JP2014055348A - Sputtering target for forming transparent oxide film and method for producing the same - Google Patents

Sputtering target for forming transparent oxide film and method for producing the same Download PDF

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JP2014055348A
JP2014055348A JP2013150310A JP2013150310A JP2014055348A JP 2014055348 A JP2014055348 A JP 2014055348A JP 2013150310 A JP2013150310 A JP 2013150310A JP 2013150310 A JP2013150310 A JP 2013150310A JP 2014055348 A JP2014055348 A JP 2014055348A
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powder
sputtering target
oxide film
sio
sputtering
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JP6278229B2 (en
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Atsushi Saito
淳 齋藤
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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Mitsubishi Materials Corp
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Priority to JP2013150310A priority Critical patent/JP6278229B2/en
Priority to TW102128640A priority patent/TWI561650B/en
Priority to PCT/JP2013/071670 priority patent/WO2014025017A1/en
Priority to KR1020157001661A priority patent/KR101990663B1/en
Priority to CN201380041837.4A priority patent/CN104540976B/en
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Abstract

PROBLEM TO BE SOLVED: To provide a sputtering target for forming a transparent oxide film based on zinc oxide that may deposit the transparent oxide film by a direct current sputtering without causing an abnormal discharge.SOLUTION: The sputtering target for forming a transparent oxide film is a sintered body having a composition which contains 0.6 to 8.0 at% of at least one of Al and Ga and 0.1 at% or more of Si, in which a total content of Al, Ga and Si is 33.0 at% or less per total metal component quantity and a remaining part is composed of Zn and inevitable impurities, in which a complex oxide of Zn and Si having a particle size of 5 μm or less exists.

Description

本発明は、特に、光ディスクに好適な光透過保護膜、タッチパネル素子、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太陽電池などに用いられるガスバリア層などに利用できる酸化亜鉛系の透明酸化物膜形成用スパッタリングターゲット及びその製造方法に関するものである。   In particular, the present invention is a light barrier protective film suitable for an optical disc, a touch panel element, a liquid crystal display element, an electroluminescence display element, an electrophoretic display element, a gas barrier layer used for electronic paper such as a toner display element, a solar cell, etc. The present invention relates to a zinc oxide-based sputtering target for forming a transparent oxide film and a method for producing the same.

従来、光ディスクに好適な光透過保護膜として、さらには、タッチパネル素子、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太陽電池などに用いられるガスバリア層として、酸化亜鉛系の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, as a light transmission protective film suitable for an optical disk, and further as a gas barrier layer used for electronic paper such as a touch panel element, a liquid crystal display element, an electroluminescence display element, an electrophoretic display element, a toner display element, and a solar cell. A technique for producing a zinc oxide-based 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を形成することが記載されている。ここでは、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種以上の酸化物を含有した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％を含有し、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 describes forming a light transmission film used as a protective film for a phase change optical disk. Here, 0.01 to 20 wt% of one or more glass-forming oxides selected from Nb 2 O 5 , V 2 O 5 , B 2 O 3 , SiO 2 , and P 2 O 5 , Al 2 O 3 or Ga 2 O 3 in an amount of 0.01 to 20% by weight, using a sputtering target containing the balance of one or more oxides selected from In 2 O 3 , SnO 2 and ZnO, by sputtering, 0.01 to 20% by weight of one or more glass-forming oxides selected from Nb 2 O 5 , V 2 O 5 , B 2 O 3 , SiO 2 and P 2 O 5 , Al 2 O 3 or Ga There has been proposed a method of forming a light-transmitting film that contains 0.01 to 20% by weight of 2 O 3 and the balance is one or more oxides selected from In 2 O 3 , SnO 2 , and ZnO. .

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

従来の技術では、例えば、特許文献１に記載のターゲットを用いて酸化物膜を成膜する場合、その成膜のスパッタリング時に、ノジュールが多く発生し、装置の掃除等に手間がかかっていた。そのため、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た。しかしながら、特許文献２に記載の透明酸化物膜では、屈折率が高いため、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、その膜の屈折率を低くする必要がある。   In the conventional technique, for example, when an oxide film is formed using the target described in Patent Document 1, many nodules are generated during sputtering of the film formation, and it takes time to clean the apparatus. Therefore, there has been a demand for a transparent oxide film that is not tin oxide-based but has an excellent gas barrier property of another composition system. However, since the transparent oxide film described in Patent Document 2 has a high refractive index, the refractive index of the resin film base material can be used for the gas barrier layer on the resin film base material used in the electronic paper and solar cell described above. In order to approach (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 of the film.

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。しかし、スパッタリングターゲットにＳｉＯ２が添加されると、ＳｉＯ２自体は、絶縁性であるため、酸化物膜の成膜には、高周波（ＲＦ）スパッタリングを採用せざるを得ない。しかしながら、この高周波スパッタリングは、成膜レートが低いために、酸化物膜の成膜にあたっては、成膜レートが早く、生産性の高い直流（ＤＣ）スパッタリングの採用が期待されている。そこで、特許文献２に記載のように、直流スパッタリングの採用が可能となるように、ターゲットの低抵抗化を図ることが提案されている。この低抵抗化のために、スパッタリングターゲットに、Ａｌ２Ｏ３又はＧａ２Ｏ３を含有させているが、ガラスの屈折率に近い透明性の確保を実現するためには、ＳｉＯ２を多く添加しなければならない。このＳｉＯ２の多量添加は、却って、直流スパッタリングの採用を困難にしている。 For this reason, it can be considered that the zinc oxide-based transparent oxide film contains more SiO 2 to lower the refractive index. However, when SiO 2 is added to the sputtering target, since the SiO 2 itself is insulative, high-frequency (RF) sputtering must be employed for forming the oxide film. However, since this high-frequency sputtering has a low film formation rate, it is expected that high-productivity direct current (DC) sputtering will be adopted when forming an oxide film. Therefore, as described in Patent Document 2, it has been proposed to reduce the resistance of the target so that DC sputtering can be employed. In order to reduce the resistance, Al 2 O 3 or Ga 2 O 3 is contained in the sputtering target, but in order to achieve transparency close to the refractive index of glass, a large amount of SiO 2 is added. Must. On the contrary, the addition of a large amount of SiO 2 makes it difficult to employ DC sputtering.

ここで、上述した要件を満たす酸化亜鉛系のスパッタリングターゲットを製造するには、ＺｎＯ粉末と、ＳｉＯ２粉末と、Ａｌ２Ｏ３粉末又はＧａ２Ｏ３を粉末とを適量配合して混合した混合粉末を所定の焼成条件で焼成した焼結体を得る必要がある。このとき、この焼結体の素地中には、焼成の仕方によっては、ＺｎＯとＳｉＯ２とが反応して、ＺｎとＳｉとの複合酸化物（組成式：Ｚｎ２ＳｉＯ４）の大きな粒子が形成される。しかしながら、この様な複合酸化物粒子が内在するスパッタリングターゲットを用いた場合に、直流スパッタリングで成膜しようとすると、異常放電に起因して、プラズマが生成されず、スパッタリングを実施できないという問題が生じ、或いは、異常放電が多発し、これが成膜に影響するという問題があった。さらに、原料粉末として、Ａｌ２Ｏ３粉末又はＧａ２Ｏ３を粉末の配合量が多い場合にも、その製造された酸化亜鉛系スパッタリングターゲットを用いて直流（ＤＣ）スパッタリングを実施しようとすると、異常放電が多発するという問題があった。 Here, in order to produce a zinc oxide-based sputtering target that satisfies the above-described requirements, mixing is performed by mixing and mixing an appropriate amount of ZnO powder, SiO 2 powder, and Al 2 O 3 powder or Ga 2 O 3 powder. It is necessary to obtain a sintered body obtained by firing the powder under predetermined firing conditions. At this time, depending on the firing method, ZnO and SiO 2 react with each other in the sintered body, and large particles of a composite oxide of Zn and Si (composition formula: Zn 2 SiO 4 ) are present. It is formed. However, when a sputtering target containing such complex oxide particles is used, if a film is formed by direct current sputtering, plasma is not generated and sputtering cannot be performed due to abnormal discharge. Alternatively, there has been a problem that abnormal discharge frequently occurs and this affects film formation. Furthermore, even when Al 2 O 3 powder or Ga 2 O 3 is used as a raw material powder in a large amount of powder, direct current (DC) sputtering is performed using the manufactured zinc oxide-based sputtering target. There was a problem that abnormal discharge occurred frequently.

そこで、本発明は、前述の課題に鑑みてなされたもので、スパッタリングターゲット中におけるＺｎとＳｉとの複合酸化物の生成を調整することにより、透明酸化物膜を直流スパッタリングで成膜でき、しかも、スパッタリング時に、異常放電が発生しにくい酸化亜鉛系の透明酸化物膜形成用スパッタリングターゲット及びその製造方法を提供することを目的とする。   Therefore, the present invention has been made in view of the above-mentioned problems, and by adjusting the generation of a composite oxide of Zn and Si in a sputtering target, a transparent oxide film can be formed by DC sputtering, An object of the present invention is to provide a zinc oxide-based sputtering target for forming a transparent oxide film that hardly causes abnormal discharge during sputtering and a method for producing the same.

本発明者らは、ＳｉＯ２、Ａｌ２Ｏ３及び／又はＧａ２Ｏ３を含有させた酸化亜鉛系スパッタリングターゲットを用いて、Ａ１（及び／又はＧａ）−Ｚｎ−Ｓｉ−Ｏ膜を直流スパッタリングにより成膜するべく研究を行った。 The inventors of the present invention used a zinc oxide-based sputtering target containing SiO 2 , Al 2 O 3 and / or Ga 2 O 3 to direct-sputter an A1 (and / or Ga) —Zn—Si—O film. Research was conducted to form a film.

上述したように、この酸化亜鉛系スパッタリングターゲットの製造にあたって、ＺｎＯ粉末と、ＳｉＯ２粉末と、Ａｌ２Ｏ３粉末及び／又はＧａ２Ｏ３を粉末とによる混合粉末を焼成して焼結体を得たのでは、この焼結体の素地中には、大きな粒径を有するＺｎ２ＳｉＯ４のＺｎとＳｉとの複合酸化物粒子が形成されてしまう。しかも、この複合酸化物粒子の形成に対する調整は、焼成条件を種々工夫しても、難しいものであった。 As described above, in manufacturing this zinc oxide-based sputtering target, a sintered powder is obtained by firing a mixed powder of ZnO powder, SiO 2 powder, Al 2 O 3 powder and / or Ga 2 O 3 powder. As a result, composite oxide particles of Zn 2 Si 4 of Zn 2 SiO 4 having a large particle size are formed in the substrate of the sintered body. Moreover, the adjustment to the formation of the composite oxide particles is difficult even if various baking conditions are devised.

