in the above amount, or at least one selected from In, Cu, Ni, and Co to Ag. And at least one other metal component selected from Au, Pd and Pt are added in the above amounts, and the temperature is about 1000 to 1200 ° C. in a suitable metal melting furnace such as a gas furnace or a high-frequency melting furnace. It can be manufactured by melting. The atmosphere at the time of dissolution is sufficient in air, but an inert gas atmosphere or a vacuum may be used if necessary.
Ag used as a raw material: In; at least one metal component selected from Cu, Ni and Co and at least one other metal component selected from Au, Pd and Pt are in the form of particles, plates, lumps, etc. However, those having a purity of 99.9% or more, particularly 99.95% or more are suitable.
Thus, in Ag, at least one metal component selected from In and Cu, Ni and Co, or at least one metal component selected from In and Cu, Ni and Co, and Au, Pd and Pt are selected. An Ag-based alloy containing at least one other metal component in the above ratio can be obtained. The sputtering target material composed of this Ag-based alloy maintains the high reflectivity inherent in Ag, and is more resistant to corrosion such as oxidation resistance and sulfidation resistance than conventional Ag and Ag-Mg alloys. Far improved.
Therefore, the sputtering target material composed of the above Ag-based alloy of the present invention is used for a reflective film of an optical disk medium represented by CD or DVD, which requires high reflectivity, and for a reflective STN liquid crystal display device or organic material. It can be advantageously used for a light reflective thin film such as an EL display device.
In addition to corrosion resistance, optical disk media represented by CD and DVD and reflective films used in reflective STN liquid crystal displays and organic EL display devices have high temperature and high humidity resistance and heat resistance under operating conditions. Required.
The high-temperature and high-humidity resistance and heat resistance are improved to some extent in Ag-In binary Ag-based alloys as compared with Ag. There is a need for improved heat resistance. The thin film formed from the sputtering target material of the present invention satisfies this requirement and is particularly useful as a reflective film for the next generation large-capacity optical recording media.
The reflective film is formed from the sputtering target material composed of the Ag-based alloy of the present invention by a known sputtering method, for example, a radio frequency (RF) sputtering method, a direct current (DC) sputtering method, a magnetron sputtering method, or the like. be able to.
Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
Examples Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3
A predetermined metal element was added to Ag, heated to a temperature of about 1050 ° C. in a gas furnace and melted, then cast in a mold and processed to produce a sputtering target material having the composition shown in Table 1.
Using this sputtering target material, a thin film having the same composition as shown in Table 1 having a thickness of about 150 nm was formed on a glass substrate by RF sputtering.
Figure 0004162652
After measuring the reflectance of the formed thin film, the substrate was immersed in an aqueous solution of 0.01% sodium sulfide (Na 2 S) for 1 hour, the reflectance was measured again, and the rate of change in reflectance before and after immersion was calculated. It was calculated by the following formula. The results are shown in Table 2 below.
Rate of change (%) = 100− (reflectance after immersion / reflectivity before immersion × 100)
Figure 0004162652
As is apparent from Table 2, the change in reflectance of the thin films of Examples 1-1 to 1-5 is far less than that of the thin films of Comparative Examples 1-1 to 1-3, and the corrosion resistance is improved. I understand that.
Examples 2-1 to 2-4 and comparative examples 2-1 to 2-2
When the reflective film is used for liquid crystal, organic EL, DVD, DVD-RW, DVD-RAM, etc., it may be exposed to a high temperature of 200 ° C. or more depending on the use conditions. When exposed to the above, the film may be agglomerated and become white and turbid and the reflectance may decrease. Therefore, in these applications, the stability of the film against heat is required. In particular, in an optical recording medium, when the wavelength of the laser used is 405 nm, heat resistance in the short wavelength region is required.
Therefore, in order to investigate the thermal stability of the thin film formed from the sputtering target material of the present invention, a sputtering target material having the composition shown in the following Table 3 was prepared in the same manner as in the above-described example, and the above-described implementation was performed using it. In the same manner as in the example, a thin film having a composition shown in the following Table 3 having a film thickness of about 150 nm was formed on a glass substrate, and the thermal stability of the film was examined.
Figure 0004162652
In order to evaluate the thermal stability of the thin film, after measuring the reflectance of the formed thin film, the thin film was heat treated in the atmosphere at 250 ° C. for 1 hour, the reflectance was measured again, and the reflectance before and after the heat treatment was measured. The change rate was calculated by the following formula. The results are shown in Table 4 below.
Rate of change (%) = 100− (reflectance after heat treatment / reflectance before heat treatment × 100)
Figure 0004162652
From the results of Table 4, when the measurement wavelength is 700 nm, there is almost no change in the reflectance before and after the heat treatment, but when the measurement wavelength is 400 nm, the thin films of Examples 2-1 to 2-4 are Comparative Example 2. It can be seen that the heat resistance is far improved compared to the thin films of -1 and 2-2.
Examples 3-1 to 3-3 and Comparative Example 3-1
When the reflective film is used for a semi-transmissive / reflective electrode film such as a liquid crystal, the reflective film is required to have patterning characteristics by wet etching for wiring.
Therefore, in order to investigate the patterning characteristics of the thin film formed from the sputtering target material of the present invention, a sputtering target material having the composition shown in Table 5 below was prepared in the same manner as in the above example, and then as in the above example. A thin film having the composition shown in Table 5 below was formed, patterned by wet etching, and its characteristics were evaluated. For wet etching, a mixed solution of phosphoric acid + nitric acid + acetic acid + water was used. The results are shown in Table 6 below.
Figure 0004162652
Figure 0004162652
As is clear from Table 6, good results were obtained with the thin films of Examples 3-1 to 3-3, but the thin film of Comparative Example 3-1 was partially dissolved in the remaining substrate after etching. It was attached. The residue was Au.

Claims (13)

Ａｇに、Ｉｎを０.０１〜５．０mass％と、Ｃｕを０．０１〜５．０mass％含有せしめてなるＡｇ基合金より構成されていることを特徴とする高反射率を有する高耐食性薄膜形成用スパッタリングターゲット材。High corrosion resistance with high reflectivity, characterized in that it is composed of an Ag-based alloy containing 0.01 to 5.0 mass% of In and 0.01 to 5.0 mass% of Cu in Ag. Sputtering target material for thin film formation. Ｉｎを０.１〜１．５mass含有する請求項１に記載のスパッタリングターゲット材。  The sputtering target material of Claim 1 containing 0.1-1.5 mass of In. Ｃｕを０．１〜１．５mass％含有する請求項１又は２に記載のスパッタリングターゲット材。The sputtering target material of Claim 1 or 2 containing 0.1-1.5 mass% of Cu. Ａｇに、Ｉｎを０Ag is 0 for In .. ０１〜５．０01-5.0 massmass ％と、Ｃｕを０．０１〜５．０% And Cu from 0.01 to 5.0 massmass ％含有せしめてなるＡｇ基合金からなる薄膜。A thin film made of an Ag-based alloy. 請求項４に記載の薄膜よりなる光ディスク媒体。An optical disk medium comprising the thin film according to claim 4. 請求項４に記載の薄膜を用いてなる反射型ＳＴＮ液晶表示又は有機ＥＬ表示装置。A reflective STN liquid crystal display or organic EL display device using the thin film according to claim 4. Ａｇに、Ｉｎを０.０１〜５．０mass％と、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０.０１〜５．０mass％と、Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種を０.０１〜０．１mass％未満含有せしめてなるＡｇ基合金より構成されていることを特徴とする高反射率を有する高耐食性薄膜形成用スパッタリングターゲット材。  Ag contains 0.01 to 5.0 mass% of In, 0.01 to 5.0 mass% of at least one selected from Cu, Ni and Co, and 0.01 to at least one selected from Au, Pd and Pt. A sputtering target material for forming a highly corrosion-resistant thin film having a high reflectivity, comprising an Ag-based alloy containing less than ~ 0.1 mass%. Ｉｎを０.１〜１．５mass含有する請求項７に記載のスパッタリングターゲット材。The sputtering target material of Claim 7 containing 0.1-1.5 mass of In. Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０．１〜１．５mass％含有する請求項７又は８に記載のスパッタリングターゲット材。The sputtering target material according to claim 7 or 8 , comprising 0.1 to 1.5 mass% of at least one selected from Cu, Ni and Co. Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種を０.０２〜０．０８mass％含有する請求項７〜９にいずれかに記載のスパッタリングターゲット材。  The sputtering target material in any one of Claims 7-9 which contains 0.02-0.08 mass% of at least 1 type chosen from Au, Pd, and Pt. Ａｇに、Ｉｎを０ . ０１〜５．０ mass ％と、Ｃｕ、Ｎｉ及びＣｏから選ばれる少なくとも一種を０ . ０１〜５．０ mass ％と、Ａｕ、Ｐｄ及びＰｔから選ばれる少なくとも一種を０ . ０１〜０．１ mass ％未満含有せしめてなるＡｇ基合金からなる薄膜。 To Ag, and 0. 01~5.0 mass% of an In, Cu, and 0. 01~5.0 mass% of at least one selected from Ni and Co, Au, at least one selected from Pd and Pt 0 A thin film made of an Ag-based alloy containing less than 01-0.1 mass % . 請求項１１に記載の薄膜よりなる光ディスク媒体。An optical disk medium comprising the thin film according to claim 11 . 請求項１１に記載の薄膜を用いてなる反射型ＳＴＮ液晶表示又は有機ＥＬ表示装置。A reflective STN liquid crystal display or organic EL display device using the thin film according to claim 11 .
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