JP2008115425A - Sputtering target for use in forming transparent electroconductive film - Google Patents
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この発明は、液晶表示装置、エレクトロルミネッセンス表示装置、帯電防止導電膜コーティング、ガスセンサーなどに用いられる透明導電膜を形成するためのスパッタリングターゲット（以下、ターゲットと云う）に関するものである。 The present invention relates to a sputtering target (hereinafter referred to as a target) for forming a transparent conductive film used for a liquid crystal display device, an electroluminescence display device, an antistatic conductive film coating, a gas sensor, and the like.
一般に、液晶表示装置、エレクトロルミネッセンス表示装置、帯電防止導電膜コーティング、ガスセンサーなどに用いられる透明導電膜として、Ｉｎ−Ｓｎ複合酸化物（以下、ＩＴＯという）、Ｚｎ−Ａｌ複合酸化物（以下、ＡＺＯという）、（Ｚｎ−Ｇａ複合酸化物（以下、ＧＺＯという）などの複合酸化物からなる透明導電膜が知られており、この透明導電膜を作製する方法の一つとしてスパッタリング法がある。このスパッタリング法により透明導電膜を形成するには、Ｉｎ−Ｓｎ合金ターゲット、Ｚｎ−Ａｌ合金ターゲット、Ｚｎ−Ｇａ合金ターゲットなど合金ターゲットを用い、酸素を含むアルゴン雰囲気中でスパッタリングすることにより形成する。前記Ｉｎ−Ｓｎ合金ターゲットはＳｎ：０．１〜３０質量％を含有し、残部がＩｎからなる組成を有し、Ｚｎ−Ａｌ合金ターゲットはＡｌ０．１〜３０質量％を含有し、残部がＺｎからなる組成を有し、さらにＺｎ−Ｇａ合金ターゲットはＧａ：０．１〜３０質量％を含有し、残部がＺｎからなる組成を有することが知られている。
これら合金ターゲットを用いてスパッタリングを行なうと、合金ターゲットを構成する各成分のスパッタ率の違いによりスパッタ初期とそれ以降とでは得られる透明導電膜の組成比が変化することから目的とする膜組成に達するまでのプレスパッタ時間を長く取る必要がある。さらに、これら合金ターゲットを用いて安定して所定の酸素含有量を有する透明導電膜を得るには、いずれもスパッタリング雰囲気中の酸素量を厳しく制御する必要があることから安定的に成膜することが難しかった。
Generally, as a transparent conductive film used for a liquid crystal display device, an electroluminescence display device, an antistatic conductive film coating, a gas sensor, etc., an In—Sn composite oxide (hereinafter referred to as ITO), a Zn—Al composite oxide (hereinafter referred to as “ITO”). A transparent conductive film made of a composite oxide such as AZO) or (Zn—Ga composite oxide (hereinafter referred to as GZO) is known, and one of methods for producing this transparent conductive film is a sputtering method. In order to form a transparent conductive film by this sputtering method, it is formed by sputtering in an argon atmosphere containing oxygen using an alloy target such as an In—Sn alloy target, a Zn—Al alloy target, or a Zn—Ga alloy target. The In—Sn alloy target contains Sn: 0.1 to 30% by mass, and the balance is the Zn-Al alloy target contains 0.1 to 30% by mass of Al, the balance is composed of Zn, and the Zn-Ga alloy target is Ga: 0.1 to 30% by mass. It is known that it has a composition that contains Zn and the balance is made of Zn.
When sputtering is performed using these alloy targets, the composition ratio of the transparent conductive film obtained varies depending on the sputtering rate of each component constituting the alloy target. It is necessary to take a long pre-sputtering time to reach. Furthermore, in order to obtain a transparent conductive film having a predetermined oxygen content stably using these alloy targets, it is necessary to strictly control the oxygen amount in the sputtering atmosphere, so that stable film formation is possible. It was difficult.
そのために、現在では、雰囲気をアルゴン雰囲気中または酸素制御を行なう必要のない酸素を含むアルゴン雰囲気中でＩＴＯ複合酸化物、ＡＺＯ複合酸化物、ＧＺＯ複合酸化物などの複合酸化物ターゲットを用いてスパッタリングする方法が主流となっている。そして、前記ＩＴＯ複合酸化物ターゲットは、ＳｎＯ2：０．１〜２０モル％を含有し、残部がＩｎ2Ｏ3からなる組成を有し、前記ＡＺＯ複合酸化物ターゲットは、Ａｌ2Ｏ3：０．１〜２０モル％を含有し、残部がＺｎＯからなる組成を有し、さらに、前記ＧＺＯ複合酸化物ターゲットはＧａ2Ｏ3：０．１〜２０モル％を含有し、残部がＺｎＯからなる組成を有することが知られている（特許文献１、２、３参照）。
しかし、近年、スパッタリング雰囲気中の酸素制御技術は以前に比べて格段に進歩し、スパッタリング雰囲気中の酸素量の制御は簡単になってきた。さらに合金ターゲットを用いるスパッタリング法の成膜速度は、複合酸化物ターゲットを用いる成膜速度よりも速いことから、コスト削減の目的で合金ターゲットを用いるスパッタリング法が再び注目され始めている。しかし、合金ターゲットを用いるスパッタリング法では形成される透明導電膜の成分組成が一定になるまでに時間がかかり過ぎ、そのためにプレスパッタ時間を長く取らなければならないという欠点は未だ解消されていない。 However, in recent years, the oxygen control technology in the sputtering atmosphere has greatly advanced compared to before, and the control of the oxygen amount in the sputtering atmosphere has become easier. Furthermore, since the film formation rate of the sputtering method using an alloy target is faster than the film formation rate using a complex oxide target, the sputtering method using an alloy target has begun to attract attention again for the purpose of cost reduction. However, in the sputtering method using an alloy target, it takes too much time for the component composition of the transparent conductive film to be formed to be constant, and thus the drawback of having to take a long pre-sputtering time has not yet been solved.
そこで、本発明者らは上述の合金ターゲットを用いるスパッタリング法の前記欠点を解消すべく研究を行った。その結果、
Ｉｎ−Ｓｎ合金結晶粒の周囲をＩＴＯ複合酸化物膜で包囲した組織を有するターゲット、
Ｚｎ−Ａｌ合金結晶粒の周囲をＡＺＯの複合酸化物膜で包囲した組織を有するターゲット、
Ｚｎ−Ｇａ合金粉末の周囲をＧＺＯの複合酸化物膜で包囲した組織を有するターゲット、
を用いてスパッタリングすると、得られた透明導電膜の成分組成が安定するまでの時間（すなわち、プレスパッタ時間）が格段に短くなり、したがって、透明導電膜の成膜時間が大幅に短縮される、などの研究結果が得られたのである。
Therefore, the present inventors have studied to eliminate the above-described drawbacks of the sputtering method using the above-described alloy target. as a result,
A target having a structure in which an In-Sn alloy crystal grain is surrounded by an ITO composite oxide film,
A target having a structure in which the periphery of Zn-Al alloy crystal grains is surrounded by a composite oxide film of AZO,
A target having a structure in which the periphery of the Zn-Ga alloy powder is surrounded by a composite oxide film of GZO,
When the sputtering is performed, the time until the component composition of the obtained transparent conductive film is stabilized (that is, the pre-sputtering time) is remarkably shortened. Therefore, the film formation time of the transparent conductive film is greatly reduced. The research results were obtained.
この発明は、かかる研究結果に基づいて成されたものであって、
（１）Ｓｎ：０．１〜３０質量％を含有し、残部がＩｎからなる組成を有するＩｎ−Ｓｎ合金結晶粒をＩｎ−Ｓｎ複合酸化物が包囲している組織を有する透明導電膜形成用スパッタリングターゲット、
（２）Ａｌ：０．１〜３０質量％を含有し、残部がＺｎからなる組成を有するＺｎ−Ａｌ合金結晶粒をＺｎ−Ａｌ複合酸化物が包囲している組織を有する透明導電膜形成用スパッタリングターゲット、
（３）Ｇａ：０．１〜３０質量％を含有し、残部がＺｎからなる組成を有するＺｎ−Ｇａ合金結晶粒をＺｎ−Ｇａ複合酸化物が包囲している組織を有する透明導電膜形成用スパッタリングターゲット、に特徴を有するものである。
前記Ｉｎ、Ｓｎ、Ｚｎ、ＡｌおよびＧａの含有量は、従来から知られているＩｎ−Ｓｎ合金ターゲット、Ｚｎ−Ａｌ合金ターゲット、Ｚｎ−Ｇａ合金ターゲットに含まれる含有量と同じであり、すでに知られている範囲であるのでその限定理由の説明は省略する。
The present invention has been made based on such research results,
(1) For forming a transparent conductive film having a structure in which an In—Sn composite oxide surrounds In—Sn alloy crystal grains containing Sn: 0.1 to 30% by mass and the balance being composed of In Sputtering target,
(2) For forming a transparent conductive film having a structure in which Zn—Al composite oxide surrounds Zn—Al alloy crystal grains containing Al: 0.1 to 30% by mass and the balance being composed of Zn Sputtering target,
(3) Ga: For forming a transparent conductive film having a structure in which Zn—Ga composite oxide surrounds Zn—Ga alloy crystal grains having a composition of 0.1 to 30% by mass and the balance being made of Zn The sputtering target is characterized.
The contents of the In, Sn, Zn, Al, and Ga are the same as the contents of the conventionally known In—Sn alloy target, Zn—Al alloy target, and Zn—Ga alloy target. Therefore, the explanation of the reason for limitation is omitted.
この発明の透明導電膜形成用スパッタリングターゲットを作製するには、まず、いずれも平均粒径：０．１〜２５０μｍを有するＩｎ−Ｓｎ合金粉末、Ｚｎ−Ａｌ合金粉末、Ｚｎ−Ｇａ合金粉末などの合金粉末を用意する。これら合金粉末は、ガスアトマイズ粉末であってもよく、また機械粉砕粉末であってもよい。つぎに、これら合金粉末を酸素雰囲気中で加熱処理することにより、Ｉｎ−Ｓｎ合金粉末の表面にＩＴＯ複合酸化物膜を形成したＩＴＯ被覆Ｉｎ−Ｓｎ合金粉末、Ｚｎ−Ａｌ合金粉末の表面にＡＺＯ複合酸化物膜を形成したＡＺＯ被覆Ｚｎ−Ａｌ合金粉末、Ｚｎ−Ｇａ合金粉末の表面にＧＺＯ複合酸化物膜を形成したＧＺＯ被覆Ｚｎ−Ｇａ合金粉末を作製する。また、ガスアトマイズにより粉末を作製する際、ガスとしてＡｒ＋１０％Ｏ２等の酸化性ガスを用いてガスアトマイズすることにより作製することができる。このとき合金粉末の表面に形成される酸化膜は厚さ：２０〜１０００ｎｍの範囲内にあることが好ましい。酸化膜の厚さが２０ｎｍ未満ではターゲット製造プロセスにおける成形過程で初期の粉末形状を保った状態で成形することが困難となるので好ましくなく、一方、１０００ｎｍを越えるようになると極端にスパッタ速度が低下し、量産に不向きとなるので好ましくないからである。このようにして得られたＩＴＯ被覆Ｉｎ−Ｓｎ合金粉末、ＡＺＯ被覆Ｚｎ−Ａｌ合金粉末、ＧＺＯ被覆Ｚｎ−Ｇａ合金粉末をそれぞれホットプレス、熱間静水圧プレスまたは冷間静水圧プレスを行なうことにより作製する。 In order to produce the sputtering target for forming a transparent conductive film of the present invention, first, all of In-Sn alloy powder, Zn-Al alloy powder, Zn-Ga alloy powder having an average particle size of 0.1 to 250 μm, etc. Prepare alloy powder. These alloy powders may be gas atomized powders or mechanically pulverized powders. Next, by heat-treating these alloy powders in an oxygen atmosphere, an ITO-coated In-Sn alloy powder in which an ITO composite oxide film is formed on the surface of the In-Sn alloy powder, and an AZO on the surface of the Zn-Al alloy powder. AZO-coated Zn-Al alloy powder having a complex oxide film formed thereon and a GZO-coated Zn-Ga alloy powder having a GZO complex oxide film formed on the surface of the Zn-Ga alloy powder are prepared. Also, making the powder by gas atomization can be produced by gas atomization using an Ar + 10% O 2 and the like oxidizing gas as a gas. At this time, the oxide film formed on the surface of the alloy powder is preferably in the range of thickness: 20 to 1000 nm. If the thickness of the oxide film is less than 20 nm, it is not preferable because it is difficult to mold the powder in the initial manufacturing process in the target manufacturing process. On the other hand, if the thickness exceeds 1000 nm, the sputtering rate is extremely reduced. However, it is not preferable for mass production. The ITO-coated In-Sn alloy powder, AZO-coated Zn-Al alloy powder, and GZO-coated Zn-Ga alloy powder thus obtained were subjected to hot pressing, hot isostatic pressing, or cold isostatic pressing, respectively. Make it.
この発明の組織を有する透明導電膜形成用ターゲットは、プレスパッタ時間を大幅に短縮することができ、透明導電膜の製造コストを大幅に下げることができるなど優れた効果を奏するものである。 The target for forming a transparent conductive film having the structure of the present invention has excellent effects such that the pre-sputtering time can be greatly shortened and the manufacturing cost of the transparent conductive film can be greatly reduced.
つぎに、この発明の透明導電膜形成用ターゲットを具体的に説明する。まず、原料粉末として、いずれもガスアトマイズして得られたＳｎ：５質量％を含有し、残部がＩｎからなる成分組成のＩｎ−Ｓｎ合金ガスアトマイズ粉末、Ａｌ：４質量％を含有し、残部がＺｎからなる成分組成のＺｎ−Ａｌ合金ガスアトマイズ粉末、およびＧａ：１０質量％を含有し、残部がＺｎからなる成分組成のＺｎ−Ｇａ合金ガスアトマイズ粉末を用意する。これらＩｎ−Ｓｎ合金ガスアトマイズ粉末を大気中：温度：１２０℃、３時間保持の条件で加熱し、Ｚｎ−Ａｌ合金ガスアトマイズ粉末を大気中：温度：２００℃、３時間保持の条件で加熱し、さらにＺｎ−Ｇａ合金ガスアトマイズ粉末をそれぞれ大気中：温度：１００℃、３時間保持の条件で加熱することにより、
Ｉｎ−Ｓｎ合金ガスアトマイズ粉末の表面にＩＴＯ複合酸化物膜を形成したＩＴＯ被覆Ｉｎ−Ｓｎ合金粉末、
Ｚｎ−Ａｌ合金ガスアトマイズ粉末の表面にＡＺＯ複合酸化物膜を形成したＡＺＯ被覆Ｚｎ−Ａｌ合金粉末、および、
Ｚｎ−Ｇａ合金ガスアトマイズ粉末の表面にＧＺＯ複合酸化物膜を形成したＧＺＯ被覆Ｚｎ−Ｇａ合金粉末を作製し用意した。
Next, the transparent conductive film forming target of the present invention will be specifically described. First, as a raw material powder, all contain Sn: 5 mass% obtained by gas atomization, the remainder contains an In—Sn alloy gas atomized powder of a component composition composed of In, Al: 4 mass%, and the balance is Zn A Zn—Al alloy gas atomized powder having a component composition consisting of Ga and 10% by mass of Ga: Zn—Ga alloy gas atomized powder having a component composition consisting of Zn is prepared. These In—Sn alloy gas atomized powders are heated in the atmosphere: temperature: 120 ° C. for 3 hours, the Zn—Al alloy gas atomized powders are heated in the atmosphere: temperature: 200 ° C. for 3 hours, and further By heating the Zn—Ga alloy gas atomized powder in the air: temperature: 100 ° C. for 3 hours,
ITO-coated In-Sn alloy powder in which an ITO composite oxide film is formed on the surface of an In-Sn alloy gas atomized powder,
An AZO-coated Zn-Al alloy powder in which an AZO composite oxide film is formed on the surface of a Zn-Al alloy gas atomized powder; and
A GZO-coated Zn—Ga alloy powder having a GZO composite oxide film formed on the surface of a Zn—Ga alloy gas atomized powder was prepared and prepared.
実施例１
先に作製したＩＴＯ被覆Ｉｎ−Ｓｎ合金粉末を金型に充填した状態で、ホットプレス装置に装入し、雰囲気：１×１０-2Ｔｏｒｒの真空雰囲気、温度：１２０℃、圧力：３０ＭＰａ、保持時間：３時間保持の条件でホットプレスすることにより、直径：１５４ｍｍ×厚さ：６ｍｍの寸法をもった本発明ターゲット１を作製した。この本発明ターゲット１の断面組織を金属顕微鏡で観察したところ、Ｉｎ−Ｓｎ合金結晶粒相互が結合している部分も見られたが、大部分のＩｎ−Ｓｎ合金結晶粒はＩＴＯ複合酸化膜が包囲している組織が見られた。
Example 1
The ITO-coated In—Sn alloy powder prepared earlier was charged into a mold and charged into a hot press apparatus, and the atmosphere was maintained in a vacuum atmosphere of 1 × 10 −2 Torr, temperature: 120 ° C., pressure: 30 MPa, and maintained. The target 1 of the present invention having a size of diameter: 154 mm × thickness: 6 mm was produced by hot pressing under a condition of time: 3 hours. When the cross-sectional structure of the target 1 of the present invention was observed with a metallurgical microscope, a portion where In—Sn alloy crystal grains were bonded to each other was also observed, but most of the In—Sn alloy crystal grains were made of an ITO composite oxide film. The surrounding organization was seen.
一方、先に作製したＩｎ−Ｓｎ合金ガスアトマイズ粉末を金型に充填した状態で、ホットプレス装置に装入し、雰囲気：１×１０-2Ｔｏｒｒの真空雰囲気、温度：１２０℃、圧力：３０ＭＰａ、保持時間：３時間保持の条件でホットプレスすることにより、直径：１５４ｍｍ×厚さ：６ｍｍの寸法をもった従来ターゲット１を作製した。この従来ターゲット１の断面を金属顕微鏡で観察したところ、Ｉｎ−Ｓｎ合金結晶粒が集合した焼結合金組織が見られた。 On the other hand, the In—Sn alloy gas atomized powder prepared earlier was charged into a mold and charged into a hot press apparatus. Atmosphere: vacuum atmosphere of 1 × 10 −2 Torr, temperature: 120 ° C., pressure: 30 MPa, Holding time: Hot pressing under the condition of holding for 3 hours, a conventional target 1 having a diameter of 154 mm × thickness: 6 mm was produced. When the cross section of this conventional target 1 was observed with a metal microscope, a sintered alloy structure in which In—Sn alloy crystal grains were aggregated was observed.
得られた本発明ターゲット１および従来ターゲット１を無酸素銅製の水冷バッキングプレートにハンダ付けした状態で、直流マグネトロンスパッタリング装置に装着し、まず装置内を真空排気装置にて１×１０-6Ｔｏｒｒ以下に排気したのち、Ａｒ＋１０％Ｏ２ガスを導入して装置内雰囲気を１．５×１０-3Ｔｏｒｒのスパッタガス圧とした。また、厚さ：０．６ｍｍのポリカーボネート基板をターゲットとの間隔：７０ｍｍにて配置した。
かかる状態で本発明ターゲット１および従来ターゲット１に、直流電源にてスパッタ電力：０．１ｋＷを印加し、スパッタリング開始から５分ごとに作製した前記ポリカーボネート基板表面に形成された厚さ：５０ｎｍを有する透明導電膜サンプルのＩｎおよびＳｎの成分組成を測定し、この測定結果を表１に示した。
The obtained target 1 of the present invention and the conventional target 1 are soldered to a water-cooled backing plate made of oxygen-free copper and mounted on a DC magnetron sputtering apparatus. First, the inside of the apparatus is 1 × 10 −6 Torr or less with a vacuum exhaust apparatus. Then, Ar + 10% O 2 gas was introduced to set the atmosphere in the apparatus to a sputtering gas pressure of 1.5 × 10 −3 Torr. In addition, a polycarbonate substrate having a thickness of 0.6 mm was disposed at a distance of 70 mm from the target.
In this state, sputtering power: 0.1 kW is applied to the target 1 of the present invention and the conventional target 1 with a DC power source, and the thickness formed on the surface of the polycarbonate substrate produced every 5 minutes from the start of sputtering has a thickness of 50 nm. The component composition of In and Sn of the transparent conductive film sample was measured, and the measurement results are shown in Table 1.
表１に示される結果から、Ｉｎ−Ｓｎ合金結晶粒をＩＴＯ複合酸化膜が包囲している組織を有する本発明ターゲット１で形成された透明導電膜サンプルはスパッタリング時間が１０分経過後からはＩｎおよびＳｎの含有量がほぼ一定となることからプレスパッタ時間は１０分必要とすることがわかる。
一方、従来ターゲット１で形成した透明導電膜サンプルはスパッタリング時間が３０分経過後からはＩｎおよびＳｎの含有量がほぼ一定となるのでプレスパッタ時間は３０分必要となることがわかる。
したがって、本発明ターゲット１のプレスパッタ時間と従来ターゲット１のプレスパッタ時間を比較すると、本発明ターゲット１のプレスパッタ時間は従来ターゲット１のプレスパッタ時間に比べて格段に短いことがわかる。
From the results shown in Table 1, the transparent conductive film sample formed with the target 1 of the present invention having a structure in which the ITO composite oxide film surrounds the In—Sn alloy crystal grains has been obtained after the sputtering time of 10 minutes has elapsed. It can be seen that the pre-sputtering time is 10 minutes because the Sn and Sn contents are almost constant.
On the other hand, it can be seen that the transparent conductive film sample formed with the conventional target 1 requires a pre-sputtering time of 30 minutes since the In and Sn contents are substantially constant after the sputtering time of 30 minutes has elapsed.
Therefore, when comparing the pre-sputtering time of the target 1 of the present invention and the pre-sputtering time of the conventional target 1, it can be seen that the pre-sputtering time of the target 1 of the present invention is much shorter than the pre-sputtering time of the conventional target 1.
実施例２
先に作製したＡＺＯ被覆Ｚｎ−Ａｌ合金粉末を金型に充填した状態で、ホットプレス装置に装入し、雰囲気：１×１０-2Ｔｏｒｒの真空雰囲気、温度：２００℃、圧力：３０ＭＰａ、保持時間：３時間保持の条件でホットプレスすることにより、直径：１５４ｍｍ×厚さ：６ｍｍの寸法をもった本発明ターゲット２を作製した。この本発明ターゲット２の断面を金属顕微鏡で観察したところ、Ｚｎ−Ａｌ合金結晶粒相互が結合している部分も見られたが、大部分のＺｎ−Ａｌ合金結晶粒はＡＺＯ複合酸化膜が包囲している組織が見られた。
Example 2
The previously prepared AZO-coated Zn-Al alloy powder was charged in a mold and charged into a hot press apparatus. Atmosphere: 1 × 10 −2 Torr vacuum atmosphere, temperature: 200 ° C., pressure: 30 MPa, holding The target 2 of the present invention having a size of diameter: 154 mm × thickness: 6 mm was produced by hot pressing under a condition of time: 3 hours. When the cross section of the target 2 of the present invention was observed with a metal microscope, a portion where Zn—Al alloy crystal grains were bonded to each other was also observed, but most of the Zn—Al alloy crystal grains were surrounded by an AZO composite oxide film. Organization was seen.
一方、先に作製したＺｎ−Ａｌ合金ガスアトマイズ粉末を金型に充填した状態で、ホットプレス装置に装入し、雰囲気：１×１０-2Ｔｏｒｒの真空雰囲気、温度：２００℃、圧力：３０ＭＰａ、保持時間：３時間保持の条件でホットプレスすることにより、直径：１５４ｍｍ×厚さ：６ｍｍの寸法をもった従来ターゲット２を作製した。この従来ターゲット２の断面を金属顕微鏡で観察したところ、Ｚｎ−Ａｌ合金結晶粒が集合した焼結合金組織が見られた。 On the other hand, in a state where the previously prepared Zn—Al alloy gas atomized powder was filled in the mold, it was charged into a hot press apparatus, atmosphere: 1 × 10 −2 Torr vacuum atmosphere, temperature: 200 ° C., pressure: 30 MPa, Holding time: Hot pressing under the condition of holding for 3 hours, a conventional target 2 having a diameter of 154 mm × thickness: 6 mm was produced. When the cross section of this conventional target 2 was observed with a metal microscope, a sintered alloy structure in which Zn-Al alloy crystal grains were aggregated was observed.
得られた本発明ターゲット２および従来ターゲット２を無酸素銅製の水冷バッキングプレートにハンダ付けした状態で、直流マグネトロンスパッタリング装置に装着し、まず装置内を真空排気装置にて１×１０-6Ｔｏｒｒ以下に排気したのち、Ａｒ＋１０％Ｏ２ガスを導入して装置内雰囲気を１．５×１０-3Ｔｏｒｒのスパッタガス圧とした。また、厚さ：０．６ｍｍのポリカーボネート基板をターゲットとの間隔：７０ｍｍにて配置した。
かかる状態で本発明ターゲット２および従来ターゲット２に、直流電源にてスパッタ電力：０．１ｋＷを印加し、スパッタリング開始から５分ごとに作製した前記ポリカーボネート基板表面に形成された厚さ：５０ｎｍを有する透明導電膜サンプルのＺｎおよびＡｌの成分組成を測定し、この測定結果を表２に示した。
The obtained target 2 of the present invention and the conventional target 2 are soldered to a water-cooled backing plate made of oxygen-free copper and mounted on a DC magnetron sputtering device. First, the inside of the device is 1 × 10 −6 Torr or less by a vacuum exhaust device. Then, Ar + 10% O 2 gas was introduced to set the atmosphere in the apparatus to a sputtering gas pressure of 1.5 × 10 −3 Torr. In addition, a polycarbonate substrate having a thickness of 0.6 mm was disposed at a distance of 70 mm from the target.
In this state, sputtering power: 0.1 kW is applied to the target 2 of the present invention and the conventional target 2 with a DC power source, and the thickness formed on the surface of the polycarbonate substrate produced every 5 minutes from the start of sputtering has a thickness of 50 nm. The component composition of Zn and Al of the transparent conductive film sample was measured, and the measurement results are shown in Table 2.
表２に示される結果から、Ｚｎ−Ａｌ合金結晶粒をＡＺＯ複合酸化膜が包囲している組織を有する本発明ターゲット２を用いて形成された透明導電膜サンプルは、
スパッタリング時間が１０分経過後からはＺｎおよびＡｌの含有量がほぼ一定となることからプレスパッタ時間は１０分必要となることがわかる。
一方、従来ターゲット２で形成した透明導電膜サンプルはスパッタリング時間が３０分経過後からはＺｎおよびＡｌの含有量がほぼ一定となるのでプレスパッタ時間は３０分必要となることがわかる。したがって、本発明ターゲット２のプレスパッタ時間と従来ターゲット２のプレスパッタ時間を比較すると、本発明ターゲット２のプレスパッタ時間は従来ターゲット２のプレスパッタ時間に比べて格段に短いことがわかる。
From the results shown in Table 2, the transparent conductive film sample formed using the target 2 of the present invention having a structure in which Zn-Al alloy crystal grains are surrounded by an AZO composite oxide film,
It can be seen that the pre-sputtering time of 10 minutes is required since the Zn and Al contents are almost constant after the sputtering time of 10 minutes has elapsed.
On the other hand, it can be seen that the transparent conductive film sample formed with the conventional target 2 requires 30 minutes of pre-sputtering time since the Zn and Al contents are substantially constant after the sputtering time of 30 minutes. Therefore, comparing the pre-sputtering time of the target 2 of the present invention with the pre-sputtering time of the conventional target 2, it can be seen that the pre-sputtering time of the target 2 of the present invention is much shorter than the pre-sputtering time of the conventional target 2.
実施例３
先に作製したＧＺＯ被覆Ｚｎ−Ｇａ合金粉末をゴム型に充填した状態で、冷間静水圧プレス装置に装入し、圧力：１００ＭＰａ、保持時間：１時間保持の条件で冷間静水圧プレスすることにより、直径：１５４ｍｍ×厚さ：６ｍｍの寸法をもった本発明ターゲット３を作製した。この本発明ターゲット３の断面を金属顕微鏡で観察したところ、Ｚｎ−Ｇａ合金結晶粒相互が結合している部分も見られたが、大部分のＺｎ−Ｇａ合金結晶粒はＧＺＯ複合酸化膜が包囲している組織が見られた。
Example 3
The GZO-coated Zn—Ga alloy powder prepared above is filled in a rubber mold and charged into a cold isostatic press, and cold isostatic press is performed under the conditions of pressure: 100 MPa, holding time: 1 hour. Thus, the target 3 of the present invention having a size of diameter: 154 mm × thickness: 6 mm was produced. When the cross section of the target 3 of the present invention was observed with a metal microscope, a portion where Zn—Ga alloy crystal grains were bonded to each other was also observed, but most of the Zn—Ga alloy crystal grains were surrounded by a GZO composite oxide film. Organization was seen.
一方、先に作製したＺｎ−Ｇａ合金ガスアトマイズ粉末をゴム型に充填した状態で、冷間静水圧プレス装置に装入し、圧力：１００ＭＰａ、保持時間：１時間保持の条件で冷間静水圧プレスすることにより、直径：１５４ｍｍ×厚さ：６ｍｍの寸法をもった従来ターゲット３を作製した。この従来ターゲット３の断面を金属顕微鏡で観察したところ、Ｚｎ−Ｇａ合金結晶粒が集合した焼結合金組織が見られた。 On the other hand, with the previously prepared Zn-Ga alloy gas atomized powder filled in a rubber mold, it was charged into a cold isostatic press, and the cold isostatic press was performed under the conditions of pressure: 100 MPa, holding time: 1 hour. Thus, a conventional target 3 having a diameter of 154 mm × thickness: 6 mm was produced. When the cross section of this conventional target 3 was observed with a metal microscope, a sintered alloy structure in which Zn—Ga alloy crystal grains were aggregated was observed.
得られた本発明ターゲット３および従来ターゲット３を無酸素銅製の水冷バッキングプレートにハンダ付けした状態で、直流マグネトロンスパッタリング装置に装着し、まず装置内を真空排気装置にて１×１０-6Ｔｏｒｒ以下に排気したのち、Ａｒ＋１０％Ｏ２ガスを導入して装置内雰囲気を１．５×１０-3Ｔｏｒｒのスパッタガス圧とした。また、厚さ：０．６ｍｍのポリカーボネート基板をターゲットとの間隔：７０ｍｍにて配置した。
かかる状態で本発明ターゲット３および従来ターゲット３に、直流電源にてスパッタ電力：０．１ｋＷを印加し、スパッタリング開始から５分ごとに作製した前記ポリカーボネート基板表面に形成された厚さ：５０ｎｍを有する透明導電膜サンプルのＺｎおよびＧａの成分組成を測定し、この測定結果を表３に示した。
The obtained target 3 of the present invention and the conventional target 3 are soldered to a water-cooled backing plate made of oxygen-free copper and mounted on a DC magnetron sputtering apparatus. First, the inside of the apparatus is 1 × 10 −6 Torr or less with a vacuum exhaust apparatus. Then, Ar + 10% O 2 gas was introduced to set the atmosphere in the apparatus to a sputtering gas pressure of 1.5 × 10 −3 Torr. In addition, a polycarbonate substrate having a thickness of 0.6 mm was disposed at a distance of 70 mm from the target.
In this state, sputtering power: 0.1 kW is applied to the target 3 of the present invention and the conventional target 3 with a DC power source, and the thickness formed on the polycarbonate substrate surface produced every 5 minutes from the start of sputtering has a thickness of 50 nm. The component composition of Zn and Ga of the transparent conductive film sample was measured, and the measurement results are shown in Table 3.
表３に示される結果から、Ｚｎ−Ｇａ合金結晶粒をＧＺＯ複合酸化膜が包囲している組織を有する本発明ターゲット３を用いて形成された透明導電膜サンプルは、
スパッタリング時間が１０分経過後からはＺｎおよびＧａの含有量がほぼ一定となることからプレスパッタ時間は１０分必要となることがわかる。一方、従来ターゲット３を用いて形成した透明導電膜サンプルはスパッタリング時間が３０分経過後からはＺｎおよびＧａの含有量がほぼ一定となるのでプレスパッタ時間は３０分必要となることがわかる。
したがって、本発明ターゲット３のプレスパッタ時間と従来ターゲット３のプレスパッタ時間を比較すると、本発明ターゲット３のプレスパッタ時間は従来ターゲット３のプレスパッタ時間に比べて格段に短いことがわかる。
From the results shown in Table 3, a transparent conductive film sample formed using the present target 3 having a structure in which Zn-Ga alloy crystal grains are surrounded by a GZO composite oxide film,
It can be seen that the pre-sputtering time of 10 minutes is required since the Zn and Ga contents are almost constant after the sputtering time of 10 minutes has elapsed. On the other hand, it can be seen that the transparent conductive film sample formed using the conventional target 3 requires a pre-sputtering time of 30 minutes since the Zn and Ga contents are substantially constant after the sputtering time of 30 minutes has elapsed.
Therefore, comparing the pre-sputtering time of the target 3 of the present invention and the pre-sputtering time of the conventional target 3, it can be seen that the pre-sputtering time of the target 3 of the present invention is much shorter than the pre-sputtering time of the conventional target 3.
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|---|---|---|---|---|
| JPS6196609A (en) * | 1984-10-15 | 1986-05-15 | 大阪特殊合金株式会社 | Transparent conductive film |
| JPH09170076A (en) * | 1995-08-18 | 1997-06-30 | Wc Heraeus Gmbh | Target for cathode sputtering and production of the same |
| JPH10237630A (en) * | 1996-04-12 | 1998-09-08 | Asahi Glass Co Ltd | Oxide coating, laminated body and heir production |
| JP2000026168A (en) * | 1998-07-06 | 2000-01-25 | Mitsubishi Materials Corp | Production of metal oxide sintered body |
| JP2003151359A (en) * | 2001-11-16 | 2003-05-23 | Bridgestone Corp | Transparent conductive film and touch panel |
| JP2008097969A (en) * | 2006-10-11 | 2008-04-24 | Bridgestone Corp | Zinc oxide based transparent conductive film, and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6196609A (en) * | 1984-10-15 | 1986-05-15 | 大阪特殊合金株式会社 | Transparent conductive film |
| JPH09170076A (en) * | 1995-08-18 | 1997-06-30 | Wc Heraeus Gmbh | Target for cathode sputtering and production of the same |
| JPH10237630A (en) * | 1996-04-12 | 1998-09-08 | Asahi Glass Co Ltd | Oxide coating, laminated body and heir production |
| JP2000026168A (en) * | 1998-07-06 | 2000-01-25 | Mitsubishi Materials Corp | Production of metal oxide sintered body |
| JP2003151359A (en) * | 2001-11-16 | 2003-05-23 | Bridgestone Corp | Transparent conductive film and touch panel |
| JP2008097969A (en) * | 2006-10-11 | 2008-04-24 | Bridgestone Corp | Zinc oxide based transparent conductive film, and its manufacturing method |
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