そこで、発明者らは、ＺｎＯ粉末と、ＳｉＯ２粉末と、Ａｌ２Ｏ３粉末又はＧａ２Ｏ３を粉末とによる混合粉末を焼成して焼結体を得るのではなく、先ず、ＺｎＯ粉末とＳｉＯ２粉末の混合粉末を仮焼成して、Ｚｎ２ＳｉＯ４のＺｎとＳｉとの複合酸化物を形成した仮焼体を得ておき、この仮焼体を微細な粉砕粉とした後に、この粉砕粉を原料粉末とし、これと、ＺｎＯ粉末と、Ａｌ２Ｏ３粉末又はＧａ２Ｏ３粉末とを、成膜目的であるＡ１（及び／又はＧａ）−Ｚｎ−Ｓｉ−Ｏ膜の成分組成となるように秤量して混合した混合粉末を焼成することにより焼成体を得るようにすれば、製造されたスパッタリングターゲット中におけるＺｎとＳｉとの複合酸化物粒子の存在を調整することが簡単になり、このＺｎとＳｉとの複合酸化物粒子も微細に形成されるとの知見が得られた。 Therefore, the inventors do not obtain a sintered body by firing a mixed powder of ZnO powder, SiO 2 powder, Al 2 O 3 powder or Ga 2 O 3 powder, but first, ZnO powder and After calcining the mixed powder of SiO 2 powder to obtain a calcined body in which a composite oxide of Zn and Si of Zn 2 SiO 4 is formed, this calcined body is made into a fine pulverized powder, the pulverized powder as a raw material powder, this and, with ZnO powder, Al 2 O 3 and powder or Ga 2 O 3 powder, a film forming object A1 (and / or Ga) composition of -Zn-Si-O film It is easy to adjust the presence of composite oxide particles of Zn and Si in the produced sputtering target by firing the mixed powder weighed and mixed so as to obtain a fired body. This complex acid of Zn and Si Things particles was also obtained knowledge that is finely formed.

そこで、本発明者らは、一試験例として、酸化亜鉛系スパッタリングターゲットの製造を試みた。先ず、ＺｎＯ、ＳｉＯ２の各原料粉末をＺｎＯ：ＳｉＯ２＝２：１（モル比）となるように秤量し、この秤量した各原料粉末を湿式混合する。得られた混合粉末を乾燥後、造粒し１２００℃、５時間、大気中で焼成し仮焼粉を得た。この仮焼粉は、Ｚｎ２ＳｉＯ４のＺｎとＳｉとの複合酸化物である。この仮焼粉を粉砕して造粒した。次に、この仮焼粉を原料粉末とし、ＺｎＯ、Ａｌ２Ｏ３の各原料粉末を所定の比率になるように秤量し、この秤量した原料粉末を混合する。得られた混合粉末を、１４００℃、３時間、窒素ガス雰囲気中で焼成して焼結体を得た。この焼結体を機械加工して所定形状にして、透明酸化物膜形成用のスパッタリングターゲットを製造した。製造されたスパッタリングターゲットにおける組成成分について分析を行った。その分析結果が図１に示されている。 Then, the present inventors tried manufacture of a zinc oxide type sputtering target as one test example. First, ZnO, each raw material powder of SiO 2 ZnO: SiO 2 = 2 : 1 were weighed so that the molar ratio, wet mixing the raw material powder this weighed. The obtained mixed powder was dried, granulated, and fired in the atmosphere at 1200 ° C. for 5 hours to obtain a calcined powder. This calcined powder is a complex oxide of Zn and Si of Zn 2 SiO 4 . The calcined powder was pulverized and granulated. Next, the calcined powder is used as a raw material powder, each raw material powder of ZnO and Al 2 O 3 is weighed so as to have a predetermined ratio, and the weighed raw material powders are mixed. The obtained mixed powder was fired in a nitrogen gas atmosphere at 1400 ° C. for 3 hours to obtain a sintered body. The sintered body was machined into a predetermined shape to produce a sputtering target for forming a transparent oxide film. The composition component in the manufactured sputtering target was analyzed. The analysis result is shown in FIG.

図１の写真は、製造されたスパッタリングターゲットについて、ＥＰＭＡ（フィールドエミッション型電子線プローブ）にて得られた元素分布像であり、図中の４枚の写真から、Ｚｎ、Ｓｉ、Ａ１、Ｏの各元素の組成分布の様子をそれぞれ観察することができる。
なお、ＥＰＭＡによる元素分布像は、本来カラー像であるが、図１の写真では、白黒像に変換して示しているため、その写真中において、白いほど、当該元素の濃度が高いことを表している。具体的には、Ａｌに関する分布像では、Ａｌ元素が白く斑点状（比較的白い部分）に分布し、Ｚｎに関する分布像では、Ｚｎ元素が全体的に存在し、その中でも、その濃度が高いと観られる白い部分が分布し、Ｏに関する分布像では、Ｏ元素が全体的にある程度の濃度で存在していることが観察される。そして、Ｓｉに関する分布像では、Ｓｉ元素が、ある程度の濃度で存在しているが、Ｚｎ元素の濃度が高い部分においては、存在していないことが観察できる。これらのことから、ＺｎＯと、ＳｉとＺｎとの複合酸化物（Ｚｎ２ＳｉＯ４）とが、別々に存在すると推定される。 The photograph in FIG. 1 is an element distribution image obtained by EPMA (field emission electron probe) for the manufactured sputtering target. From the four photographs in the figure, Zn, Si, A1, and O The state of composition distribution of each element can be observed individually.
Note that the element distribution image by EPMA is originally a color image, but in the photograph of FIG. 1, it is converted into a black and white image. Therefore, the whiter in the photograph, the higher the concentration of the element. ing. Specifically, in the distribution image related to Al, the Al element is distributed in white spots (relatively white portions), and in the distribution image related to Zn, the Zn element exists as a whole, and among them, the concentration is high. The white parts to be observed are distributed, and in the distribution image relating to O, it is observed that the O element is present at a certain concentration as a whole. In the distribution image relating to Si, it can be observed that the Si element is present at a certain concentration, but is not present in the portion where the Zn element concentration is high. From these, and ZnO, composite oxides of Si and Zn and (Zn 2 SiO 4), but is presumed to exist separately.

一方、図２のグラフは、上述したように製造された透明酸化物膜形成用のスパッタリングターゲットのＸ線回折（ＸＲＤ）による分析結果を示している。図２の上段のグラフは、全体のピークを示しているが、その中段のグラフには、Ｚｎ２ＳｉＯ４に係るピークが、そして、その下のグラフは、ＺｎＯに係るピークが示されている。図１に示された分布画像と図２のグラフに現れたピークとを併せて考慮すると、ＺｎＯおよび、またはＡＺＯ（ＡｌがドープされたＺｎＯ）と、ＺｎとＳｉとの複合酸化物とが別々に検出され、しかも、ＳｉＯ２の結晶相が存在していないことが分かる。なお、ＳｉＯ２が単独で存在し、かつ、結晶相析出しているのであれば、ＸＲＤ回折の結果に、それに対応するピークが現れるはずであるが、図２の回折結果のグラフには、そのピークが現れておらず、ＳｉＯ２の結晶相は検出されなかった。 On the other hand, the graph of FIG. 2 has shown the analysis result by X-ray diffraction (XRD) of the sputtering target for transparent oxide film formation manufactured as mentioned above. The upper graph in FIG. 2 shows the entire peak, the middle graph shows the peak related to Zn 2 SiO 4 , and the lower graph shows the peak related to ZnO. . Considering the distribution image shown in FIG. 1 and the peak appearing in the graph of FIG. 2 together, ZnO and / or AZO (Al-doped ZnO) and the composite oxide of Zn and Si are separated. It can be seen that there is no SiO 2 crystal phase. If SiO 2 is present alone and crystal phase is precipitated, a corresponding peak should appear in the XRD diffraction result. In the diffraction result graph of FIG. No peak appeared and no SiO 2 crystal phase was detected.

以上を総合すれば、製造したスパッタリングターゲットには、Ａｌ−Ｚｎ−Ｓｉ−Ｏ四元系元素でなる焼成体の素地中において、Ｓｉは、少なくとも、ＺｎとＳｉとの複合酸化物として存在し、ＳｉＯ２の結晶相は存在していないことが確認された。従って、Ａ１（及び／又はＧａ）−Ｚｎ−Ｓｉ−Ｏ透明酸化物膜を形成するためのスパッタリングターゲットを製造するとき、予め仮焼成されたＺｎ２ＳｉＯ４のＺｎとＳｉとの複合酸化物を原料粉末として作成しておき、この原料粉末と、ＺｎＯ粉末と、Ａｌ２Ｏ３粉末及び／又はＧａ２Ｏ３粉末とを用いて、成膜目的であるＡ１（及び／又はＧａ）−Ｚｎ−Ｓｉ−Ｏ膜の成分組成となるように秤量された混合粉末を焼成するという手順が、スパッタリングターゲット中におけるＺｎとＳｉとの複合酸化物粒子の存在を調整するのに有効であることが確認された。この手順の採用により、スパッタリング時には、異常放電・パーティクルの発生を低減することができ、透明酸化物膜を直流スパッタリングで成膜できるという知見が得られた。なお、ＡｌがＧａに置き換えられたＧａ−Ｚｎ−Ｓｉ−Ｏ四元系元素でなる焼成体の場合も、同様であった。 To sum up the above, in the manufactured sputtering target, Si exists as a composite oxide of at least Zn and Si in the substrate of the fired body made of the Al—Zn—Si—O quaternary element, It was confirmed that no SiO 2 crystal phase was present. Therefore, when manufacturing a sputtering target for forming an A1 (and / or Ga) -Zn-Si-O transparent oxide film, a pre-fired Zn 2 SiO 4 composite oxide of Zn and Si is used. leave prepared as raw material powder, this the raw material powder, with a ZnO powder and Al 2 O 3 powder and / or Ga 2 O 3 powder, a film forming object A1 (and / or Ga) -Zn- It was confirmed that the procedure of firing the mixed powder weighed so as to obtain the component composition of the Si—O film is effective in adjusting the presence of complex oxide particles of Zn and Si in the sputtering target. It was. By adopting this procedure, it was found that, during sputtering, abnormal discharge and generation of particles can be reduced, and a transparent oxide film can be formed by DC sputtering. Note that the same was true for a fired body made of a Ga—Zn—Si—O quaternary element in which Al was replaced with Ga.

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。
（１）本発明の透明酸化物膜形成用スパッタリングターゲットは、全金属成分量に対して、Ａｌ及びＧａのいずれか１種又は２種：０．６〜８．０ａｔ％と、Ｓｉ：０．１ａｔ％以上とを、ＡｌとＧａとＳｉとの合計で３３．０ａｔ％以下含有し、残部がＺｎおよび不可避不純物からなる組成の焼成体であり、該焼成体中において、５μｍ以下の粒径を有するＺｎとＳｉとの複合酸化物が存在していることを特徴とし、さらに、前記焼成体の抗折強度が、９０ＭＰａ以上であり、前記焼成体の相対密度が、９０％以上であり、前記焼成体の熱伝導率が、７．５Ｗ／ｍ・ｋ以上であることを特徴としている。 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.
(1) The sputtering target for forming a transparent oxide film according to the present invention has one or two of Al and Ga: 0.6 to 8.0 at%, Si: 0.0. 1 at% or more, and a total of 33.0 at% or less of Al, Ga and Si, and the balance is a fired body having a composition composed of Zn and inevitable impurities, and the fired body has a particle size of 5 μm or less. The composite oxide of Zn and Si is present, the bending strength of the fired body is 90 MPa or more, the relative density of the fired body is 90% or more, The heat conductivity of the fired body is 7.5 W / m · k or more.

（２）また、本発明の透明酸化物膜形成用スパッタリングターゲットの製造方法は、前記（１）の透明酸化物膜形成用スパッタリングターゲットを製造する方法であって、ＺｎＯ粉末とＳｉＯ２粉末とをモル比２：１で配合し混合した原料粉末を焼成した後に粉砕して複合酸化物粉末とし、前記複合酸化物粉末とＡｌ２Ｏ３粉末及びＧａ２Ｏ３粉末のいずれか１種又は２種と、ＺｎＯ粉末とを配合し混合して得られた混合粉末を焼成して焼成体を得ることを特徴とし、さらに、前記製造方法では、前記混合粉末は、１１００〜１４５０℃の温度、非酸化性雰囲気で、１〜１０時間を保持して焼成され、前記焼成体は、冷却速度：３０〜１５０℃／ｈで冷却されることを特徴としている。或いは、上記透明酸化物膜形成用スパッタリングターゲットの製造方法は、平均粒径：０．１〜３．０μｍのＺｎＯ粉末と、平均粒径：０．２〜４．０μｍのＳｉＯ２粉末とＡｌ２Ｏ３粉末及びＧａ２Ｏ３粉末のいずれか１種又は２種とを配合し混合し、１１５０〜１３００℃の温度、１００〜４００ｋｇｆ/ｃｍ２の圧力、非酸化性雰囲気で、１〜１０時間を保持して加圧焼成して焼成体を得ることを特徴としている。 (2) A method of manufacturing a transparent oxide film forming sputtering target of the present invention is a method for producing a transparent oxide film-forming sputtering target of (1), a ZnO powder and SiO 2 powder The raw material powder blended and mixed at a molar ratio of 2: 1 is fired and then pulverized to obtain a composite oxide powder, and any one or two of the composite oxide powder, Al 2 O 3 powder and Ga 2 O 3 powder And a mixed powder obtained by mixing and mixing ZnO powder to obtain a fired body, and in the manufacturing method, the mixed powder has a temperature of 1100 to 1450 ° C. and non-oxidation. It is characterized by being baked for 1 to 10 hours in a neutral atmosphere, and the fired body is cooled at a cooling rate of 30 to 150 ° C./h. Alternatively, the production method of the transparent oxide film for forming a sputtering target, the average particle size: and ZnO powder 0.1 to 3.0 m, an average particle diameter: SiO 2 powder 0.2~4.0μm and Al 2 One or two of O 3 powder and Ga 2 O 3 powder are blended and mixed, and the temperature is 1150 to 1300 ° C., the pressure is 100 to 400 kgf / cm 2 , and the atmosphere is non-oxidizing atmosphere for 1 to 10 hours. And is fired under pressure to obtain a fired body.

本発明の透明酸化物膜形成用スパッタリングターゲットにおける各元素の限定理由について、以下に述べる。
１）Ｓｉ：０．１ａｔ％以上
スパッタリングターゲット中のＳｉの含有量が、全金属成分量に対して、０．０１ａｔ％未満であると、結晶化を抑制する効果が小さいので添加の効果がなく、一方、多すぎると、ＳｉＯ２の結晶相が析出してしまうので、Ｓｉの含有量については、０．１ａｔ％以上とし、かつ、ＡｌとＧａとの合計で３３ａｔ％以下とすることが好ましく、効果的に結晶化を抑制することができる。
２）Ａｌ及びＧａのいずれか１種又は２種：０．６〜８．０ａｔ％
スパッタリングターゲット中のＡｌ及びＧａのいずれか１種又は２種の含有合計量が、０．６ａｔ％未満では、直流スパッタリング行うに十分な導電性が得られない。一方、それが、８．０ａｔ％を超えるとＡｌ又はＧａとＺｎとの複合酸化物であるＺｎＡｌ２Ｏ４、ＺｎＧａ２Ｏ４が発生しやすくなり、これに起因して、異常放電が発生して、直流スパッタリングができなくなる。なお、異常放電の発生を抑制するためには、これらの複合酸化物の（３１１）回折ピークが、ＺｎＯの（１０１）回折ピーク以下であることが望ましい。
３）Ｓｉ+Ａｌ＋Ｇａ：３３ａｔ％以下
スパッタリングターゲット中のＡｌとＧａとＳｉとの合計含有量が、３３ａｔ％を超えると、スパッタリングターゲット自体の比抵抗が高くなり、異常放電が発生しやすくなり、安定した直流スパッタリングが困難になるので、そのＡｌとＧａとＳｉとの合計含有量を、３３ａｔ％以下とした。
４）ＺｎとＳｉとの複合酸化物の粒径
スパッタリングターゲット中に存在するＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）の平均粒径（Ｄ５０）を、５μｍ以下とした理由は、この粒径が、５μｍを超えて大きくなると、スパッタリング時に、異常放電が多発するためであり、５μｍ以下とすることにより、異常放電の発生を抑制した。なお、ＺｎとＳｉとの複合酸化物の粒径は、４．５μｍ以下がより好ましく、４．１μｍ以下が最も好ましい。
５）焼成体の抗折強度・相対密度・熱伝導率
焼成体における抗折強度を、９０ＭＰａ以上とし、焼成体の相対密度を、９０％以上とし、さらに、焼成体の熱伝導率を、７．５Ｗ／ｍ・ｋ以上とした。この様に限定した理由は、ターゲット割れの発生を抑制できるからである。 The reasons for limiting each element in the sputtering target for forming a transparent oxide film of the present invention will be described below.
1) Si: 0.1 at% or more If the Si content in the sputtering target is less than 0.01 at% relative to the total metal component amount, the effect of suppressing crystallization is small, so there is no effect of addition. On the other hand, if it is too much, a crystal phase of SiO 2 is precipitated, so the Si content is preferably 0.1 at% or more and the total of Al and Ga is preferably 33 at% or less. , Crystallization can be effectively suppressed.
2) Any one or two of Al and Ga: 0.6 to 8.0 at%
If the total content of any one or two of Al and Ga in the sputtering target is less than 0.6 at%, sufficient conductivity for direct current sputtering cannot be obtained. On the other hand, if it exceeds 8.0 at%, ZnAl 2 O 4 and ZnGa 2 O 4 which are complex oxides of Al or Ga and Zn are likely to be generated, and abnormal discharge occurs due to this. Therefore, direct current sputtering cannot be performed. In order to suppress the occurrence of abnormal discharge, it is desirable that the (311) diffraction peak of these composite oxides is not more than the (101) diffraction peak of ZnO.
3) Si + Al + Ga: 33 at% or less If the total content of Al, Ga, and Si in the sputtering target exceeds 33 at%, the specific resistance of the sputtering target itself increases, abnormal discharge is likely to occur, and is stable. Therefore, the total content of Al, Ga and Si is set to 33 at% or less.
4) Particle size of composite oxide of Zn and Si The reason why the average particle size (D50) of the composite oxide of Zn and Si (Zn 2 SiO 4 ) present in the sputtering target is 5 μm or less is When the particle size is larger than 5 μm, abnormal discharge occurs frequently during sputtering. By setting the particle size to 5 μm or less, the occurrence of abnormal discharge was suppressed. The particle size of the composite oxide of Zn and Si is more preferably 4.5 μm or less, and most preferably 4.1 μm or less.
5) Bending strength, relative density, and thermal conductivity of fired body The bending strength of the fired body is 90 MPa or more, the relative density of the fired body is 90% or more, and the thermal conductivity of the fired body is 7 It was set to 5 W / m · k or more. The reason for this limitation is that the generation of target cracks can be suppressed.

また、本発明の透明酸化物膜形成用スパッタリングターゲットの製造方法では、スパッタリングターゲットの素材である焼結体を作製する前に、予め、ＺｎＯとＳｉＯ２の各原料粉末をＺｎＯ：ＳｉＯ２＝２：１（モル比）となるように秤量した混合粉末を焼成して、ＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）の仮焼体を得ることとした。この仮焼体を用いて、これを粉砕し、平均粒径（Ｄ５０）の微細なＺｎ２ＳｉＯ４粉末を作製することができる。この粉末を、上記焼結体を得るための原料粉末とした。この仮焼体を得るときの焼成条件としては、１０００〜１５００℃、望ましくは、１１００〜１２００℃の温度にて、２〜９時間、大気中又は酸素雰囲気中で焼成することができる。なお、Ｚｎ２ＳｉＯ４粉末の粒径が３０μｍ以下であれば、この粉末と、Ａｌ２Ｏ３粉末、ＺｎＯ粉末とを粉砕、混合して得られる混合粉末の平均粒径（Ｄ５０）を、５μｍ以下にすることが容易である。その粒径が３０μｍを超えると、その混合粉末の平均粒径（Ｄ５０）を５μｍ以下にするには、ボールミルする時間がかかりすぎ、生産性が低下するので、好ましくない。 Further, in the transparent oxide film-forming sputtering target production method of the present invention, prior to making a sintered body which is a material of the sputtering target, in advance, ZnO each raw material powder of ZnO and SiO 2: SiO 2 = 2 The powder mixture weighed so as to be 1 (molar ratio) was fired to obtain a calcined body of a complex oxide of Zn and Si (Zn 2 SiO 4 ). Using this calcined body, it can be pulverized to produce a fine Zn 2 SiO 4 powder having an average particle diameter (D50). This powder was used as a raw material powder for obtaining the sintered body. As a firing condition for obtaining this calcined body, it can be fired at 1000 to 1500 ° C., preferably 1100 to 1200 ° C. for 2 to 9 hours in the air or in an oxygen atmosphere. If the particle diameter of the Zn 2 SiO 4 powder is 30 μm or less, the average particle diameter (D50) of the mixed powder obtained by pulverizing and mixing this powder, the Al 2 O 3 powder, and the ZnO powder is 5 μm. It is easy to: If the particle size exceeds 30 μm, it takes too much time to ball mill and make the average particle size (D50) of the mixed powder 5 μm or less, which is not preferable.

次に、仮焼体を粉砕して得た仮焼粉、即ち、微細なＺｎ２ＳｉＯ４粉末を、焼成体を得るための一原料粉末とし、ＺｎＯ粉末、Ａｌ２Ｏ３粉末及びＧａ２Ｏ３粉末のいずれか１種又は２種の各原料粉末を、成膜目的であるＡ１（又はＧａ）−Ｚｎ−Ｓｉ−Ｏ四元系酸化物膜の成分組成となるように、所定の比率に秤量し、この秤量された各原料粉末を混合し混合粉末を得る。この混合粉末を冷間等方圧加圧（ＣＩＰ）で成形した後に、１２００〜１４５０℃の温度、望ましくは、１３５０〜１４００℃の温度にて、２〜９時間、窒素等の不活性ガス雰囲気中で焼成する。この焼成は、ホットプレス（ＨＰ）、熱間等方圧プレス（ＨＩＰ）としても良い。この焼成体に対して、所定形状に機械加工を施して、所定形状のスパッタリングターゲットが製作される。 Next, the calcined powder obtained by pulverizing the calcined body, that is, a fine Zn 2 SiO 4 powder is used as one raw material powder for obtaining a fired body, and ZnO powder, Al 2 O 3 powder and Ga 2 O are obtained. Any one or two raw material powders of the three powders are adjusted to a predetermined ratio so as to have a component composition of the A1 (or Ga) -Zn-Si-O quaternary oxide film that is the purpose of film formation. Weighing and mixing the weighed raw material powders to obtain a mixed powder. After this mixed powder is formed by cold isostatic pressing (CIP), it is an atmosphere of inert gas such as nitrogen at a temperature of 1200 to 1450 ° C., preferably at a temperature of 1350 to 1400 ° C. for 2 to 9 hours. Bake in. This baking may be performed by hot pressing (HP) or hot isostatic pressing (HIP). The fired body is machined into a predetermined shape to produce a sputtering target having a predetermined shape.

また、本発明の透明酸化物膜形成用スパッタリングターゲットの製造方法においては、前記混合粉末を、１１００〜１４５０℃の温度、非酸化性雰囲気（Ｎ２ガス、Ａｒガス、真空）で、１〜１０時間を保持して焼成することもでき、前記焼成体を、冷却速度：３０〜１５０℃／ｈで冷却することもできる。
混合粉末を焼成するとき、焼成保持時間が短すぎて、冷却速度が小さすぎると、抗折強度、相対密度、熱伝導率のいずれも下がるため、異常放電が多発するので好ましくない。これに対して、焼成保持時間が長すぎて、冷却速度が大きすぎると、ターゲット割れが発生するので好ましくない。これらの条件に従ってスパッタリングターゲットを製造することにより、焼成体の抗折強度・相対密度・熱伝導率を適切な範囲に調整することが可能となり、異常放電の低減や、ターゲット割れの発生を抑制できる。 In the transparent oxide film-forming sputtering target production method of the present invention, the mixed powder, the temperature of from 1100 to 1,450 ° C., a non-oxidizing atmosphere (N 2 gas, Ar gas, vacuum) at from 1 to 10 It can also be fired while maintaining the time, and the fired body can be cooled at a cooling rate of 30 to 150 ° C./h.
When the mixed powder is fired, if the firing holding time is too short and the cooling rate is too low, all of the bending strength, relative density, and thermal conductivity are lowered, and abnormal discharge occurs frequently. On the other hand, if the firing holding time is too long and the cooling rate is too high, target cracks occur, which is not preferable. By producing a sputtering target according to these conditions, it is possible to adjust the bending strength, relative density, and thermal conductivity of the fired body to appropriate ranges, and it is possible to reduce abnormal discharge and suppress the generation of target cracks. .

また、本発明の透明酸化物形成用スパッタリングターゲットの製造方法においては、平均粒径：０．１〜３．０μｍのＺｎＯ粉末と、平均粒径：０．２〜４．０μｍのＳｉＯ２粉末とＡｌ２Ｏ３粉末及びＧａ２Ｏ３粉末のいずれか１種又は２種とを配合し混合し、１１５０〜１３００℃の温度、１００〜４００ｋｇｆ/ｃｍ２の圧力、非酸化性雰囲気で、１〜１０時間を保持して加圧焼成して焼成体を得ることができる。 前記原料粉末を、平均粒径：０．１〜３．０μｍのＺｎＯ粉末、平均粒径：０．２〜４．０μｍのＳｉＯ２粉末を用いることで、前記仮焼体の製造工程を省略することが可能である。
また、前記混合粉末を、１１５０〜１３００℃の温度、１００〜４００ｋｇｆ/ｃｍ２、非酸化性雰囲気（Ｎ２ガス、Ａｒガス、真空）で、１〜１０時間を保持して焼成することもできる。焼成方法としては、例えばホットプレス、ＨＩＰを用いることができる。 In the method for producing a transparent oxide sputtering target for forming the present invention, the average particle diameter and ZnO powder 0.1 to 3.0 m, an average particle diameter and the SiO 2 powder 0.2~4.0μm One or two of Al 2 O 3 powder and Ga 2 O 3 powder are blended and mixed, and the temperature is 1150 to 1300 ° C., the pressure is 100 to 400 kgf / cm 2 , and the non-oxidizing atmosphere is 1 to 1. A fired body can be obtained by pressure firing while holding for 10 hours. By using ZnO powder having an average particle diameter of 0.1 to 3.0 μm and SiO 2 powder having an average particle diameter of 0.2 to 4.0 μm as the raw material powder, the manufacturing process of the calcined body is omitted. It is possible.
In addition, the mixed powder can be fired at a temperature of 1150 to 1300 ° C., 100 to 400 kgf / cm 2 , and a non-oxidizing atmosphere (N 2 gas, Ar gas, vacuum) for 1 to 10 hours. . As the firing method, for example, hot press or HIP can be used.

ＺｎＯ粉末及びＳｉＯ２粉末の平均粒径が小さすぎると、混合時の取り扱いが難しくなり、一方、それが大きすぎると、焼成時にＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）の粒径が５μｍを超えて大きくなり、異常放電が多発するので、好ましくない。混合粉末を焼成するとき、焼成保持時間が短すぎて、冷却速度が小さすぎると、抗折強度、相対密度、熱伝導率のいずれも下がるため、異常放電が多発するので好ましくない。これに対して、焼成保持時間が長すぎて、冷却速度が大きすぎると、ターゲット割れが発生するので好ましくない。これらの条件に従ってスパッタリングターゲットを製造することにより、焼成体の抗折強度・相対密度・熱伝導率を適切な範囲に調整することが可能となり、異常放電の低減や、ターゲット割れの発生を抑制できる。 If the average particle size of the ZnO powder and the SiO 2 powder is too small, handling during mixing becomes difficult. On the other hand, if it is too large, the particle size of the complex oxide of Zn and Si (Zn 2 SiO 4 ) during firing Is larger than 5 μm, and abnormal discharge occurs frequently. When the mixed powder is fired, if the firing holding time is too short and the cooling rate is too low, all of the bending strength, relative density, and thermal conductivity are lowered, and abnormal discharge occurs frequently. On the other hand, if the firing holding time is too long and the cooling rate is too high, target cracks occur, which is not preferable. By producing a sputtering target according to these conditions, it is possible to adjust the bending strength, relative density, and thermal conductivity of the fired body to appropriate ranges, and it is possible to reduce abnormal discharge and suppress the generation of target cracks. .

なお、本発明の透明酸化物膜形成用スパッタリングターゲットの製造方法では、酸素含有量が大気より少ない雰囲気で焼成を行うことが好ましい。これは、酸素含有量が大気より少ない雰囲気での焼結を行うと、スパッタリングターゲットの比抵抗が低くなる傾向があり、直流スパッタリングの異常放電が少なくなる傾向があるためである。   In addition, in the manufacturing method of the sputtering target for transparent oxide film formation of this invention, it is preferable to bake in the atmosphere with less oxygen content than air | atmosphere. This is because if the sintering is performed in an atmosphere having a lower oxygen content than the air, the specific resistance of the sputtering target tends to be low, and abnormal discharge of direct current sputtering tends to be low.

以上の様に、本発明の透明酸化物膜形成用スパッタリングターゲットは、直流スパッタリングによる低屈折率の透明酸化物膜の成膜に使用でき、光ディスクに好適な光透過保護膜、タッチパネル素子、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太陽電池などに用いられるガスバリア層などの成膜に使用するのに好適である。   As described above, the sputtering target for forming a transparent oxide film of the present invention can be used for the formation of a transparent oxide film having a low refractive index by direct current sputtering, and is suitable for a light transmission protective film, a touch panel element, and a liquid crystal display suitable for optical disks. It is suitable for use in forming a film such as a gas barrier layer used in electronic paper such as an element, an electroluminescence display element, an electrophoretic display element, and a toner display element, and a solar cell.

本発明の透明酸化物膜形成用スパッタリングターゲットによると、５μｍ以下の粒径（Ｄ５０）を有した微細なＺｎとＳｉとの複合酸化物が、焼成体中に存在しているので、直流スパッタリングで成膜するときに、異常放電の発生を無くし、或いは、低減することができ、直流スパッタリングで効率的に透明酸化物膜を成膜できるようになる。そして、透明酸化物膜形成用スパッタリングターゲットの製造においては、予め仮焼成されたＺｎ２ＳｉＯ４のＺｎとＳｉとの複合酸化物を原料粉末として作成しておき、この原料粉末と、ＺｎＯ粉末と、Ａｌ２Ｏ３粉末及び／又はＧａ２Ｏ３粉末とを用いて、成膜目的であるＡ１（及び／又はＧａ）−Ｚｎ−Ｓｉ−Ｏ膜の成分組成となるように秤量された混合粉末を焼成するという手順を採用することにより、そのスパッタリングターゲット中に存在するＺｎ２ＳｉＯ４のＺｎとＳｉとの複合酸化物を微細化することが容易になり、しかも、その量も容易に調整することができる。 According to the sputtering target for forming a transparent oxide film of the present invention, since a fine composite oxide of Zn and Si having a particle size (D50) of 5 μm or less is present in the fired body, direct current sputtering is used. When forming the film, the occurrence of abnormal discharge can be eliminated or reduced, and the transparent oxide film can be formed efficiently by direct current sputtering. Then, in the production of the transparent oxide film-forming sputtering target, advance to create a composite oxide of a previously tentatively calcined Zn 2 SiO 4 and Zn and Si as raw material powder, and the raw material powder, and ZnO powder , Al 2 O 3 powder and / or Ga 2 O 3 powder, mixed powder weighed to have a component composition of A1 (and / or Ga) —Zn—Si—O film for film formation By adopting the procedure of firing, it becomes easy to refine the composite oxide of Zn and Si of Zn 2 SiO 4 existing in the sputtering target, and the amount thereof can be easily adjusted. be able to.

本発明に係る透明酸化物膜形成用スパッタリングターゲットの一具体例について、スパッタリングターゲットの組織をＥＰＭＡにより測定した各元素の元素分布像である。It is an element distribution image of each element which measured the structure | tissue of the sputtering target by EPMA about one specific example of the sputtering target for transparent oxide film formation which concerns on this invention. 本発明に係る透明酸化物膜形成用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。It is a graph which shows the analysis result of the X-ray diffraction (XRD) of the sputtering target for transparent oxide film formation which concerns on this invention.

つぎに、本発明の透明酸化物膜形成用ターゲット及びその製造方法について、以下に、実施例により具体的に説明する。   Next, the transparent oxide film forming target of the present invention and the method for producing the same will be specifically described below with reference to examples.

〔第１実施例〕
第１実施例では、透明酸化物膜形成用スパッタリングターゲットを製造するにあたり、先ず、酸化亜鉛粉末と酸化ケイ素粉末との原料粉末を焼成した、ＺｎとＳｉとの複合酸化物からなる仮焼体を作製し、この仮焼体を粉砕してＺｎとＳｉとの複合酸化物粉末を得る。次に、得られたＺｎとＳｉとの複合酸化物粉末と、酸化亜鉛粉と、酸化アルミニウム粉末及び酸化ガリウム粉末の１種又は２種との混合粉末を成形後に焼成することにより焼成体を得て、これを機械加工して、スパッタリングターゲットを製造した。この製造について、以下に、詳述する。 [First embodiment]
In the first embodiment, in producing a sputtering target for forming a transparent oxide film, first, a calcined body made of a composite oxide of Zn and Si, obtained by firing a raw material powder of zinc oxide powder and silicon oxide powder. The calcined body is prepared and pulverized to obtain a composite oxide powder of Zn and Si. Next, the obtained composite oxide powder of Zn and Si, zinc oxide powder, and mixed powder of one or two of aluminum oxide powder and gallium oxide powder are fired after molding to obtain a fired body. This was machined to produce a sputtering target. This production will be described in detail below.

１）ＺｎとＳｉとの複合酸化物粉末と、酸化亜鉛粉と、酸化アルミニウム粉末との混合粉末を用いる場合について説明する。
先ず、酸化亜鉛（化学式：ＺｎＯ、Ｄ５０＝１μｍ）、酸化珪素（化学式：ＳｉＯ２、Ｄ５０＝２．０μｍ）の各原料粉末を、ＺｎＯ：ＳｉＯ２＝２：１（モル比）となるように秤量する。この秤量した各原料粉末とその３倍量（重量比）のジルコニアボール（直径５ｍｍと１０ｍｍを同重量）とをポリ容器に入れ、ボールミル装置にて、１６時間、湿式混合し、混合粉末を得る。なお、この際の溶媒に、例えば、アルコールを用いる。 1) A case where a mixed powder of a composite oxide powder of Zn and Si, a zinc oxide powder, and an aluminum oxide powder is used will be described.
First, each raw material powder of zinc oxide (chemical formula: ZnO, D 50 = 1 μm) and silicon oxide (chemical formula: SiO 2 , D 50 = 2.0 μm) becomes ZnO: SiO 2 = 2: 1 (molar ratio). Weigh as follows. Each of the weighed raw material powders and three times the weight (weight ratio) of zirconia balls (diameters 5 mm and 10 mm are the same weight) are placed in a plastic container and wet-mixed for 16 hours in a ball mill apparatus to obtain a mixed powder . In addition, alcohol is used for the solvent in this case, for example.

次に、得られた混合粉末を乾燥後、造粒し、１２００℃、５時間、大気中で焼成して、仮焼体（ＺｎとＳｉとの複合酸化物：Ｚｎ２ＳｉＯ４）とする。この仮焼体とその５倍量（重量比）のジルコニアボール（直径５ｍｍと１０ｍｍを同重量）とをポリ容器に入れ、ボールミル装置にて２４時間湿式粉砕する。なお、この際の溶媒には、例えば、アルコールを用いる。粉砕後、乾燥、造粒した仮焼粉（ＺｎとＳｉとの複合酸化物粉末）（化学式：Ｚｎ２ＳｉＯ４、Ｄ５０＝１２μｍ）と、酸化亜鉛（化学式：ＺｎＯ、Ｄ５０＝１μｍ）と、酸化アルミニウム（化学式：Ａｌ２Ｏ３、Ｄ５０＝０．２μｍ）との各原料粉末を所定の比率になるように秤量する。これらの配合比率は、表１に示されている。 Next, the obtained mixed powder is dried, granulated, and fired in the atmosphere at 1200 ° C. for 5 hours to obtain a calcined body (complex oxide of Zn and Si: Zn 2 SiO 4 ). This calcined body and a zirconia ball of 5 times the weight (weight ratio) (diameters of 5 mm and 10 mm are the same weight) are put in a plastic container and wet pulverized in a ball mill apparatus for 24 hours. In addition, alcohol is used for the solvent in this case, for example. After pulverized, dried and granulated calcined powder (composite oxide powder of Zn and Si) (chemical formula: Zn 2 SiO 4 , D 50 = 12 μm) and zinc oxide (chemical formula: ZnO, D 50 = 1 μm) Each raw material powder with aluminum oxide (chemical formula: Al 2 O 3 , D 50 = 0.2 μm) is weighed to a predetermined ratio. These blending ratios are shown in Table 1.

この秤量した各原料粉末とその５倍量（重量比）のジルコニアボール（直径５ｍｍと１０ｍｍを同重量）とをポリ容器に入れ、ボールミル装置にて２４時間湿式混合する。なお、この際の溶媒には、例えば、アルコールを用いる。次いで、得られた混合粉末を乾燥後、造粒し、冷間等方圧加圧（ＣＩＰ）で成形した後、１４００℃、３時間、窒素ガス雰囲気中で焼成し、焼成体を得た。なお、この焼成は、真空または不活性雰囲気において１２００℃、３時間、荷重２００ｋｇｆ・ｃｍ−２でのホットプレス（ＨＰ）で行うことも可能である。この焼成体を、機械加工することにより、直径１２５ｍｍ×厚さ５ｍｍのスパッタリングターゲットを得た。これで、表１に示された実施例１〜８及び比較例１〜４のスパッタリングターゲットが製造された。なお、比較例４の場合における仮焼体は、９５０℃の温度で焼成された。 Each of the weighed raw material powders and zirconia balls of 5 times the weight (weight ratio) (diameters 5 mm and 10 mm are the same weight) are put in a plastic container and wet-mixed for 24 hours in a ball mill apparatus. In addition, alcohol is used for the solvent in this case, for example. Next, the obtained mixed powder was dried, granulated, molded by cold isostatic pressing (CIP), and then fired in a nitrogen gas atmosphere at 1400 ° C. for 3 hours to obtain a fired body. In addition, this baking can also be performed by hot press (HP) with a load of 200 kgf · cm −2 at 1200 ° C. for 3 hours in a vacuum or an inert atmosphere. The fired body was machined to obtain a sputtering target having a diameter of 125 mm and a thickness of 5 mm. Thus, the sputtering targets of Examples 1 to 8 and Comparative Examples 1 to 4 shown in Table 1 were manufactured. In addition, the calcined body in the case of the comparative example 4 was baked at the temperature of 950 degreeC.

２）ＺｎとＳｉとの複合酸化物粉末と、酸化亜鉛粉（ＺｎＯ）と、酸化ガリウム粉末（Ｇａ２Ｏ３）との混合粉末を用いる場合について説明する。
この場合についても、上述した、ＺｎとＳｉとの複合酸化物粉末と、酸化亜鉛粉と、酸化アルミニウム粉末との混合粉末を用いる場合と同様の手順で、スパッタリングターゲットが製造された。つまり、酸化アルミニウム粉末の代わりに、酸化ガリウム粉末が用いられ、表１に示された配合比率により混合粉末を得た。これで、表１に示された実施例９〜１２及び比較例５、６のスパッタリングターゲットが製造された。 2) The case of using a mixed powder of a composite oxide powder of Zn and Si, zinc oxide powder (ZnO), and gallium oxide powder (Ga 2 O 3 ) will be described.
Also in this case, the sputtering target was manufactured in the same procedure as the case of using the mixed oxide powder of Zn and Si, the zinc oxide powder, and the aluminum oxide powder described above. That is, gallium oxide powder was used in place of the aluminum oxide powder, and a mixed powder was obtained according to the blending ratio shown in Table 1. Thus, the sputtering targets of Examples 9 to 12 and Comparative Examples 5 and 6 shown in Table 1 were manufactured.

３）ＺｎとＳｉとの複合酸化物粉末と、酸化亜鉛粉（ＺｎＯ）と、酸化アルミニウム粉末（Ａｌ２Ｏ３）及び酸化ガリウム粉末（Ｇａ２Ｏ３）との混合粉末を用いる場合について説明する。
この場合についても、上述した、ＺｎとＳｉとの複合酸化物粉末と、酸化亜鉛粉と、酸化アルミニウム粉末との混合粉末を用いる場合と同様の手順で、スパッタリングターゲットが製造された。つまり、酸化アルミニウム粉末に加えて、酸化ガリウム粉末も用いられ、表１に示された配合比率により混合粉末を得た。これで、表１に示された実施例１３及び比較例７のスパッタリングターゲットが製造された。 3) A case where a mixed powder of a composite oxide powder of Zn and Si, zinc oxide powder (ZnO), aluminum oxide powder (Al 2 O 3 ), and gallium oxide powder (Ga 2 O 3 ) is used will be described. .
Also in this case, the sputtering target was manufactured in the same procedure as the case of using the mixed oxide powder of Zn and Si, the zinc oxide powder, and the aluminum oxide powder described above. That is, in addition to the aluminum oxide powder, gallium oxide powder was also used, and a mixed powder was obtained according to the blending ratio shown in Table 1. Thus, the sputtering targets of Example 13 and Comparative Example 7 shown in Table 1 were manufactured.

これまでに説明されたスパッタリングターゲットの製造では、ＺｎとＳｉとの複合酸化物粉末を原料粉末とし、この粉末と他の原料粉末とを配合した混合粉末を焼成して焼成体を得ていた。ここで、比較のため、ＺｎとＳｉとの複合酸化物粉末を、酸化亜鉛（ＺｎＯ）と酸化ケイ素（ＳｉＯ２）の仮焼成により原料粉末を得るのではなく、即ち、従来から行われているように、酸化亜鉛（ＺｎＯ）と酸化ケイ素（ＳｉＯ２）との原料粉末を所定の比になるよう混合し、上述と同様の条件で焼成して焼成体を得る場合を用意した。この場合には、この焼成時に、ＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）が、酸化亜鉛（ＺｎＯ）と酸化ケイ素（ＳｉＯ２）とから焼成体中に形成される。表１には、比較例８のスパッタリングターゲットとして示した。 In the production of the sputtering target described so far, a composite oxide powder of Zn and Si is used as a raw material powder, and a mixed powder containing this powder and other raw material powders is fired to obtain a fired body. Here, for comparison, a composite oxide powder of Zn and Si is not obtained as a raw material powder by calcination of zinc oxide (ZnO) and silicon oxide (SiO 2 ). Thus, the raw material powder of zinc oxide (ZnO) and silicon oxide (SiO 2 ) was mixed so as to have a predetermined ratio, and fired under the same conditions as described above to prepare a fired body. In this case, during this firing, a composite oxide of Zn and Si (Zn 2 SiO 4 ) is formed in the fired body from zinc oxide (ZnO) and silicon oxide (SiO 2 ). Table 1 shows the sputtering target of Comparative Example 8.


次に、上記実施例１〜１３及び比較例１〜８のスパッタリングターゲットにおける金属組成を表２に示した。   Next, Table 2 shows metal compositions in the sputtering targets of Examples 1 to 13 and Comparative Examples 1 to 8.


次に、表１及び表２に示された上記実施例１〜１３及び比較例１〜８のスパッタリングターゲットについて、ＸＲＤ分析、ＥＰＭＡによる分析及び比抵抗測定を行った。   Next, XRD analysis, analysis by EPMA, and specific resistance measurement were performed on the sputtering targets of Examples 1 to 13 and Comparative Examples 1 to 8 shown in Tables 1 and 2.

＜ＸＲＤ分析＞
ＸＲＤ分析は、図２に示したＸＲＤ分析の場合と同様の手法で行った。スパッタリングターゲットについてのＸＲＤ分析により、ＸＲＤピークの有無を確認した。このＸＲＤ分析は、以下の条件で行った。
試料の準備：試料はＳｉＣ−Ｐａｐｅｒ（ｇｒｉｔ １８０）にて湿式研磨、乾燥の後、測定試料とした。
装置：理学電気社製（ＲＩＮＴ−Ｕｌｔｉｍａ／ＰＣ）
管球：Ｃｕ
管電圧：４０ｋＶ
管電流：４０ｍＡ
走査範囲（２θ）：５°〜８０°
スリットサイズ：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、受光（ＲＳ）０.８ｍｍ
測定ステップ幅：２θで０.０２度
スキャンスピード：毎分２度
試料台回転スピード：３０ｒｐｍ <XRD analysis>
The XRD analysis was performed by the same method as the XRD analysis shown in FIG. The presence or absence of an XRD peak was confirmed by XRD analysis on the sputtering target. This XRD analysis was performed under the following conditions.
Preparation of sample: The sample was wet-polished with SiC-Paper (grit 180) and dried, and then used as a measurement sample.
Equipment: Rigaku Electric (RINT-Ultima / PC)
Tube: Cu
Tube voltage: 40 kV
Tube current: 40 mA
Scanning range (2θ): 5 ° -80 °
Slit size: Divergence (DS) 2/3 degree, Scattering (SS) 2/3 degree, Light reception (RS) 0.8mm
Measurement step width: 0.02 degrees at 2θ Scan speed: 2 degrees per minute Sample stage rotation speed: 30 rpm

＜ＥＰＭＡ分析＞
スパッタリングターゲットの組織中におけるＺｎとＳｉとＡｌとＧａとＯの分布についてＥＰＭＡで得られた元素分布像から、その組織を確認した。 <EPMA analysis>
The distribution of Zn, Si, Al, Ga, and O in the structure of the sputtering target was confirmed from the element distribution image obtained by EPMA.

＜ＥＢＳＤ分析＞
スパッタリングターゲットの組織中におけるＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）の粒子についてＥＢＳＤで得られたＩＱマップから、その大きさを確認した。なお、ＩＱマップは９５μｍ×３３μｍの断面範囲を観察し粒子サイズを定量測定した。
なお、ＥＢＳＤは株式会社ＴＳＬソリューションズのＯＩＭ Ｄａｔａ Ｃｏｌｌｅｃｔｉｏｎを用いてパターンを収集し、同社製ＯＩＭ Ａｎａｌｙｓｉｓ ５．３１を用いて粒子の大きさを算出した。 <EBSD analysis>
The size of the composite oxide (Zn 2 SiO 4 ) particles of Zn and Si in the structure of the sputtering target was confirmed from the IQ map obtained by EBSD. In addition, the IQ map measured the particle size quantitatively by observing a cross-sectional area of 95 μm × 33 μm.
In addition, EBSD collected the pattern using OIM Data Collection of TSL Solutions, Inc., and calculated the particle size using OIM Analysis 5.31 manufactured by the company.

＜比抵抗測定＞
スパッタリングターゲットの比抵抗測定は、三菱化学(株)製の抵抗測定器ロレスタＧＰを用いて測定した。 <Specific resistance measurement>
The specific resistance of the sputtering target was measured using a resistance measuring instrument Loresta GP manufactured by Mitsubishi Chemical Corporation.

次に、上述した実施例１〜１３及び比較例１〜８のスパッタリングターゲットを用いて、以下の成膜条件により、成膜試験を行った。
＜成膜条件＞
・電源：ＤＣ１０００ＷまたはＲＦ１０００Ｗ
・全圧：０．４Ｐａ
・スパッタリングガス：Ａｒ＝４５ｓｃｃｍ、Ｏ２：５ｓｃｃｍ
・ターゲット−基板（ＴＳ）距離：７０ｍｍ Next, a film formation test was performed using the sputtering targets of Examples 1 to 13 and Comparative Examples 1 to 8 described above under the following film formation conditions.
<Film formation conditions>
・ Power supply: DC1000W or RF1000W
・ Total pressure: 0.4Pa
Sputtering gas: Ar = 45 sccm, O 2 : 5 sccm
-Target-substrate (TS) distance: 70 mm

上記の成膜条件に従った成膜試験により、異常放電回数を測定した。この測定結果により、実施例１〜１３及び比較例１〜８のスパッタリングターゲットの直流（ＤＣ）スパッタリングの可否を評価した。その測定・評価の結果を表３に示した。   The number of abnormal discharges was measured by a film formation test according to the above film formation conditions. Based on this measurement result, the possibility of direct current (DC) sputtering of the sputtering targets of Examples 1 to 13 and Comparative Examples 1 to 8 was evaluated. The results of the measurement / evaluation are shown in Table 3.

＜異常放電回数の測定＞
上述の条件において１２時間のスパッタリングを行い、異常放電の回数を計測した。その後、スパッタチャンバーを開放し、チャンバー内のパーティクルを確認した。 <Measurement of abnormal discharge times>
Sputtering was performed for 12 hours under the above conditions, and the number of abnormal discharges was measured. Thereafter, the sputtering chamber was opened, and particles in the chamber were confirmed.

なお、表３においては、プラズマが生じず、スパッタリング不能な場合に、「スパッタ不能」と表記した。
以上の結果を表３に示した。 In Table 3, when plasma is not generated and sputtering is impossible, “sputtering impossible” is indicated.
The above results are shown in Table 3.


表３に示されるように、上記実施例１〜１３のスパッタリングターゲットのいずれにおいても、ターゲットの組織中に、上述したＸＲＤ分析及びＥＰＭＡ分析では、ＺｎＯ及びＺｎ２ＳｉＯ４が形成されていることが確認できた。 As shown in Table 3, in any of the sputtering targets of Examples 1 to 13, ZnO and Zn 2 SiO 4 were formed in the target structure in the XRD analysis and EPMA analysis described above. It could be confirmed.

表３によれば、実施例１〜１３のスパッタリングターゲットを使用して、直流スパッタリングを行った結果、いずれにおいても、異常放電の発生回数が極めて少ない（１時間当たり０〜３回）ことが確認でき、いずれの実施例の場合にも、直流スパッタリングを行えることが実証され、パーティクル発生も確認できなかった。これに対して、比較例１、３、５のスパッタリングターゲットを直流スパッタリングで成膜しようとした場合には、プラズマが生じず、スパッタリング不能となり、或いは、比較例２、４、６、７、８の場合には、異常放電の多発（１時間当たり１００００回以上）により、１０秒以上の連続スパッタリングができなかった。各比較例では、高周波スパッタリングを行えば、成膜することができた。   According to Table 3, as a result of performing direct current sputtering using the sputtering targets of Examples 1 to 13, it was confirmed that in all cases, the number of occurrences of abnormal discharge was extremely small (0 to 3 times per hour). In any of the examples, it was proved that direct current sputtering can be performed, and generation of particles could not be confirmed. On the other hand, when the sputtering targets of Comparative Examples 1, 3, and 5 are to be formed by direct current sputtering, plasma is not generated and sputtering becomes impossible, or Comparative Examples 2, 4, 6, 7, and 8 In the case of, continuous sputtering for 10 seconds or more could not be performed due to frequent abnormal discharge (10,000 times or more per hour). In each comparative example, the film could be formed by high frequency sputtering.

また、比較例４の場合には、ＺｎＯ粉末とＳｉＯ２粉末の混合粉末を仮焼成するとき、その焼成温度が、低くかったため、仮焼体中に、ＺｎとＳｉとの複合酸化物が十分に形成されず、この仮焼体の粉砕粉と、ＺｎＯ粉末と、Ａｌ２Ｏ３粉末との混合粉末を焼成して焼結体を得たときに、大きなＺｎとＳｉとの複合酸化物粒子が形成されたものと考えられる。さらに、比較例８の場合には、最初から、ＺｎＯ粉末とＳｉＯ２粉末の混合粉末を焼成して焼結体を得ているため、そのときに、大きなサイズのＺｎとＳｉとの複合酸化物粒子が形成されている。 Further, in the case of Comparative Example 4, when the mixed powder of ZnO powder and SiO 2 powder was calcined, the calcining temperature was low, so that a complex oxide of Zn and Si was sufficient in the calcined body. When a sintered body is obtained by firing a mixed powder of the pulverized powder of this calcined body, ZnO powder, and Al 2 O 3 powder, a large composite oxide particle of Zn and Si It is thought that was formed. Furthermore, in the case of Comparative Example 8, since a sintered body is obtained by firing a mixed powder of ZnO powder and SiO 2 powder from the beginning, at that time, a large-sized composite oxide of Zn and Si Particles are formed.

〔第２実施例〕
上記した第１実施例では、透明酸化物膜形成用スパッタリングターゲットを製造するにあたり、先ず、酸化亜鉛（ＺｎＯ）粉末と酸化珪素（ＳｉＯ２）粉末とをモル比２：１で配合し混合した原料粉末を焼成した後に粉砕して焼成した、ＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）からなる仮焼体を作製し、この仮焼体を粉砕してＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）粉末を得る。次に、得られたＺｎ２ＳｉＯ４粉末と、ＺｎＯ粉末と、酸化アルミニウム（Ａｌ２Ｏ３）粉末及び酸化ガリウム（Ｇａ２Ｏ３）粉末の１種又は２種との混合粉末を成形後に焼成することにより焼成体を得て、これを機械加工して、スパッタリングターゲットを製造した。 [Second Embodiment]
In the first embodiment described above, in manufacturing a sputtering target for forming a transparent oxide film, first, a raw material in which zinc oxide (ZnO) powder and silicon oxide (SiO 2 ) powder are mixed and mixed in a molar ratio of 2: 1. A calcined body made of a complex oxide of Zn and Si (Zn 2 SiO 4 ), pulverized and fired after firing the powder, and the calcined body is ground to a composite oxide of Zn and Si (Zn 2 SiO 4 ) powder is obtained. Next, the obtained mixed powder of Zn 2 SiO 4 powder, ZnO powder, and one or two of aluminum oxide (Al 2 O 3 ) powder and gallium oxide (Ga 2 O 3 ) powder is fired after molding. By doing this, a fired body was obtained and machined to produce a sputtering target.

第２実施例では、上記透明酸化物膜形成用スパッタリングターゲットの製造方法において、上記の混合粉末の成形体を焼成した焼成体に係る抗折強度、熱伝導率及び相対密度に影響を与える焼成保持時間と、焼成後の冷却速度とを、表４に示されるように調整し、実施例１０１〜１２７の透明酸化物膜形成用スパッタリングターゲットを作製した。実施例１０１〜１０９は、Ｚｎ２ＳｉＯ４粉末：５０．０ｍｏｌ％と、Ａｌ２Ｏ３粉末：３．０ｍｏｌ％と、ＺｎＯ粉末：残部との混合粉末を用いた場合を、実施例１１０〜１１８は、Ｚｎ２ＳｉＯ４粉末：８０．０ｍｏｌ％と、Ａｌ２Ｏ３粉末：１．０ｍｏｌ％と、ＺｎＯ粉末：残部との混合粉末を用いた場合を、そして、実施例１１９〜１２７は、Ｚｎ２ＳｉＯ４粉末：２２．０ｍｏｌ％と、Ａｌ２Ｏ３粉末：０．６ｍｏｌ％と、ＺｎＯ粉末：残部との混合粉末を用いた場合を代表的に示している。 In the second embodiment, in the method for producing the sputtering target for forming a transparent oxide film, firing holding that affects the bending strength, thermal conductivity, and relative density of the fired body obtained by firing the above-mentioned mixed powder compact. The time and the cooling rate after firing were adjusted as shown in Table 4, and the transparent oxide film-forming sputtering targets of Examples 101 to 127 were produced. In Examples 110 to 109, the case where a mixed powder of Zn 2 SiO 4 powder: 50.0 mol%, Al 2 O 3 powder: 3.0 mol%, and ZnO powder: remainder was used was used in Examples 110 to 118. In the case of using a mixed powder of Zn 2 SiO 4 powder: 80.0 mol%, Al 2 O 3 powder: 1.0 mol%, ZnO powder: balance, and Examples 119 to 127 are Zn 2 SiO 4 powder: 22.0 mol%, Al 2 O 3 powder: 0.6 mol%, and a mixed powder of ZnO powder: remainder are shown representatively.

そこで、作製された実施例１０１〜１２７の透明酸化物膜形成用スパッタリングターゲットについて、抗折強度、熱伝導率及び相対速度を測定した。それらの測定結果が、表４に示されている。   Therefore, the bending strength, thermal conductivity, and relative speed of the produced sputtering targets for forming a transparent oxide film of Examples 101 to 127 were measured. The measurement results are shown in Table 4.

＜抗折強度の測定＞
上記で得られた焼成体から、幅：４ｍｍ、長さ：４０ｍｍ、厚さ：３ｍｍの寸法を有する板を切り出して、抗折試験片を作製した。
この試験片を用いて、ＪＩＳ Ｒ−１６０１に規定される方法により、三点曲げ試験を行い、抗折強度（ＭＰａ）を求めた。 <Measurement of bending strength>
A plate having dimensions of width: 4 mm, length: 40 mm, thickness: 3 mm was cut out from the fired body obtained above to produce a bending test piece.
Using this test piece, a three-point bending test was performed by the method prescribed in JIS R-1601 to determine the bending strength (MPa).

＜熱伝導率の測定＞
上記で得られた焼成体から得た試料について、レーザーフラッシュ法により、熱伝導率（Ｗ／ｍ／ｋ）の測定を行った。
分析装置：ＮＥＴＺＳＣＨ−GeratebauGmbH製、Ｘｅフラッシュアナライザー、試料サイズ：１０ｍｍ×１０ｍｍ、厚さ：２ｍｍ、測定温度：２５℃、標準比較試料：ＳＵＳ３１０、パルス幅：０．２ｍｓ、チャージレベル：２７０Ｖの条件で測定を行った。この測定では、同じ試料にて３回行い、それらの測定値の平均値を求めた。 <Measurement of thermal conductivity>
About the sample obtained from the sintered body obtained above, the thermal conductivity (W / m / k) was measured by a laser flash method.
Analytical apparatus: manufactured by NETZSCH-Geratebau GmbH, Xe flash analyzer, sample size: 10 mm × 10 mm, thickness: 2 mm, measurement temperature: 25 ° C., standard comparison sample: SUS310, pulse width: 0.2 ms, charge level: 270 V Measurements were made. This measurement was performed three times on the same sample, and the average value of the measured values was obtained.

＜相対密度の測定＞
相対密度比（％）は、焼成体を所定寸法に機械加工した後、重量を測定し、嵩密度を求めた後、理論密度ρｆｎで割ることで算出した。なお、理論密度ρｆｎについては、原料の重量に基づいて、以下に示した式により求めた。この式は、Ａｌ２Ｏ３粉末とＧａ２Ｏ３粉末の両方を混合した場合を示しているので、第２実施例では、Ａｌ２Ｏ３粉末のみを混合しているので、Ｃ４：Ｇａ２Ｏ３に係る項は無いものとして求める。 <Measurement of relative density>
The relative density ratio (%) was calculated by machining the fired body to a predetermined size, measuring the weight, obtaining the bulk density, and dividing by the theoretical density ρ fn . The theoretical density ρ fn was determined by the following formula based on the weight of the raw material. Since this formula shows a case where both Al 2 O 3 powder and Ga 2 O 3 powder are mixed, in the second embodiment, only Al 2 O 3 powder is mixed, so C4: Ga 2 It is determined that there is no term relating to O 3 .



次に、表４に示された上記実施例１０１〜１２７のスパッタリングターゲットについて、ＸＲＤ分析、ＥＰＭＡによる分析及び比抵抗測定を行った。ＸＲＤ分析、ＥＰＭＡによる分析及び比抵抗測定は、第１実施例のスパッタリングターゲットについて行ったのと同様の条件で行われた。それらの結果が表５に示されている。
また、実施例１０１〜１２７のスパッタリングターゲットを用いて、第１実施例と同様の成膜条件により、成膜試験を行った。
上記の成膜条件に従った成膜試験により、異常放電回数を測定した。この測定結果により、実施例１０１〜１２７のスパッタリングターゲットの直流（ＤＣ）スパッタリングの可否を評価した。その測定・評価の結果を表５に示した。 Next, XRD analysis, analysis by EPMA, and specific resistance measurement were performed on the sputtering targets of Examples 101 to 127 shown in Table 4. XRD analysis, analysis by EPMA, and specific resistance measurement were performed under the same conditions as those for the sputtering target of the first example. The results are shown in Table 5.
In addition, using the sputtering targets of Examples 101 to 127, a film formation test was performed under the same film formation conditions as in the first example.
The number of abnormal discharges was measured by a film formation test according to the above film formation conditions. Based on the measurement results, the possibility of direct current (DC) sputtering of the sputtering targets of Examples 101 to 127 was evaluated. The results of the measurement / evaluation are shown in Table 5.


表５に示されるように、上記実施例１０１〜１２７のスパッタリングターゲットのいずれにおいても、ターゲットの組織中に、上述したＸＲＤ分析及びＥＰＭＡ分析では、ＺｎＯ及びＺｎ２ＳｉＯ４が形成されていることが確認でき、Ｚｎ２ＳｉＯ４粒径は、５μｍ以下である。さらに、実施例１０１〜１２７のスパッタリングターゲットを使用して、直流スパッタリングを行った結果、いずれにおいても、異常放電の発生回数が少なく、いずれの実施例の場合にも、直流スパッタリングを行えることが実証され、パーティクル発生も確認できなかった。そして、焼成保持時間と、焼成後の冷却速度を調整することにより、適切な抗折強度、熱伝導率及び相対密度を有するスパッタリングターゲットが得られることが確認され、異常放電の発生を低減でき、ターゲット割れを抑制できた。なお、Ａｌ２Ｏ３粉末の代わりに、Ｇａ２Ｏ３粉末のみを、或いは、Ａｌ２Ｏ３粉末とＧａ２Ｏ３粉末の両方を混合した場合においても、上記と同様の結果が得られた。 As shown in Table 5, in any of the sputtering targets of Examples 101 to 127, ZnO and Zn 2 SiO 4 were formed in the target structure in the XRD analysis and EPMA analysis described above. It can be confirmed that the Zn 2 SiO 4 particle size is 5 μm or less. Furthermore, as a result of performing direct current sputtering using the sputtering targets of Examples 101 to 127, in all cases, the number of occurrences of abnormal discharge was small, and it was demonstrated that direct current sputtering can be performed in any of the Examples. The generation of particles could not be confirmed. And by adjusting the firing holding time and the cooling rate after firing, it is confirmed that a sputtering target having an appropriate bending strength, thermal conductivity and relative density can be obtained, the occurrence of abnormal discharge can be reduced, Target cracking could be suppressed. Incidentally, instead of Al 2 O 3 powder, only Ga 2 O 3 powder, or in the case of mixing of both Al 2 O 3 powder and Ga 2 O 3 powder is also similar to the above results were obtained .

〔第３実施例〕
上記第１実施例における透明酸化物膜形成用スパッタリングターゲットの製造方法では、ＺｎＯ粉末とＳｉＯ２粉末とを仮焼成したＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）を原料粉末とし、表１に示される原料組成となる混合粉末を焼成したが、第３実施例では、仮焼体の製造工程を省略しており、Ｚｎ２ＳｉＯ４粉末を用いる代わりに、相当量のＺｎＯ粉末とＳｉＯ２粉末を原料粉末として使用することとした。第３実施例による透明酸化物膜形成用スパッタリングターゲットの製造方法では、ＳｉＯ２粉末、Ａｌ２Ｏ３粉末及びＺｎＯ粉末を原料粉末とした。原料粉末のうち、ＺｎＯ粉末及びＳｉＯ２粉末については、表６に示される粒径のＺｎＯ粉末及びＳｉＯ２粉末を用いた。さらに、上記の焼成体に係る抗折強度、熱伝導率及び相対密度に影響を与える焼成温度と焼成保持時間とを、表６に示されるように調整し、実施例２０１〜２２７の透明酸化物膜形成用スパッタリングターゲットを作製した。実施例２０１〜２０９は、ＳｉＯ２粉末：２５．４ｍｏｌ％と、Ａｌ２Ｏ３粉末：１．６ｍｏｌ％と、ＺｎＯ粉末：残部との混合粉末を用いた場合を、実施例２１０〜２１８は、ＳｉＯ２粉末：３０．６ｍｏｌ％と、Ａｌ２Ｏ３粉末：０．４ｍｏｌ％と、ＺｎＯ粉末：残部との混合粉末を用いた場合を、そして、実施例２１９〜２２７は、ＳｉＯ２粉末：１５．３ｍｏｌ％と、Ａｌ２Ｏ３粉末：０．４ｍｏｌ％と、ＺｎＯ粉末：残部との混合粉末を用いた場合を代表的に示している。 [Third embodiment]
Above the transparent oxide film for forming a sputtering target manufacturing method of the first embodiment, a composite oxide of Zn and Si was calcined and ZnO powder and SiO 2 powder (Zn 2 SiO 4) as a raw material powder, Table Although the mixed powder having the raw material composition shown in FIG. 1 was fired, in the third example, the manufacturing process of the calcined body was omitted, and instead of using the Zn 2 SiO 4 powder, a considerable amount of ZnO powder and SiO 2 were used. Two powders were used as raw powders. In the third embodiment a transparent oxide film-forming sputtering target manufacturing method of according to, SiO 2 powder, the Al 2 O 3 powder and ZnO powder as the raw material powder. Of the raw material powder, for ZnO powder and SiO 2 powder were used ZnO powder and SiO 2 powder having a particle diameter shown in Table 6. Furthermore, the firing temperature and firing retention time affecting the bending strength, thermal conductivity and relative density of the fired body were adjusted as shown in Table 6, and the transparent oxides of Examples 201 to 227 were used. A sputtering target for film formation was produced. In Examples 201 to 209, when using a mixed powder of SiO 2 powder: 25.4 mol%, Al 2 O 3 powder: 1.6 mol%, and ZnO powder: balance, Examples 210 to 218 are When using a mixed powder of SiO 2 powder: 30.6 mol%, Al 2 O 3 powder: 0.4 mol% and ZnO powder: balance, Examples 219 to 227 are SiO 2 powder: 15 The case where a mixed powder of .3 mol%, Al 2 O 3 powder: 0.4 mol%, and ZnO powder: remainder is used is representatively shown.

そこで、作製された実施例２０１〜２２７の透明酸化物膜形成用スパッタリングターゲットについて、上記第２実施例の場合と同様の手法で、抗折強度、熱伝導率及び相対速度を測定した。それらの測定結果が、表６に示されている。   Therefore, with respect to the produced sputtering targets for forming transparent oxide films of Examples 201 to 227, the bending strength, the thermal conductivity, and the relative velocity were measured by the same method as in the case of the second example. The measurement results are shown in Table 6.


次に、表６に示された上記実施例２０１〜２２７のスパッタリングターゲットについて、ＸＲＤ分析、ＥＰＭＡによる分析及び比抵抗測定を行った。ＸＲＤ分析、ＥＰＭＡによる分析及び比抵抗測定は、第１実施例のスパッタリングターゲットについて行ったのと同様の条件で行われた。それらの結果が表７に示されている。
また、実施例２０１〜２２７のスパッタリングターゲットを用いて、第１実施例と同様の成膜条件により、成膜試験を行った。
上記の成膜条件に従った成膜試験により、異常放電回数を測定した。この測定結果により、実施例２０１〜２２７のスパッタリングターゲットの直流（ＤＣ）スパッタリングの可否を評価した。その測定・評価の結果を表７に示した。 Next, the sputtering targets of Examples 201 to 227 shown in Table 6 were subjected to XRD analysis, EPMA analysis, and specific resistance measurement. XRD analysis, analysis by EPMA, and specific resistance measurement were performed under the same conditions as those for the sputtering target of the first example. The results are shown in Table 7.
Further, using the sputtering targets of Examples 201 to 227, a film formation test was performed under the same film formation conditions as in the first example.
The number of abnormal discharges was measured by a film formation test according to the above film formation conditions. Based on the measurement results, the possibility of direct current (DC) sputtering of the sputtering targets of Examples 201 to 227 was evaluated. The results of the measurement / evaluation are shown in Table 7.


表７に示されるように、上記実施例２０１〜２２７のスパッタリングターゲットのいずれにおいても、ターゲットの組織中に、上述したＸＲＤ分析及びＥＰＭＡ分析では、ＺｎＯ及びＺｎ２ＳｉＯ４が形成されていることが確認でき、Ｚｎ２ＳｉＯ４粒径は、５μｍ以下である。さらに、実施例２０１〜２２７のスパッタリングターゲットを使用して、直流スパッタリングを行った結果、いずれにおいても、異常放電の発生回数が少なく、いずれの実施例の場合にも、直流スパッタリングを行えることが実証され、パーティクル発生も確認できなかった。そして、焼成温度と焼成保持時間とを調整することにより、適切な抗折強度、熱伝導率及び相対密度を有するスパッタリングターゲットが得られることが確認され、異常放電の発生を低減でき、ターゲット割れを抑制できた。なお、Ａｌ２Ｏ３粉末の代わりに、Ｇａ２Ｏ３粉末のみを、或いは、Ａｌ２Ｏ３粉末とＧａ２Ｏ３粉末の両方を混合した場合においても、上記と同様の結果が得られた。 As shown in Table 7, in any of the sputtering targets of Examples 201 to 227, ZnO and Zn 2 SiO 4 were formed in the target structure in the XRD analysis and EPMA analysis described above. It can be confirmed that the Zn 2 SiO 4 particle size is 5 μm or less. Furthermore, as a result of performing direct current sputtering using the sputtering targets of Examples 201 to 227, in all cases, the number of occurrences of abnormal discharge was small, and it was proved that direct current sputtering can be performed in any case. The generation of particles could not be confirmed. And by adjusting the firing temperature and firing holding time, it is confirmed that a sputtering target having an appropriate bending strength, thermal conductivity and relative density can be obtained, the occurrence of abnormal discharge can be reduced, and target cracking can be reduced. I was able to suppress it. Incidentally, instead of Al 2 O 3 powder, only Ga 2 O 3 powder, or in the case of mixing of both Al 2 O 3 powder and Ga 2 O 3 powder is also similar to the above results were obtained .

以上の様に、本発明による透明酸化物膜形成用スパッタリングターゲットの製造方法によると、ＺｎＯ粉末とＳｉＯ２粉末の混合粉末を仮焼成して、Ｚｎ２ＳｉＯ４の組成を有するＺｎとＳｉとの複合酸化物を形成して仮焼体を得ておき、この仮焼体を微細な粉砕粉とした後に、この粉砕粉を原料粉末とし、これと、ＺｎＯ粉末と、Ａｌ２Ｏ３粉末及びＧａ２Ｏ３粉末の１種又は２種とを混合した混合粉末を焼成することにより焼成体を得るようにしたので、その焼成体中には、微細なＺｎとＳｉとの複合酸化物（Ｚｎ２ＳｉＯ４）が存在していることが確認され、そして、そのスパッタリングターゲットでは、比抵抗も低減することができて、直流（ＤＣ）スパッタリングを可能とすることができた。さらに、適切な抗折強度、熱伝導率及び相対密度を有するスパッタリングターゲットが得られるので、異常放電の発生を低減でき、ターゲット割れを抑制できた。



As described above, according to the method for manufacturing a sputtering target for forming a transparent oxide film according to the present invention, a mixed powder of ZnO powder and SiO 2 powder is temporarily fired to obtain Zn and Si having a composition of Zn 2 SiO 4 . A calcined body is obtained by forming a composite oxide, and the calcined body is made into a fine pulverized powder. Then, the pulverized powder is used as a raw material powder, ZnO powder, Al 2 O 3 powder, and Ga. Since a fired body is obtained by firing a mixed powder obtained by mixing one or two kinds of 2 O 3 powder, a fine complex oxide of Zn and Si (Zn 2) is contained in the fired body. The presence of SiO 4 ) was confirmed, and the sputtering target was able to reduce the specific resistance and enable direct current (DC) sputtering. Furthermore, since a sputtering target having appropriate bending strength, thermal conductivity and relative density can be obtained, occurrence of abnormal discharge can be reduced and target cracking can be suppressed.



Claims (7)

全金属成分量に対して、Ａｌ及びＧａのいずれか１種又は２種：０．６〜８．０ａｔ％と、Ｓｉ：０．１ａｔ％以上とを、ＡｌとＧａとＳｉとの合計で３３．０ａｔ％以下含有し、残部がＺｎおよび不可避不純物からなる組成の焼成体であり、
前記焼成体中において、ＺｎとＳｉとの複合酸化物の粒径が５μｍ以下であることを特徴とする透明酸化物膜形成用スパッタリングターゲット。 One or two of Al and Ga with respect to the total amount of metal components: 0.6 to 8.0 at%, Si: 0.1 at% or more, and a total of 33 of Al, Ga, and Si 0.0 at% or less, and the balance is a fired body having a composition consisting of Zn and inevitable impurities,
A sputtering target for forming a transparent oxide film, wherein a particle size of a complex oxide of Zn and Si is 5 μm or less in the fired body. 前記焼成体の抗折強度が、９０ＭＰａ以上であることを特徴とする請求項１に記載の透明酸化物膜形成用スパッタリングターゲット。   2. The sputtering target for forming a transparent oxide film according to claim 1, wherein the bending strength of the fired body is 90 MPa or more. 前記焼成体の相対密度が、９０％以上であることを特徴とする請求項１に記載の透明酸化物膜形成用スパッタリングターゲット。   2. The sputtering target for forming a transparent oxide film according to claim 1, wherein a relative density of the fired body is 90% or more. 前記焼成体の熱伝導率が、７．５Ｗ／ｍ・ｋ以上であることを特徴とする請求項１に記載の透明酸化物膜形成用スパッタリングターