JP2013189657A - Transparent oxide film and method of producing the same - Google Patents

Transparent oxide film and method of producing the same Download PDF

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JP2013189657A
JP2013189657A JP2012039041A JP2012039041A JP2013189657A JP 2013189657 A JP2013189657 A JP 2013189657A JP 2012039041 A JP2012039041 A JP 2012039041A JP 2012039041 A JP2012039041 A JP 2012039041A JP 2013189657 A JP2013189657 A JP 2013189657A
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oxide film
transparent oxide
sputtering
film
substrate
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JP5884549B2 (en
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Takeshi Yamaguchi
山口　　剛
Shuhin Cho
守斌 張
Yuichi Kondo
佑一 近藤
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Mitsubishi Materials Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a zinc oxide-based transparent oxide film which has a low refractive index and excellent gas barrier properties, and to provide a method of producing the same.SOLUTION: A transparent oxide film is amorphous, and has a composition which contains, based on the total metal component amount, 0.9-20.0 at% Al and 25.5-68.0 at% Si with the balance consisting of Zn and unavoidable impurities. In a production method, DC sputtering is conducted under the environment being at least one of in an inert gas atmosphere that contains oxygen and in the state of heating a substrate, using a sputtering target consisting of an oxide sintered compact which has a composition that contains, based on the total metal component amount, 0.3-4.0 wt% Al and 6.0-14.5 wt% Si with the balance consisting of Zn and unavoidable impurities, and has a composite oxide ZnSiOand ZnO present in the structure of the sintered compact.

Description

本発明は、有機発光表示素子、液晶表示素子、エレクトロルミネッセンス表示素子、電気泳動方式表示素子、トナー表示素子などの電子ペーパーやフィルム型太陽電池などに用いられるガスバリア層や薄膜封止層に含まれる無機膜、および化合物半導体による薄膜太陽電池の透明電極層上のガスバリア層として利用される酸化亜鉛系のガスバリア性に優れる透明酸化物膜およびその製造方法に関するものである。   The present invention is included in a gas barrier layer or a thin film sealing layer used for an electronic paper such as an organic light emitting display element, a liquid crystal display element, an electroluminescence display element, an electrophoretic display element, a toner display element, or a film type solar cell. The present invention relates to a transparent oxide film having excellent gas barrier properties based on zinc oxide, which is used as a gas barrier layer on a transparent electrode layer of a thin film solar cell made of an inorganic film and a compound semiconductor, and a method for producing the same.

従来、液晶表示素子やエレクトロルミネッセンス表示素子、電気泳動方式表示素子、トナー表示素子などの電子ペーパーやフィルム型太陽電池などに用いられるガスバリア層、および化合物半導体による薄膜太陽電池（例えば、ＣＩＧＳ（Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ）系太陽電池）の透明電極層上のガスバリア層として、透明酸化物膜をスパッタリング法で作製する技術が知られている。   Conventionally, a gas barrier layer used for electronic paper such as a liquid crystal display element, an electroluminescence display element, an electrophoretic display element, a toner display element, a film type solar cell, and the like, and a thin film solar cell using a compound semiconductor (for example, CIGS (Cu-- As a gas barrier layer on a transparent electrode layer of an (In-Ga-Se) solar cell), a technique for producing a transparent oxide film by a sputtering method is known.

例えば、特許文献１では、酸化スズと、Ｓｉ、Ｇｅ、Ａｌからなる群から選ばれる少なくとも１種の添加元素とを含有し、該添加元素は、添加元素とＳｎの含有量の総和に対して１５原子％〜６３原子％の割合で含まれ、結晶相の構成に、添加元素の金属相、該添加元素の酸化物相、該添加元素とＳｎの複合酸化物相のうちの１種以上が含まれ、該添加元素の酸化物相、および、該添加元素とＳｎの複合酸化物相が、平均粒径５０μｍ以下の大きさで分散している酸化物焼結体をスパッタリングターゲットとして用い、直流パルシング法を利用したスパッタリング法により、樹脂フィルム基材の表面に透明酸化物膜を形成する方法が提案されている。   For example, Patent Document 1 contains tin oxide and at least one additive element selected from the group consisting of Si, Ge, and Al. The additive element is based on the total content of the additive element and Sn. It is contained at a ratio of 15 atomic% to 63 atomic%, and the composition of the crystal phase includes at least one of a metal phase of the additive element, an oxide phase of the additive element, and a composite oxide phase of the additive element and Sn. Using the oxide sintered body in which the oxide phase of the additive element and the composite oxide phase of the additive element and Sn are dispersed with an average particle size of 50 μm or less as a sputtering target, A method of forming a transparent oxide film on the surface of a resin film substrate by a sputtering method using a pulsing method has been proposed.

この方法で得られた透明酸化物膜は、酸化スズと、Ｓｉ、Ｇｅ、Ａｌからなる群から選ばれる少なくとも１種の添加元素とを含有する透明酸化物膜であって、該添加元素は、添加元素とＳｎの総和に対して１５原子％〜６３原子％の割合で含まれ、非晶質膜であり、かつ、波長６３３ｎｍにおける屈折率が１．９０以下であるとされている。   The transparent oxide film obtained by this method is a transparent oxide film containing tin oxide and at least one additional element selected from the group consisting of Si, Ge, and Al. It is contained at a ratio of 15 atomic% to 63 atomic% with respect to the total of the additive element and Sn, is an amorphous film, and has a refractive index of 1.90 or less at a wavelength of 633 nm.

また、特許文献２には、相変化光ディスク用保護膜に使用される光透過膜であって用途は異なるが、Ｎｂ２Ｏ５、Ｖ２Ｏ５、Ｂ２Ｏ３、ＳｉＯ２、Ｐ２Ｏ５から選択された１種以上のガラス形成酸化物を０．０１〜２０重量％と、Ａｌ２Ｏ３又はＧａ２Ｏ３を０．０１〜２０重量％含有し、残部Ｉｎ２Ｏ３、ＳｎＯ２、ＺｎＯから選択された１種以上の酸化物であるスパッタリングターゲットを用いて、スパッタリング法により、Ｎｂ２Ｏ５、Ｖ２Ｏ５、Ｂ２Ｏ３、ＳｉＯ２、Ｐ２Ｏ５から選択された１種以上のガラス形成酸化物を０．０１〜２０重量％と、Ａｌ２Ｏ３又はＧａ２Ｏ３を０．０１〜２０重量％含有し、残部Ｉｎ２Ｏ３、ＳｎＯ２、ＺｎＯから選択された１種以上の酸化物である光透過膜を成膜する方法が提案されている。 Patent Document 2 discloses a light-transmitting film used as a protective film for a phase change optical disk and uses thereof are different, but Nb 2 O 5 , V 2 O 5 , B 2 O 3 , SiO 2 , P 2 O. 1 to 20% by weight of one or more glass-forming oxides selected from 5 and 0.01 to 20% by weight of Al 2 O 3 or Ga 2 O 3 with the balance being In 2 O 3 , SnO 2 , selected from Nb 2 O 5 , V 2 O 5 , B 2 O 3 , SiO 2 , P 2 O 5 by a sputtering method using a sputtering target that is one or more oxides selected from ZnO In addition, 0.01 to 20% by weight of one or more kinds of glass-forming oxides and 0.01 to 20% by weight of Al 2 O 3 or Ga 2 O 3 , and the balance from In 2 O 3 , SnO 2 and ZnO Translucent being one or more selected oxides A method for forming an overfilm has been proposed.

特開２００７−２９０９１６号公報JP 2007-290916 A 特開２０００−１１９０６２号公報JP 2000-119062 A

上記従来の技術には、以下の課題が残されている。
すなわち、上記特許文献１の技術に記載のターゲットでは、スパッタリング時にノジュールが多く発生して装置の掃除等に手間がかかるため、酸化スズ系ではなく他の組成系のガスバリア性に優れる透明酸化物膜が要望されている。しかしながら、上記特許文献２の技術で作製する透明酸化物膜は、光ディスク用であるために屈折率が高く、上述した電子ペーパーや太陽電池に用いる樹脂フィルム基材上のガスバリア層に採用するには、樹脂フィルム基材の屈折率（例えば波長６３３ｎｍで屈折率ｎ：１．５〜１．７）に近づけるために屈折率を低くする必要がある。このため、酸化亜鉛系の透明酸化物膜にＳｉＯ２をより多く含有させて屈折率を下げることが考えられるが、特許文献２で記載されているように、ＳｉＯ２が２０ｗｔ％を超えると添加した成分であるＳｉＯ２の結晶相が析出してしまう不都合があった。結晶相が析出してしまうとガスバリア性（例えば水蒸気バリア性）としての機能が低下してしまうため、保護膜として採用することができない。 The following problems remain in the conventional technology.
That is, in the target described in the technique of Patent Document 1, a large amount of nodules is generated at the time of sputtering, and it takes time to clean the apparatus. Is desired. However, the transparent oxide film produced by the technique of the above-mentioned Patent Document 2 has a high refractive index because it is used for an optical disk, and is used for a gas barrier layer on a resin film substrate used in the above-described electronic paper or solar cell. In order to approach the refractive index of the resin film substrate (for example, the refractive index n: 1.5 to 1.7 at a wavelength of 633 nm), it is necessary to lower the refractive index. For this reason, it is conceivable to reduce the refractive index by adding more SiO 2 to the zinc oxide-based transparent oxide film. However, as described in Patent Document 2, it is added when SiO 2 exceeds 20 wt%. There was a disadvantage that the crystal phase of SiO 2 , which was a component, was precipitated. If the crystal phase is precipitated, the function as gas barrier property (for example, water vapor barrier property) is deteriorated, so that it cannot be employed as a protective film.

本発明は、前述の課題に鑑みてなされたもので、成膜速度が速いスパッタリング法を用いて屈折率が低く良好なガスバリア性を有した酸化亜鉛系の透明酸化物膜およびその製造方法を提供することを目的とする。   The present invention has been made in view of the above-mentioned problems, and provides a zinc oxide-based transparent oxide film having a low refractive index and good gas barrier properties using a sputtering method having a high film formation rate, and a method for producing the same. The purpose is to do.

本発明者らは、ＡＺＯ（Al-Zn-O：Aluminium doped Zinc Oxide：アルミニウム添加酸化亜鉛）膜にＳｉＯ２を含有させると屈折率が低くなることから、透明酸化物膜としてＺｎＯ−ＳｉＯ２−Ａｌ２Ｏ３膜をスパッタリングにより成膜するべく研究を行った。この研究において、特定の組織からなるスパッタリングターゲットを用い、スパッタ成膜時の雰囲気または基板の温度を特定の条件に設定することで、透明で低屈折率かつ高ガスバリア性能を有するＺｎＯ−ＳｉＯ２−Ａｌ２Ｏ３膜を得られることを突き止めた。 Since the refractive index is lowered when SiO 2 is contained in an AZO (Al-Zn-O: Aluminum doped Zinc Oxide) film, the present inventors have used ZnO—SiO 2 — as a transparent oxide film. Research was conducted to form an Al 2 O 3 film by sputtering. In this research, ZnO-SiO 2 — having a transparent, low refractive index and high gas barrier performance is obtained by using a sputtering target having a specific structure and setting the atmosphere or substrate temperature during sputtering film formation to a specific condition. It has been found that an Al 2 O 3 film can be obtained.

したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。すなわち、本発明の透明酸化物膜は、全金属成分量に対してＡｌ：０．９〜２０．０ａｔ％、Ｓｉ：２５．５〜６８．０ａｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有し、非晶質であることを特徴とする。
すなわち、この透明酸化物膜では、全金属成分量に対してＡｌ：０．９〜２０．０ａｔ％、Ｓｉ：２５．５〜６８．０ａｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有し、非晶質であるので、従来よりも可視光域で低い屈折率が得られると共に高いガスバリア性（例えば、水蒸気バリア性）を有している。さらに、可視光域で９５％以上の高い透過率が得られ、良好な透明性を有している。 Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems. That is, the transparent oxide film of the present invention contains Al: 0.9 to 20.0 at%, Si: 25.5 to 68.0 at% with respect to the total amount of metal components, and the balance is made of Zn and inevitable impurities. The composition is characterized by being amorphous.
That is, in this transparent oxide film, Al: 0.9 to 20.0 at%, Si: 25.5 to 68.0 at% with respect to the total amount of metal components, with the balance being Zn and inevitable impurities Since it has a composition and is amorphous, it has a lower refractive index in the visible light region than the conventional one and has a high gas barrier property (for example, a water vapor barrier property). Furthermore, a high transmittance of 95% or more is obtained in the visible light region, and the film has good transparency.

なお、上記Ａｌの含有量を０．９〜２０．０ａｔ％とした理由は、０．９ａｔ％未満の膜を得るための組成に設定したスパッタリングターゲットでは異常放電が発生し、安定なＤＣスパッタができないためであり、２０．０ａｔ％を超える膜を得るための組成に設定したスパッタリングターゲットでも異常放電が発生し、安定なＤＣスパッタができない。なお、Ａｌの含有量は、１２ａｔ％以下がより好ましい。すなわち、Ａｌの含有量が１２ａｔ％以下であると、相対的にＳｉ含有量を高く維持できるため、より低い屈折率および、より高いガスバリア性が得られるためである。
また、上記Ｓｉの含有量を２５．５〜６８．０ａｔ％とした理由は、２５．５ａｔ％未満であると所望の低屈折率およびガスバリア性が得られず、６８．０ａｔ％を超える膜を得るための組成に設定したスパッタリングターゲットではＳｉ量が多くなりＤＣスパッタができないためである。 The reason why the Al content is 0.9-20.0 at% is that abnormal discharge occurs in the sputtering target set to a composition for obtaining a film of less than 0.9 at%, and stable DC sputtering is caused. This is because an abnormal discharge occurs even in a sputtering target set to a composition for obtaining a film exceeding 20.0 at%, and stable DC sputtering cannot be performed. Note that the Al content is more preferably 12 at% or less. That is, when the Al content is 12 at% or less, the Si content can be maintained relatively high, so that a lower refractive index and higher gas barrier properties can be obtained.
The reason why the Si content is 25.5 to 68.0 at% is that if it is less than 25.5 at%, a desired low refractive index and gas barrier property cannot be obtained, and a film exceeding 68.0 at% is formed. This is because the sputtering target set to the composition to obtain has a large amount of Si and cannot perform DC sputtering.

また、本発明の透明酸化物膜は、波長７５０ｎｍの光透過率が９３％以上であることを特徴とする。
すなわち、一般のＤＣスパッタで成膜可能な酸化物とは異なり、導電性酸化物にあるような電子による長波長側の吸収が少ないため、ＤＣスパッタで成膜され、かつ可視光長波長の光を損失しない可視光全域で高い透明性を持つ膜となる。 The transparent oxide film of the present invention is characterized in that the light transmittance at a wavelength of 750 nm is 93% or more.
In other words, unlike oxides that can be formed by general DC sputtering, there is little absorption on the long wavelength side by electrons as in conductive oxides, so that light is formed by DC sputtering and has a long wavelength of visible light. It becomes a film having high transparency in the entire visible light range without losing the light.

また、本発明の透明酸化物膜は、可視光域での屈折率平均値が、１．５９〜１．８０であり、厚み５０ｎｍ以上で水蒸気透過率が０．０１ｇ／（ｍ２・ｄａｙ）以下であることを特徴とする。
すなわち、この透明酸化物膜では、可視光域での屈折率平均値が、１．５９〜１．８０であり、厚み５０ｎｍ以上で水蒸気透過率が０．０１ｇ／（ｍ２・ｄａｙ）以下であるので、電子ペーパーや太陽電池で採用される樹脂フィルム基材上に成膜されたガスバリア層として好適である。なお、ここで可視光域は、波長３８０ｎｍ〜７５０ｎｍの範囲とする。 The transparent oxide film of the present invention has an average refractive index in the visible light range of 1.59 to 1.80, a thickness of 50 nm or more and a water vapor transmission rate of 0.01 g / (m 2 · day). It is characterized by the following.
That is, in this transparent oxide film, the average refractive index in the visible light region is 1.59 to 1.80, the thickness is 50 nm or more, and the water vapor transmission rate is 0.01 g / (m 2 · day) or less. Therefore, it is suitable as a gas barrier layer formed on a resin film substrate used in electronic paper and solar cells. Here, the visible light region has a wavelength range of 380 nm to 750 nm.

本発明の透明酸化物膜の製造方法は、上記発明の透明酸化物膜を製造する方法であって、全金属成分量に対してＡｌ：０．３〜４．０ｗｔ％、Ｓｉ：６．０〜１４．５ｗｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有した酸化物焼結体からなり、該焼結体の組織中に複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが存在するスパッタリングターゲットを用い、酸素を含有させた不活性ガス雰囲気中および基板を加熱した状態の少なくとも一方の環境下で、直流電流を投入してスパッタすることを特徴とする。
すなわち、この透明酸化物膜の製造方法では、上記酸化物焼結体の組織中に複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが存在するスパッタリングターゲットを用いるので、ＤＣスパッタが可能になり、さらに酸素を含有させた不活性ガス雰囲気中および基板を加熱した状態の少なくとも一方の環境下で、直流電流を投入してスパッタ(ＤＣスパッタ)するので、Ｓｉを多く含有させた非晶質の透明酸化物膜（ＺｎＯ−ＳｉＯ２−Ａｌ２Ｏ３膜）を成膜することができる。したがって、本発明の製法によれば、従来よりもＳｉＯ２を多く添加可能であり、屈折率を下げつつ、非晶質でガスバリア性の高い透明酸化物膜をＤＣスパッタで成膜可能である。 The method for producing a transparent oxide film of the present invention is a method for producing the transparent oxide film of the above invention, wherein Al: 0.3 to 4.0 wt%, Si: 6.0 with respect to the total amount of metal components. It is composed of an oxide sintered body having a component composition of ˜14.5 wt%, the balance being composed of Zn and inevitable impurities, and the composite oxide Zn 2 SiO 4 and ZnO are present in the structure of the sintered body A sputtering target is used, and sputtering is performed by applying a direct current in an atmosphere of an inert gas containing oxygen and at least one of a heated state of the substrate.
That is, in this method for producing a transparent oxide film, a sputtering target in which the composite oxide Zn 2 SiO 4 and ZnO are present in the structure of the oxide sintered body is used, so that DC sputtering is possible, and oxygen Sputtering (DC sputtering) by applying a direct current in at least one of an atmosphere containing an inert gas and a state in which the substrate is heated. Therefore, an amorphous transparent oxide containing a large amount of Si A film (ZnO—SiO 2 —Al 2 O 3 film) can be formed. Therefore, according to the production method of the present invention, more SiO 2 can be added than before, and an amorphous transparent oxide film having a high gas barrier property can be formed by DC sputtering while lowering the refractive index.

なお、上記Ａｌの含有量を０．３〜４．０ｗｔ％とした理由は、０．３ｗｔ％未満では、異常放電が発生してＤＣスパッタができないためであり、４．０ｗｔ％を超えると、発生したＡｌ２Ｏ３とＺｎＯとの複合酸化物ＺｎＡｌ２Ｏ４に起因する異常放電が発生してＤＣスパッタができないためである。
また、上記Ｓｉの含有量を６．０〜１４．５ｗｔ％とした理由は、６．０ｗｔ％未満では、屈折率を下げる十分な効果が得られないためであり、１４．５ｗｔ％を超えると、十分な導電性を得ることができず、異常放電が発生してＤＣスパッタができないためである。 The reason why the Al content is set to 0.3 to 4.0 wt% is that if it is less than 0.3 wt%, abnormal discharge occurs and DC sputtering cannot be performed. If the content exceeds 4.0 wt%, This is because the abnormal discharge caused by the generated composite oxide ZnAl 2 O 4 of Al 2 O 3 and ZnO occurs, and DC sputtering cannot be performed.
The reason why the Si content is 6.0 to 14.5 wt% is that if it is less than 6.0 wt%, a sufficient effect of lowering the refractive index cannot be obtained, and if it exceeds 14.5 wt%. This is because sufficient conductivity cannot be obtained, abnormal discharge occurs, and DC sputtering cannot be performed.

また、本発明の透明酸化物膜の成膜方法は、前記基板が樹脂フィルム基材であり、前記基板の加熱温度を、１００〜２００℃の範囲に設定することを特徴とする。
すなわち、この透明酸化物膜の製造方法では、基板の加熱温度を、１００〜２００℃の範囲に設定するので、成膜する樹脂フィルム基材への熱影響を抑えつつ、電子ペーパーや太陽電池で採用されるガスバリア層として十分な透明性と低い屈折率とを有する透明酸化物膜が得られる。
なお、上記基板の加熱温度を１００〜２００℃の範囲に設定した理由は、１００℃未満であると膜中のＳｉ含有量が少なくなり透明性が低下すると共に屈折率が変化してしまうためであり、２００℃を超えると樹脂フィルム基材が損傷を受けるためである。 Moreover, the film-forming method of the transparent oxide film of the present invention is characterized in that the substrate is a resin film base material, and the heating temperature of the substrate is set in a range of 100 to 200 ° C.
That is, in this method for producing a transparent oxide film, since the heating temperature of the substrate is set in a range of 100 to 200 ° C., the heat effect on the resin film base material to be formed is suppressed, and electronic paper or solar cells are used. A transparent oxide film having sufficient transparency and a low refractive index as the gas barrier layer employed can be obtained.
The reason why the heating temperature of the substrate is set in the range of 100 to 200 ° C. is that when it is less than 100 ° C., the Si content in the film is reduced, the transparency is lowered and the refractive index is changed. Yes, if the temperature exceeds 200 ° C., the resin film substrate is damaged.

また、本発明の透明酸化物膜の成膜方法は、前記酸素と不活性ガスとの雰囲気ガス全体に対する酸素のガス分圧を、０．０５以上に設定することを特徴とする。
すなわち、この透明酸化物膜の製造方法では、酸素と不活性ガスとの雰囲気ガス全体に対する酸素のガス分圧を、０．０５以上に設定するので、電子ペーパーや太陽電池で採用されるガスバリア層として十分な透明性と低い屈折率とを有する透明酸化物膜が得られる。これは、酸素のガス分圧を０．０５未満にすると、膜中のＳｉ含有量が少なくなり透明性が低下すると共に屈折率が変化してしまうためである。なお、酸素のガス分圧は、０．２を超えるとスパッタの成膜速度が遅くなって生産性が低下するため、０．２以下とすることが好ましい。
このように本発明では、上記基板加熱温度および上記酸素のガス分圧の少なくとも一方を調整してＤＣスパッタすることで、膜中のＳｉの含有量を調整可能である。 Further, the transparent oxide film forming method of the present invention is characterized in that a partial pressure of oxygen with respect to the whole atmosphere gas of oxygen and inert gas is set to 0.05 or more.
That is, in this method for producing a transparent oxide film, the gas partial pressure of oxygen with respect to the entire atmospheric gas of oxygen and inert gas is set to 0.05 or more, so that the gas barrier layer employed in electronic paper and solar cells As a result, a transparent oxide film having sufficient transparency and a low refractive index can be obtained. This is because when the oxygen partial pressure of oxygen is less than 0.05, the Si content in the film decreases, the transparency decreases and the refractive index changes. Note that if the oxygen partial pressure of oxygen exceeds 0.2, the film formation rate of the sputtering is reduced and the productivity is lowered. Therefore, the oxygen partial pressure is preferably 0.2 or less.
As described above, in the present invention, the content of Si in the film can be adjusted by performing DC sputtering by adjusting at least one of the substrate heating temperature and the gas partial pressure of oxygen.

本発明によれば、以下の効果を奏する。
すなわち、本発明に係る透明酸化物膜によれば、全金属成分量に対してＡｌ：０．９〜２８．５ａｔ％、Ｓｉ：２５．５〜６８．０ａｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有し、非晶質であるので、従来よりも可視光域で低い屈折率が得られると共に高いガスバリア性を有している。また、本発明に係る透明酸化物膜の製造方法によれば、上記酸化物焼結体の組織中に複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが存在するスパッタリングターゲットを用いるので、ＤＣスパッタが可能になり、酸素を含有させた不活性ガス雰囲気中および基板を加熱した状態の少なくとも一方の環境下で、直流電流を投入してスパッタするので、非晶質の上記組成の透明酸化物膜（ＺｎＯ−ＳｉＯ２−Ａｌ２Ｏ３膜）を成膜することができる。
したがって、本発明の透明酸化物膜を電子ペーパーや太陽電池などのガスバリア層に採用することで、要求される高透明性、低屈折率および高ガスバリア性が得られ、高信頼性を有すると共に視認性の高い電子ペーパーや変換効率の良好な太陽電池などを作製可能である。 The present invention has the following effects.
That is, according to the transparent oxide film according to the present invention, Al: 0.9-28.5 at%, Si: 25.5-68.0 at% with respect to the total metal component amount, with the balance being Zn and Since it has a component composition composed of inevitable impurities and is amorphous, it has a lower refractive index in the visible light region than the conventional one and has a high gas barrier property. Further, according to the method for producing a transparent oxide film according to the present invention, since a sputtering target in which the composite oxide Zn 2 SiO 4 and ZnO are present in the structure of the oxide sintered body is used, DC sputtering is possible. Therefore, sputtering is performed by applying a direct current in at least one of an inert gas atmosphere containing oxygen and a state in which the substrate is heated. Therefore, an amorphous transparent oxide film (ZnO it can be deposited -SiO 2 -Al 2 O 3 film).
Therefore, by adopting the transparent oxide film of the present invention for gas barrier layers such as electronic paper and solar cells, the required high transparency, low refractive index and high gas barrier properties can be obtained, and it has high reliability and is visible. High-performance electronic paper, solar cells with good conversion efficiency, and the like can be manufactured.

本発明に係る透明酸化物膜およびその製造方法の一実施形態において、使用するスパッタリングターゲットの製造工程を示すフローチャートである。It is a flowchart which shows the manufacturing process of the sputtering target to be used in one Embodiment of the transparent oxide film which concerns on this invention, and its manufacturing method. 本発明に係る透明酸化物膜およびその製造方法の実施例において、透明酸化物膜（実施例３）のＸ線回折（ＸＲＤ）の分析結果を示すグラフである。It is a graph which shows the analysis result of the X-ray diffraction (XRD) of a transparent oxide film (Example 3) in the Example of the transparent oxide film which concerns on this invention, and its manufacturing method. 本発明に係る透明酸化物膜およびその製造方法の実施例において、透明酸化物膜（実施例５）のＸ線回折の分析結果を示すグラフである。It is a graph which shows the analysis result of the X-ray diffraction of a transparent oxide film (Example 5) in the Example of the transparent oxide film which concerns on this invention, and its manufacturing method. 本発明に係る透明酸化物膜およびその製造方法の実施例において、透明酸化物膜（実施例６）のＸ線回折の分析結果を示すグラフである。It is a graph which shows the analysis result of the X-ray diffraction of a transparent oxide film (Example 6) in the Example of the transparent oxide film which concerns on this invention, and its manufacturing method. 本発明に係る透明酸化物膜およびその製造方法の実施例において、透明酸化物膜（実施例１１）のＸ線回折の分析結果を示すグラフである。In the Example of the transparent oxide film which concerns on this invention, and its manufacturing method, it is a graph which shows the analysis result of the X-ray diffraction of a transparent oxide film (Example 11). 本発明に係る透明酸化物膜およびその製造方法の比較例において、透明酸化物膜（比較例４）のＸ線回折の分析結果を示すグラフである。In the comparative example of the transparent oxide film which concerns on this invention, and its manufacturing method, it is a graph which shows the analysis result of the X-ray diffraction of a transparent oxide film (comparative example 4). 本発明に係る透明酸化物膜およびその製造方法の実施例および比較例において、波長に対する透過率を示すグラフである。It is a graph which shows the transmittance | permeability with respect to a wavelength in the Example and comparative example of the transparent oxide film which concern on this invention, and its manufacturing method. 本発明に係る透明酸化物膜およびその製造方法の実施例および比較例において、波長に対する屈折率を示すグラフである。It is a graph which shows the refractive index with respect to a wavelength in the Example and comparative example of the transparent oxide film which concern on this invention, and its manufacturing method. 参考例において、スパッタリングターゲットのＸ線回折（ＸＲＤ）の分析結果を示すグラフである。In a reference example, it is a graph which shows the analysis result of X-ray diffraction (XRD) of a sputtering target. 比較参考例において、スパッタリングターゲットのＸ線回折（ＸＲＤ）の分析結果を示すグラフである。In a comparative reference example, it is a graph which shows the analysis result of X-ray diffraction (XRD) of a sputtering target.

以下、本発明に係る透明酸化物膜およびその製造方法の一実施形態を、図１を参照して説明する。   Hereinafter, an embodiment of a transparent oxide film and a method for producing the same according to the present invention will be described with reference to FIG.

本実施形態の透明酸化物膜は、上述した用途のガスバリア層として利用される膜であって、全金属成分量に対してＡｌ：０．９〜２０．０ａｔ％、Ｓｉ：２５．５〜６８．０ａｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有し、非晶質である。
また、この透明酸化物膜は、膜厚１００ｎｍにおけるシート抵抗値が、１．０×１０１４Ω／ｓｑ以上である。
さらに、この透明酸化物膜は、可視光域での屈折率平均値が、１．５９〜１．８０であり、厚み５０ｎｍ以上で水蒸気透過率が０．０１ｇ／（ｍ２・ｄａｙ）以下である。なお、水蒸気透過率は、ＪＩＳ規格のＫ７１２９法にしたがってモコン法により測定されたものである。 The transparent oxide film of this embodiment is a film used as a gas barrier layer for the above-described applications, and Al: 0.9 to 20.0 at%, Si: 25.5 to 68 with respect to the total amount of metal components. 0.0at%, the balance having a component composition consisting of Zn and inevitable impurities, and being amorphous.
Further, this transparent oxide film has a sheet resistance value of 1.0 × 10 14 Ω / sq or more at a film thickness of 100 nm.
Further, this transparent oxide film has an average refractive index in the visible light region of 1.59 to 1.80, a thickness of 50 nm or more, and a water vapor transmission rate of 0.01 g / (m 2 · day) or less. is there. The water vapor transmission rate is measured by the Mocon method in accordance with JIS standard K7129 method.

また、本実施形態の透明酸化物膜の製造方法は、全金属成分量に対してＡｌ：０．３〜４．０ｗｔ％、Ｓｉ：６．０〜１４．５ｗｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有した酸化物焼結体からなり、該焼結体の組織中に複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが存在するスパッタリングターゲットを用い、酸素を含有させた不活性ガス雰囲気中および基板を加熱した状態の少なくとも一方の環境下で、直流電流を投入してスパッタ（ＤＣスパッタ）する。 Moreover, the manufacturing method of the transparent oxide film of this embodiment contains Al: 0.3-4.0wt%, Si: 6.0-14.5wt% with respect to the total amount of metal components, and the balance is Zn. And a sputtering target in which a composite oxide Zn 2 SiO 4 and ZnO are present in the structure of the sintered body, and an oxygen-containing non-oxidized body. Sputtering (DC sputtering) is performed by applying a direct current in an active gas atmosphere and / or in an environment where the substrate is heated.

このとき、樹脂フィルム基材を基板として用い、基板の加熱温度は１００〜２００℃の範囲に設定する。また、酸素と不活性ガスとの雰囲気ガス全体に対する酸素のガス分圧は０．０５以上に設定する。
上記透明フィルム基材としては、アクリル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエステル樹脂セルロースおよびこれらの共重合樹脂、合成した透明な基板が例示できる。詳しい例として、ポリエステル、ポリエチレンテレフタレート（PET）、ポリブチレンテレフタレート、ポリメチルメタクリレート（PMMA）、アクリル、ポリカーボネート（PC）、ポリスチレン、ポリビニルアルコール、ポリエチレンなどがあげられるが、この限りではない。
なお、上記スパッタリングターゲットは、焼結体の密度が、理論密度の１００〜１０８％である。さらに、このスパッタリングターゲットは、バルク抵抗値が、１Ω・ｃｍ以下である。 At this time, the resin film base material is used as the substrate, and the heating temperature of the substrate is set in the range of 100 to 200 ° C. The gas partial pressure of oxygen with respect to the whole atmosphere gas of oxygen and inert gas is set to 0.05 or more.
Examples of the transparent film substrate include acrylic resins, polyamide resins, polyimide resins, polyester resin celluloses, copolymer resins thereof, and synthesized transparent substrates. Specific examples include, but are not limited to, polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), acrylic, polycarbonate (PC), polystyrene, polyvinyl alcohol, and polyethylene.
In the sputtering target, the density of the sintered body is 100 to 108% of the theoretical density. Furthermore, this sputtering target has a bulk resistance value of 1 Ω · cm or less.

上記焼結体の密度を理論密度比で１００〜１０８％とした理由は、１００％未満では、ターゲットが割れてしまう等の問題が生じるためであり、１０８％を超えると、ほとんどが複合酸化物Ｚｎ２ＳｉＯ４の組織となってしまい、ＤＣスパッタによる放電ができなくなるためである。
ここで、理論密度比の計算には、ＺｎＯは５．６１ｇ／ｃｍ３、ＳｉＯ２は２．２０ｇ／ｃｍ３、Ａｌ2Ｏ３は３．９９ｇ／ｃｍ３の値を用いて計算を行っている。
また、スパッタリングターゲットのバルク抵抗値が、１Ω・ｃｍ以下であるので、安定して良好なＤＣスパッタが可能である。 The reason why the density of the sintered body is set to 100 to 108% in terms of the theoretical density ratio is that if it is less than 100%, there is a problem such as the target being cracked. This is because the structure becomes Zn 2 SiO 4 and discharge by DC sputtering cannot be performed.
Here, the calculation of the theoretical density ratio is performed using the values of 5.61 g / cm 3 for ZnO, 2.20 g / cm 3 for SiO 2 and 3.99 g / cm 3 for Al 2 O 3. Yes.
Further, since the bulk resistance value of the sputtering target is 1 Ω · cm or less, stable and good DC sputtering is possible.

このスパッタリングターゲットを作製する方法は、Ａｌ２Ｏ３粉末とＳｉＯ２粉末とＺｎＯ粉末とを、Ａｌ２Ｏ３：０．５〜５．０ｗｔ％、ＳｉＯ２：１０〜２２ｗｔ％、残部：ＺｎＯおよび不可避不純物からなるように混合して混合粉末とする工程と、この混合粉末を真空中でホットプレスにて焼結する工程とを有している。 A method for producing this sputtering target includes Al 2 O 3 powder, SiO 2 powder, and ZnO powder, Al 2 O 3 : 0.5 to 5.0 wt%, SiO 2 : 10 to 22 wt%, balance: ZnO and It has the process of mixing so that it may consist of an unavoidable impurity, and making it a mixed powder, and the process of sintering this mixed powder in a hot press in a vacuum.

上記製法の一例について詳述すれば、例えば、図１に示すように、まず純度９９．９％以上のＡｌ２Ｏ３粉末とＳｉＯ２粉末とＺｎＯ粉末とを上記含有量範囲となるように秤量し、湿式ボールミルによって粉砕、混合して混合粉末を作製する。例えば、秤量して得られた各粉末とジルコニアボールとをポリ容器（ポリエチレン製ポット）に入れ、ボールミル装置にて所定時間湿式混合し、混合粉末とする。なお、溶媒には、例えばアルコールを用いる。 If an example of the said manufacturing method is explained in full detail, for example, as shown in FIG. 1, first, Al 2 O 3 powder having a purity of 99.9% or more, SiO 2 powder, and ZnO powder are weighed so as to be in the above content range. Then, it is pulverized and mixed by a wet ball mill to produce a mixed powder. For example, each powder obtained by weighing and zirconia balls are placed in a poly container (polyethylene pot) and wet-mixed for a predetermined time in a ball mill apparatus to obtain a mixed powder. For example, alcohol is used as the solvent.

次に、得られた混合粉末を乾燥後、例えば目開き：２５０μｍの篩にかけて造粒し、さらに真空乾燥後、例えば１２００℃にて５時間、２００ｋｇｆ／ｃｍ２の圧力で真空中でホットプレスし、焼結体とする。なお、ホットプレス温度は、１１００〜１２５０℃の範囲が好ましく、圧力は、１５０〜３５０ｋｇｆ／ｃｍ２の範囲が好ましい。
このようにホットプレスした焼結体は、通常放電加工、切削または研削工法を用いて、ターゲットの指定形状に機械加工し、加工後のターゲットをＩｎを半田として、ＣｕまたはＳＵＳ（ステンレス）またはその他金属（例えば、Ｍｏ）からなるバッキングプレートにボンディングし、スパッタに供する。 Next, the obtained mixed powder is dried and then granulated through, for example, a sieve having a mesh opening of 250 μm, and further vacuum dried, and then hot-pressed in vacuum at a pressure of 200 kgf / cm 2 at 1200 ° C. for 5 hours, for example. And a sintered body. The hot press temperature is preferably in the range of 1100 to 1250 ° C., and the pressure is preferably in the range of 150 to 350 kgf / cm 2 .
The hot-pressed sintered body is usually machined to a target shape using electrical discharge machining, cutting or grinding, and the processed target is In or soldered to Cu or SUS (stainless steel) or others. Bonding to a backing plate made of metal (for example, Mo) and subjecting to sputtering.

なお、他の製造方法としては、上記製造方法の湿式ボールミルによる粉砕、混合を、純水を溶媒として内容積３００Ｌのボールミル装置を用いて行い、その後、スプレードライにより乾燥造粒したものを、さらに乾式ボールミルで壊砕し、この壊砕粉末を上記と同様にホットプレスする方法でも構わない。また、上記乾式ボールミルによる壊砕工程を省略した方法でも構わない。   In addition, as another manufacturing method, pulverization and mixing by the wet ball mill of the above manufacturing method is performed using a ball mill apparatus having an internal volume of 300 L with pure water as a solvent, and then dried and granulated by spray drying. A method of crushed with a dry ball mill and hot pressing the crushed powder in the same manner as described above may be used. Moreover, the method which abbreviate | omitted the crushing process by the said dry-type ball mill may be used.

このスパッタリングターゲットを用いて本実施形態の透明酸化物膜をＤＣスパッタするには、上記スパッタリングターゲットを、マグネトロンスパッタリング装置にセットし、所定の投入電力、到達真空度およびスパッタ圧力にて、スパッタガス分圧をＯ２／（Ａｒ＋Ｏ２）が０．０５〜０．２の範囲、基板加熱を１００℃から２００℃とした条件で、樹脂フィルム基材上に成膜する。 In order to DC-sputter the transparent oxide film of this embodiment using this sputtering target, the sputtering target is set in a magnetron sputtering apparatus, and the sputtering gas component is set at a predetermined input power, ultimate vacuum, and sputtering pressure. The film is formed on the resin film substrate under the condition that the pressure is O 2 / (Ar + O 2 ) in the range of 0.05 to 0.2 and the substrate heating is 100 ° C. to 200 ° C.

このように本実施形態の透明酸化物膜では、全金属成分量に対してＡｌ：０．９〜２０．０ａｔ％、Ｓｉ：２５．５〜６８．０ａｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有し、非晶質であるので、従来よりも可視光域で低い屈折率が得られると共に高いガスバリア性（例えば、水蒸気バリア性）を有している。特に、可視光域での屈折率平均値が、１．５９〜１．８０であり、厚み５０ｎｍ以上で水蒸気透過率を０．０１ｇ／（ｍ２・ｄａｙ）以下とすることで、電子ペーパーや太陽電池で採用される樹脂フィルム基材上に成膜されたガスバリア層として好適である。 As described above, the transparent oxide film of this embodiment contains Al: 0.9 to 20.0 at% and Si: 25.5 to 68.0 at% with respect to the total metal component amount, with the balance being Zn and inevitable. Since it has a component composition consisting of impurities and is amorphous, it has a lower refractive index in the visible light region than the prior art and has high gas barrier properties (for example, water vapor barrier properties). In particular, the average value of the refractive index in the visible light region is 1.59 to 1.80, and the water vapor transmission rate is 0.01 g / (m 2 · day) or less at a thickness of 50 nm or more. It is suitable as a gas barrier layer formed on a resin film substrate used in solar cells.

また、この透明酸化物膜の製造方法では、上記酸化物焼結体の組織中に複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが存在するスパッタリングターゲットを用いるので、ＤＣスパッタが可能になり、さらに酸素を含有させた不活性ガス雰囲気中および基板を加熱した状態の少なくとも一方の環境下で、直流電流を投入してスパッタするので、Ｓｉを多く含有させた非晶質の透明酸化物膜（ＺｎＯ−ＳｉＯ２−Ａｌ２Ｏ３膜）を成膜することができる。したがって、本発明の製法によれば、従来よりもＳｉＯ２を多く添加可能であり、屈折率を下げつつ、非晶質でガスバリア性の高い透明酸化物膜をＤＣスパッタで成膜可能である。さらに、可視光域で９５％以上の高い透過率が得られ、良好な透明性を有した膜を得ることができる。 Further, in this method for producing a transparent oxide film, since a sputtering target in which the composite oxide Zn 2 SiO 4 and ZnO are present in the structure of the oxide sintered body is used, DC sputtering is possible, and oxygen Since sputtering is performed by applying a direct current in at least one of an inert gas atmosphere containing silicon and a state where the substrate is heated, an amorphous transparent oxide film containing a large amount of Si (ZnO- SiO 2 —Al 2 O 3 film) can be formed. Therefore, according to the production method of the present invention, more SiO 2 can be added than before, and an amorphous transparent oxide film having a high gas barrier property can be formed by DC sputtering while lowering the refractive index. Furthermore, a high transmittance of 95% or more in the visible light region can be obtained, and a film having good transparency can be obtained.

また、基板の加熱温度を、１００〜２００℃の範囲に設定するので、成膜する樹脂フィルム基材への熱影響を抑えつつ、電子ペーパーや太陽電池で採用されるガスバリア層として十分な透明性と低い屈折率とを有する透明酸化物膜が得られる。
さらに、酸素と不活性ガスとの雰囲気ガス全体に対する酸素のガス分圧を、０．０５以上に設定するので、電子ペーパーや太陽電池で採用されるガスバリア層として十分な透明性と低い屈折率とを有する透明酸化物膜が得られる。 In addition, since the heating temperature of the substrate is set in the range of 100 to 200 ° C., it is sufficiently transparent as a gas barrier layer employed in electronic paper and solar cells while suppressing the thermal effect on the resin film substrate to be formed. And a transparent oxide film having a low refractive index.
Furthermore, since the partial pressure of oxygen with respect to the whole atmospheric gas of oxygen and inert gas is set to 0.05 or more, sufficient transparency and a low refractive index as a gas barrier layer employed in electronic paper and solar cells A transparent oxide film having

上記本実施形態に基づいて作製した透明酸化物膜の実施例について評価した結果を、図２から図８を参照して以下に説明する。   The result evaluated about the Example of the transparent oxide film produced based on the said this embodiment is demonstrated below with reference to FIGS.

本発明の実施例の製造は、以下の条件で行った。
まず、表１に示す組成割合になるようにＡｌ２Ｏ３粉末とＳｉＯ２粉末とＺｎＯ粉末とを秤量し、得られた粉末とその４倍量（重量比）のジルコニアボール（直径５ｍｍのボールと直径１０ｍｍのボールとを半分ずつ）とを１０Ｌのポリ容器（ポリエチレン製ポット）に入れ、ボールミル装置にて４８時間湿式混合し、混合粉末とする。なお、溶媒には、例えばアルコールを用いた。 Manufacture of the Example of this invention was performed on condition of the following.
First, Al 2 O 3 powder, SiO 2 powder, and ZnO powder were weighed so as to have the composition ratio shown in Table 1, and the obtained powder and four times (weight ratio) zirconia balls (balls with a diameter of 5 mm). And a 10 mm diameter ball in half) are placed in a 10 L plastic container (polyethylene pot) and wet mixed for 48 hours in a ball mill apparatus to obtain a mixed powder. For example, alcohol was used as the solvent.

次に、得られた混合粉末を乾燥後、例えば目開き：２５０μｍの篩にかけて造粒し、さらに真空乾燥後、１２００℃にて５時間、２００ｋｇｆ／ｃｍ２の圧力で真空ホットプレスし、焼結体とした。
このようにホットプレスした焼結体を、ターゲットの指定形状（直径１２５ｍｍ、厚さ１０ｍｍ）に機械加工し、加工したものを無酸素銅からなるバッキングプレートにボンディングして本実施例１〜１６のスパッタリングターゲットを作製した。 Next, the obtained mixed powder is dried, then granulated through, for example, a sieve having an opening of 250 μm, vacuum dried, vacuum hot pressed at 1200 ° C. for 5 hours at a pressure of 200 kgf / cm 2 , and sintered. The body.
The sintered body thus hot pressed was machined into a target shape (diameter 125 mm, thickness 10 mm), and the processed one was bonded to a backing plate made of oxygen-free copper. A sputtering target was produced.

さらに、これらのスパッタリングターゲットを、マグネトロンスパッタリング装置にセットし、電源：ＤＣ、投入電力：５００Ｗ、到達真空度：１×１０−４Ｐａ、スパッタガス分圧（酸素と不活性ガスとの雰囲気ガス全体に対する酸素のガス分圧：Ｏ２／（Ａｒ＋Ｏ２）が０．０５以上、スパッタ圧力：０．６７Ｐａ、基板加熱を１００℃から２００℃とした条件で屈折率および透過率測定用としてガラス基板（コーニング社１７３７＃ 縦：２０×横：２０、厚さ：０．７ｍｍ）の上に膜厚１５０ｎｍ、また、水蒸気透過測定用としてＰＥＴフィルム（縦：１００ｍｍ×横：１００、厚さ：１２０μｍ）に５０ｎｍを有する透明膜の形成を試みた。
また、密着性試験用にポリイミドフィルム（縦：１００ｍｍ×横：１００ｍｍ、厚さ：１２０μｍ）に５０ｎｍを有する透明膜の形成を試みた。 Further, these sputtering targets were set in a magnetron sputtering apparatus, and the power source: DC, input power: 500 W, ultimate vacuum: 1 × 10 −4 Pa, sputtering gas partial pressure (the whole atmosphere gas of oxygen and inert gas Oxygen gas partial pressure: O 2 / (Ar + O 2 ) is 0.05 or more, sputtering pressure: 0.67 Pa, substrate heating is 100 ° C. to 200 ° C. Corning 1737 # Vertical: 20 × Horizontal: 20, Thickness: 0.7 mm), 150 nm in thickness, and PET film (Vertical: 100 mm × Horizontal: 100, Thickness: 120 μm) for water vapor transmission measurement An attempt was made to form a transparent film having 50 nm.
For the adhesion test, an attempt was made to form a transparent film having a thickness of 50 nm on a polyimide film (length: 100 mm × width: 100 mm, thickness: 120 μm).

なお、比較例の透明酸化物膜として、表１に示す条件において、基板の加熱温度を１００〜２００℃の範囲外に設定したもの（比較例１，２）と、スパッタリングターゲットのＳｉ含有量を６．０８ｗｔ％未満としたもの（比較例３，４）とを上記実施例と同様に作製した。さらに、従来例として、スパッタリングターゲットのＳｉ含有量を６．０８ｗｔ％未満とすると共にＲＦスパッタにより成膜したものを上記実施例と同様に作製した。   In addition, as a transparent oxide film of a comparative example, on the conditions shown in Table 1, what set the heating temperature of the board | substrate out of the range of 100-200 degreeC (comparative examples 1 and 2), and Si content of a sputtering target were set. What was made less than 6.08 wt% (Comparative Examples 3 and 4) was produced in the same manner as in the above Example. Further, as a conventional example, a sputtering target having a Si content of less than 6.08 wt% and a film formed by RF sputtering was produced in the same manner as in the above example.

Figure 2013189657
Figure 2013189657

このように作製した本発明の実施例、比較例および従来例の透明酸化物膜について膜組成をＩＣＰ発光分析法で測定したところ、全金属成分に対する各金属成分は表１に示すようになった。
また、本発明の実施例および比較例の透明酸化物膜についてＸ線回折（ＸＲＤ）の分析を行い、結晶ピークの有無について調べた結果を表１に示す。なお、代表的に実施例３，５，６，１１および比較例４について、ＸＲＤ分析結果のグラフを図２〜図６にそれぞれ示す。 When the film compositions of the transparent oxide films of Examples, Comparative Examples, and Conventional Examples of the present invention thus prepared were measured by ICP emission analysis, each metal component relative to all metal components was as shown in Table 1. .
Table 1 shows the results of X-ray diffraction (XRD) analysis of the transparent oxide films of Examples and Comparative Examples of the present invention and the presence or absence of crystal peaks. In addition, about Example 3, 5, 6, 11 and the comparative example 4, the graph of a XRD analysis result is each shown in FIGS.

また、得られた各透明酸化物膜の屈折率は分光エリプソメーター（HORIBA Jobin Yvon社製UVISEL NIA AGMS）によって、透過率は分光光度計（日本分光社製 Ｖ−５５０）によって測定した。測定したそれぞれの結果は表１に示す。なお、代表的に実施例３，５，６，１１および比較例４について、波長に対する透過率特性を示すグラフを図７に示す。また、透明酸化物膜の膜厚５０ｎｍ、１００ｎｍ、３００ｎｍにおける波長７５０ｎｍでの透過率結果を表２に示す。   The refractive index of each transparent oxide film obtained was measured with a spectroscopic ellipsometer (UVISEL NIA AGMS manufactured by HORIBA Jobin Yvon), and the transmittance was measured with a spectrophotometer (V-550 manufactured by JASCO Corporation). The measured results are shown in Table 1. In addition, about Example 3, 5, 6, 11 and the comparative example 4, the graph which shows the transmittance | permeability characteristic with respect to a wavelength is shown in FIG. Further, Table 2 shows the transmittance results at a wavelength of 750 nm when the film thickness of the transparent oxide film is 50 nm, 100 nm, and 300 nm.

Figure 2013189657
Figure 2013189657

さらに、水蒸気透過率（水蒸気バリア性）は、モコン法を用い、mocon社製PERMATRAN-WMODEL 3/33を用いてＪＩＳ規格のＫ７１２９法に基づいて測定した。測定されたそれぞれの結果は表１に示す。なお、代表的に実施例３，５，６，１１および比較例４について、波長に対する屈折率特性を示すグラフを図８に示す。   Furthermore, the water vapor transmission rate (water vapor barrier property) was measured based on JIS standard K7129 method using the Mocon method and using PERMATRAN-WMODEL 3/33 manufactured by mocon. The measured results are shown in Table 1. In addition, about Example 3, 5, 6, 11 and the comparative example 4, the graph which shows the refractive index characteristic with respect to a wavelength typically is shown in FIG.

これらの評価の結果、比較例１，３，４では、ＸＲＤ分析において結晶ピークが認められ膜中に結晶が析出しており、水蒸気透過率も０．０１ｇ／（ｍ２・ｄａｙ）を超えてしまっていた。また、可視光域の屈折率が１．８０を超えていると共に透過率も９５％未満と低い。なお、比較例２は、基板加熱温度が２１０℃と高いために樹脂フィルム基材が熱変形してしまい評価ができなかった。さらに、ＲＦスパッタで成膜した従来例では、Ｓｉの含有量が低く可視光域の屈折率が２．０５と高いと共に透過率も９０．６％と低かった。 As a result of these evaluations, in Comparative Examples 1, 3, and 4, a crystal peak was observed in the XRD analysis, crystals were precipitated in the film, and the water vapor transmission rate exceeded 0.01 g / (m 2 · day). I was sorry. Further, the refractive index in the visible light region exceeds 1.80 and the transmittance is as low as less than 95%. In Comparative Example 2, since the substrate heating temperature was as high as 210 ° C., the resin film base material was thermally deformed and could not be evaluated. Furthermore, in the conventional example formed by RF sputtering, the Si content was low, the refractive index in the visible light region was as high as 2.05, and the transmittance was as low as 90.6%.

これらに対して本発明の実施例はいずれも、ＸＲＤ分析において結晶ピークが認められず、非晶質な膜であり、水蒸気透過率についても０．０１ｇ／（ｍ２・ｄａｙ）以下であり、高い水蒸気バリア性を有している。また、いずれの実施例も可視光域の屈折率が１．８０以下であると共に透過率も９５％以上と高く、低屈折率かつ高透明性の膜が得られている。このように本発明の実施例の透明酸化物膜は、いずれも電子ペーパーや太陽電池に採用されるガスバリア層として好適な膜特性を備えている。ただし、実施例１６に記載の条件では膜の特性は優れているが、スパッタ時の雰囲気でのＯ２量が多いため、成膜速度が遅くなる。 In contrast, in all of the examples of the present invention, no crystal peak was observed in the XRD analysis, the film was an amorphous film, and the water vapor transmission rate was 0.01 g / (m 2 · day) or less. Has high water vapor barrier properties. In any of the examples, the refractive index in the visible light region is 1.80 or less and the transmittance is as high as 95% or more, and a low refractive index and highly transparent film is obtained. Thus, the transparent oxide film of the Example of this invention is equipped with the film | membrane characteristic suitable for all as a gas barrier layer employ | adopted as an electronic paper or a solar cell. However, the film characteristics are excellent under the conditions described in Example 16, but the film formation rate is slow because of the large amount of O 2 in the atmosphere during sputtering.

＜密着性の測定＞
密着性の測定として、まず得られたフィルム上の透明酸化物膜（実施例１〜１７、比較例１〜７、従来例）をガラス基板の上に両面テープで貼り付け、透明酸化物膜の上から、カッターで碁盤の目状に１００個の切り込みを入れた。次に、セロハン粘着テープを強く貼り付けた後、９０゜方向に急速に剥し、透明酸化物膜の剥離の有無を調べた。その結果を表３に示す。１００目のうち、剥離しない目の数をＸで表示した。すなわち、剥離箇所がある場合はＸ／１００、剥離箇所がない場合は１００／１００と示される。 <Measurement of adhesion>
For the measurement of adhesion, first, the transparent oxide films (Examples 1 to 17, Comparative Examples 1 to 7, Conventional Examples) on the obtained films were pasted on a glass substrate with a double-sided tape. From above, 100 cuts were made in a grid pattern with a cutter. Next, after strongly attaching a cellophane adhesive tape, it was peeled off rapidly in the 90 ° direction, and the presence or absence of peeling of the transparent oxide film was examined. The results are shown in Table 3. Of the 100 eyes, the number of eyes that do not peel is indicated by X. That is, X / 100 is indicated when there is a peeling portion, and 100/100 when there is no peeling portion.

Figure 2013189657
Figure 2013189657

これらの結果からわかるように、比較例や従来例では、剥離が生じているのに対し、本発明の実施例は、いずれも剥離が発生しておらず、高い密着性が得られている。   As can be seen from these results, peeling occurred in the comparative example and the conventional example, whereas no peeling occurred in the examples of the present invention, and high adhesion was obtained.

なお、本発明の技術範囲は上記実施形態および上記実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。
例えば、樹脂フィルム上に成膜するだけでなく、逆にガラス上に透明酸化物膜を成膜し、その上に樹脂膜をつけ、さらにガラスから樹脂膜と共に透明酸化物膜を剥がすようにしても構わない。 The technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.
For example, in addition to forming a film on a resin film, conversely, a transparent oxide film is formed on glass, a resin film is attached on the glass, and the transparent oxide film is peeled off from the glass together with the resin film. It doesn't matter.

（スパッタリングターゲットに関する参考例）
本発明においては、ＤＣスパッタによる成膜が求められるが、ＤＣスパッタが可能なスパッタリングターゲットに関して検討結果を以下に示す。
本参考例に係るスパッタリングターゲットの製造は、以下の条件で行った。
まず、Ａｌ２Ｏ３粉末とＳｉＯ２粉末とＺｎＯ粉末とを表１に示した各割合で秤量し、得られた粉末とその４倍量（重量比）のジルコニアボール（直径５ｍｍのボールと直径１０ｍｍのボールとを半分ずつ）とを１０Ｌのポリ容器（ポリエチレン製ポット）に入れ、ボールミル装置にて４８時間湿式混合し、混合粉末とする。なお、溶媒には、例えばアルコールを用いた。 (Reference example regarding sputtering target)
In the present invention, although film formation by DC sputtering is required, the results of studies on a sputtering target capable of DC sputtering are shown below.
The sputtering target according to this reference example was manufactured under the following conditions.
First, Al 2 O 3 powder, SiO 2 powder, and ZnO powder were weighed in the proportions shown in Table 1, and the obtained powder and four times (weight ratio) zirconia balls (balls having a diameter of 5 mm and diameters). A 10 mm ball and a half are put into a 10 L plastic container (polyethylene pot) and wet-mixed for 48 hours in a ball mill apparatus to obtain a mixed powder. For example, alcohol was used as the solvent.

次に、得られた混合粉末を乾燥後、例えば目開き：２５０μｍの篩にかけて造粒し、さらに真空乾燥後、１２００℃にて５時間、２００ｋｇｆ／ｃｍ２の圧力で真空ホットプレスし、焼結体とした。
このようにホットプレスした焼結体を、ターゲットの指定形状（直径１２５ｍｍ、厚さ１０ｍｍ）に機械加工し、加工したものを無酸素銅からなるバッキングプレートにボンディングして本参考例のスパッタリングターゲットを作製した。 Next, the obtained mixed powder is dried, then granulated through, for example, a sieve having an opening of 250 μm, vacuum dried, vacuum hot pressed at 1200 ° C. for 5 hours at a pressure of 200 kgf / cm 2 , and sintered. The body.
The sintered body thus hot-pressed is machined into a target shape (diameter 125 mm, thickness 10 mm), and the processed product is bonded to a backing plate made of oxygen-free copper to produce the sputtering target of this reference example. Produced.

なお、比較参考例１〜１１として、Ａｌ２Ｏ３粉末とＳｉＯ２粉末とＺｎＯ粉末とを表２に示した各割合で秤量し、得られた各粉末を混合し、０．６ｔ／ｃｍ２でプレスし、さらにＣＩＰ（冷間静水等方圧プレス）にて１７５ＭＰａで成形して、それを１４００℃で大気焼成してスパッタリングターゲットを作製した。また、比較参考例１２〜１４として、本発明の成分組成の範囲外であって表２に示す各割合で秤量し、本参考例と同様の条件で真空ホットプレスしてスパッタリングターゲットを作製した。 In addition, as Comparative Reference Examples 1 to 11, Al 2 O 3 powder, SiO 2 powder, and ZnO powder were weighed at the respective ratios shown in Table 2, and the obtained powders were mixed to obtain 0.6 t / cm 2. Then, it was molded at 175 MPa by CIP (cold isostatic pressing) and fired in air at 1400 ° C. to produce a sputtering target. Moreover, as Comparative Reference Examples 12 to 14, they were weighed at respective ratios shown in Table 2 outside the range of the component composition of the present invention, and vacuum hot pressed under the same conditions as in this Reference Example to prepare sputtering targets.

さらに、これらのスパッタリングターゲットを、マグネトロンスパッタリング装置にセットし、電源：ＤＣ、投入電力：２００Ｗ、到達真空度：１×１０−４Ｐａ、スパッタガス：Ａｒ、スパッタ圧力：０．６７Ｐａとした条件で、２００℃に加熱されたガラス基板（コーニング社１７３７＃ 縦：２０×横：２０、厚さ：０．７ｍｍ）の上に膜厚：３００ｎｍを有する透明膜の形成を試みた。 Furthermore, these sputtering targets were set in a magnetron sputtering apparatus, and the conditions were as follows: power source: DC, input power: 200 W, ultimate vacuum: 1 × 10 −4 Pa, sputtering gas: Ar, sputtering pressure: 0.67 Pa An attempt was made to form a transparent film having a thickness of 300 nm on a glass substrate heated to 200 ° C. (Corning 1737 # length: 20 × width: 20, thickness: 0.7 mm).

このように作製した本発明の参考例および比較参考例について、焼結体の密度（理論密度比）、Ｘ線回折法（ＸＲＤ）によるＺｎＯ（１０１）およびＺｎ２ＳｉＯ４（４１０）の回折ピークの有無、ＤＣスパッタの可否、バルク抵抗値、６０分間のＤＣスパッタ時の異常放電回数、ＤＣスパッタした透明膜の屈折率（波長３８０ｎｍ、５５０ｎｍ、７５０ｎｍの光に対して）をそれぞれ測定、評価した。この結果を表４に示す。 About the reference example and comparative reference example of the present invention thus produced, the sintered body density (theoretical density ratio), diffraction peaks of ZnO (101) and Zn 2 SiO 4 (410) by X-ray diffraction (XRD) Presence / absence, DC sputtering availability, bulk resistance value, number of abnormal discharges during DC sputtering for 60 minutes, and refractive index of the DC-sputtered transparent film (with respect to light with wavelengths of 380 nm, 550 nm, and 750 nm) were measured and evaluated. . The results are shown in Table 4.

Figure 2013189657
Figure 2013189657

この結果からわかるように、大気焼成を用いた比較参考例のうちＡｌ２Ｏ３の含有量が少なくＳｉＯ２を含まない比較参考例１，２では、異常放電回数が多く安定したＤＣスパッタができず、Ａｌ２Ｏ３の含有量がある程度あるがＳｉＯ２を含まない比較参考例３〜５では、低い屈折率が得られていない。また、大気焼成を用いた比較参考例のうちＡｌ２Ｏ３の含有量が多くＳｉＯ２を含まない比較参考例６，７では、異常放電回数が多く安定したＤＣスパッタができず、Ａｌ２Ｏ３とＳｉＯ２とを含む比較参考例８〜１１では、異常放電回数が多いまたはターゲットに導電性がなくＤＣスパッタができなかった。なお、比較参考例１〜７は、いずれも密度が理論密度の１００％未満であった。 As can be seen from these results, in Comparative Reference Examples 1 and 2 that have a low content of Al 2 O 3 and do not contain SiO 2 among Comparative Reference Examples that use atmospheric firing, stable DC sputtering can be performed with a large number of abnormal discharges. In Comparative Reference Examples 3 to 5 having a certain amount of Al 2 O 3 but not containing SiO 2 , a low refractive index was not obtained. Moreover, in Comparative Reference Examples 6 and 7 in which the content of Al 2 O 3 is large and does not contain SiO 2 among the Comparative Reference Examples using atmospheric firing, stable DC sputtering cannot be performed with a large number of abnormal discharges, and Al 2 O In Comparative Reference Examples 8 to 11 containing 3 and SiO 2 , the number of abnormal discharges was large or the target was not conductive and DC sputtering could not be performed. In all of Comparative Reference Examples 1 to 7, the density was less than 100% of the theoretical density.

さらに、ホットプレスを用いた比較参考例のうちＳｉＯ２の含有量が本発明の範囲よりも少ない比較参考例１２では、低い屈折率が得られず、ＳｉＯ２の含有量が本発明の範囲よりも多い比較参考例１３では、ターゲットに導電性がなくＤＣスパッタができなかった。また、Ａｌ２Ｏ３の含有量が本発明の範囲よりも多い比較参考例１４では、異常放電回数が多く安定したＤＣスパッタができなかった。なお、比較参考例８，１２，１４では、ＸＲＤにおいてＺｎＯ（１０１）およびＺｎ２ＳｉＯ４（４１０）の両ピークが観察されたが、ＡｌまたはＳｉの含有量が本発明の範囲から外れているため、上述した不都合が生じている。 Furthermore, in the comparative reference example 12 in which the content of SiO 2 is smaller than the range of the present invention among the comparative reference examples using the hot press, a low refractive index cannot be obtained, and the content of SiO 2 is smaller than the range of the present invention. In Comparative Reference Example 13 having many, the target was not conductive and DC sputtering could not be performed. Further, in Comparative Reference Example 14 in which the content of Al 2 O 3 was larger than the range of the present invention, the number of abnormal discharges was large and stable DC sputtering could not be performed. In Comparative Reference Examples 8, 12, and 14, both peaks of ZnO (101) and Zn 2 SiO 4 (410) were observed in XRD, but the content of Al or Si deviated from the scope of the present invention. Therefore, the inconvenience described above occurs.

これらに対して本参考例は、いずれもＸＲＤにおいてＺｎＯ（１０１）およびＺｎ２ＳｉＯ４（４１０）の両ピークが観察され、異常放電回数が非常に少なく安定に良好なＤＣスパッタができており、屈折率についてもいずれもＡＺＯ膜よりも低い屈折率が得られている。また、密度についても、本参考例ではいずれも理論密度の１００〜１０８％の範囲内であった。 On the other hand, in this reference example, both peaks of ZnO (101) and Zn 2 SiO 4 (410) were observed in XRD, the number of abnormal discharges was very small, and stable and good DC sputtering was achieved. As for the refractive index, a refractive index lower than that of the AZO film is obtained. Also, the density was within the range of 100 to 108% of the theoretical density in this reference example.

次に、表１に示す参考例３（ＳｉＯ２：２０ｗｔ％）について、Ｘ線回折法（ＸＲＤ）にて観察した結果を、図９に示す。この参考例３では、複合酸化物Ｚｎ２ＳｉＯ４の（４１０）の回折ピークとＺｎＯの（１０１）の回折ピークとが、いずれも高い強度で観察されている。これに対して、参考例３と同じ成分組成により大気焼成で作製した比較参考例では、図１０に示すようにＺｎＯの（１０１）の回折ピークが得られていない。このように、導電性を得るには、本参考例のように、複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが組織中に共存することが必要である。 Next, FIG. 9 shows the result of observation by X-ray diffraction (XRD) for Reference Example 3 (SiO 2 : 20 wt%) shown in Table 1. In Reference Example 3, the (410) diffraction peak of the complex oxide Zn 2 SiO 4 and the (101) diffraction peak of ZnO are both observed with high intensity. On the other hand, as shown in FIG. 10, the (101) diffraction peak of ZnO was not obtained in the comparative reference example produced by atmospheric firing with the same component composition as in Reference example 3. Thus, in order to obtain conductivity, it is necessary that the composite oxides Zn 2 SiO 4 and ZnO coexist in the structure as in this reference example.

Claims (6)

全金属成分量に対してＡｌ：０．９〜２０．０ａｔ％、Ｓｉ：２５．５〜６８．０ａｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有し、非晶質であることを特徴とする透明酸化物膜。   Al: 0.9 to 20.0 at%, Si: 25.5 to 68.0 at% with respect to the total amount of metal components, the balance is composed of Zn and inevitable impurities, and is amorphous. A transparent oxide film characterized by being. 請求項１に記載の透明酸化物膜において、
波長７５０ｎｍにおける透過率が、９３％以上であることを特徴とする透明酸化物膜。 The transparent oxide film according to claim 1,
A transparent oxide film having a transmittance of 93% or more at a wavelength of 750 nm. 請求項１又は２に記載の透明酸化物膜において、
可視光域での屈折率平均値が、１．５９〜１．８０であり、
厚み５０ｎｍ以上で水蒸気透過率が０．０１ｇ／（ｍ２・ｄａｙ）以下であることを特徴とする透明酸化物膜。 The transparent oxide film according to claim 1 or 2,
The average refractive index in the visible light region is 1.59 to 1.80,
A transparent oxide film having a thickness of 50 nm or more and a water vapor transmission rate of 0.01 g / (m 2 · day) or less. 請求項１から３のいずれか一項に記載の透明酸化物膜を製造する方法であって、
全金属成分量に対してＡｌ：０．３〜４．０ｗｔ％、Ｓｉ：６．０〜１４．５ｗｔ％を含有し、残部がＺｎおよび不可避不純物からなる成分組成を有した酸化物焼結体からなり、該焼結体の組織中に複合酸化物Ｚｎ２ＳｉＯ４とＺｎＯとが存在するスパッタリングターゲットを用い、酸素を含有させた不活性ガス雰囲気中および基板を加熱した状態の少なくとも一方の環境下で、直流電流を投入してスパッタすることを特徴とする透明酸化物膜の製造方法。 A method for producing the transparent oxide film according to any one of claims 1 to 3,
Oxide sintered body containing Al: 0.3 to 4.0 wt%, Si: 6.0 to 14.5 wt% with respect to the total amount of metal components, with the balance being composed of Zn and inevitable impurities At least one environment in which an oxygen-containing inert gas atmosphere and a substrate are heated using a sputtering target in which a composite oxide Zn 2 SiO 4 and ZnO are present in the structure of the sintered body A method for producing a transparent oxide film, comprising: sputtering under direct current. 請求項４に記載の透明酸化物膜の製造方法において、
前記基板が樹脂フィルム基材であり、
前記基板の加熱温度を、１００〜２００℃の範囲に設定することを特徴とする透明酸化物膜の製造方法。 In the manufacturing method of the transparent oxide film of Claim 4,
The substrate is a resin film substrate;
A method for producing a transparent oxide film, wherein a heating temperature of the substrate is set in a range of 100 to 200 ° C. 請求項４に記載の透明酸化物膜の製造方法において、
前記酸素と不活性ガスとの雰囲気ガス全体に対する酸素のガス分圧を、０．０５以上に設定することを特徴とする透明酸化物膜の製造方法。 In the manufacturing method of the transparent oxide film of Claim 4,
A method for producing a transparent oxide film, wherein a partial pressure of oxygen with respect to the whole atmosphere gas of oxygen and inert gas is set to 0.05 or more.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5550768B1 (en) * 2012-07-03 2014-07-16 Ｊｘ日鉱日石金属株式会社 Sintered body and amorphous film
US20160285027A1 (en) * 2013-12-26 2016-09-29 Japan Science And Technology Agency Thin film of metal oxide, organic electroluminescent device including the thin film, photovoltaic cell including the thin film and organic photovoltaic cell including the thin film
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Families Citing this family (11)

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JP5730729B2 (en) * 2011-09-20 2015-06-10 株式会社カネカ Substrate with transparent electrode
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CN110793937B (en) * 2018-08-03 2022-08-16 张家港康得新光电材料有限公司 Membrane type determination method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006129410A1 (en) * 2005-05-30 2006-12-07 Nippon Mining & Metals Co., Ltd. Sputtering target and process for producing the same
JP2007311041A (en) * 2006-05-16 2007-11-29 Bridgestone Corp Film-forming method of crystalline zno system transparent conductive thin film, crystalline zno system transparent conductive thin film and film, as well as resistance film type touch panel
WO2009078330A1 (en) * 2007-12-19 2009-06-25 Hitachi Metals, Ltd. Zinc oxide sintered compact, process for producing the zinc oxide sintered compact, sputtering target, and electrode formed using the sputtering target
JP2009199986A (en) * 2008-02-25 2009-09-03 Sumitomo Metal Mining Co Ltd Zinc oxide transparent conductive film lamination layer, transparent conductive substrate and device

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3841388B2 (en) * 1998-02-16 2006-11-01 日鉱金属株式会社 Protective film for optical disk and sputtering target for forming protective film of optical disk
JPH11236219A (en) * 1998-02-20 1999-08-31 Sumitomo Metal Mining Co Ltd Zinc oxide-base sintered compact and its production
JPH11322332A (en) * 1998-05-21 1999-11-24 Sumitomo Metal Mining Co Ltd Zno-based sintered product and its production
JP2000040429A (en) * 1998-07-24 2000-02-08 Sumitomo Metal Mining Co Ltd Manufacturing of zinc oxide transparent conductive film
JP2007327079A (en) * 2006-06-06 2007-12-20 Sony Corp Transparent conductive laminate film, and its manufacturing method
WO2009078329A1 (en) * 2007-12-19 2009-06-25 Hitachi Metals, Ltd. Zinc oxide sintered compact, process for producing the zinc oxide sintered compact, sputtering target, and electrode
WO2009145152A1 (en) * 2008-05-27 2009-12-03 株式会社カネカ Transparent conductive film and method for producing the same
WO2010032542A1 (en) * 2008-09-17 2010-03-25 三井金属鉱業株式会社 Electrically conductive transparent zinc oxide film, and method for producing same
EP2415597A4 (en) * 2009-03-31 2014-12-31 Teijin Ltd Transparent conductive laminate and transparent touch panel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006129410A1 (en) * 2005-05-30 2006-12-07 Nippon Mining & Metals Co., Ltd. Sputtering target and process for producing the same
JP2007311041A (en) * 2006-05-16 2007-11-29 Bridgestone Corp Film-forming method of crystalline zno system transparent conductive thin film, crystalline zno system transparent conductive thin film and film, as well as resistance film type touch panel
WO2009078330A1 (en) * 2007-12-19 2009-06-25 Hitachi Metals, Ltd. Zinc oxide sintered compact, process for producing the zinc oxide sintered compact, sputtering target, and electrode formed using the sputtering target
JP2009199986A (en) * 2008-02-25 2009-09-03 Sumitomo Metal Mining Co Ltd Zinc oxide transparent conductive film lamination layer, transparent conductive substrate and device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JPN6015019805; ＤＥＮＧ，Ｚ．　ｅｔ　ａｌ: '"Ｅｆｆｅｃｔｓ　ｏｆ　Ａｌ　ｃｏｎｔｅｎｔ　ｏｎ　ｔｈｅ　ｐｒｏｐｅｒｔｉｅｓ　ｏｆ　ＺｎＯ：Ａｌ　ｆｉｌｍｓ　ｐｒｅｐａｒｅｄ　ｂｙ　Ａｌ２Ｏ３　ａｎｄ　ＺｎＯ　ｃｏ-ｓｐｕｔｔｅｒｉｎｇ"' Ｊｏｕｒｎａｌ　ｏｆ　Ｍａｔｅｒｉａｌｓ　Ｓｃｉｅｎｃｅ．　Ｍａｔｅｒｉａｌｓ　ｉｎ　Ｅｌｅｃｔｒｏｎｉｃｓ Ｖｏｌ．２１，　Ｎｏ．１０, 201010, ｐｐ．１０３０-１０３５ *

Cited By (17)

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Publication number Priority date Publication date Assignee Title
JP5550768B1 (en) * 2012-07-03 2014-07-16 Ｊｘ日鉱日石金属株式会社 Sintered body and amorphous film
JP2014141386A (en) * 2012-07-03 2014-08-07 Jx Nippon Mining & Metals Corp Sintered body and amorphous film
JP2014159634A (en) * 2012-07-03 2014-09-04 Jx Nippon Mining & Metals Corp Sintered body and amorphous film
JP2014166950A (en) * 2012-07-03 2014-09-11 Jx Nippon Mining & Metals Corp Sintered body and amorphous film
US20160285027A1 (en) * 2013-12-26 2016-09-29 Japan Science And Technology Agency Thin film of metal oxide, organic electroluminescent device including the thin film, photovoltaic cell including the thin film and organic photovoltaic cell including the thin film
US11094909B2 (en) * 2013-12-26 2021-08-17 Japan Science And Technology Agency Thin film of metal oxide, organic electroluminescent device including the thin film, photovoltaic cell including the thin film and organic photovoltaic cell including the thin film
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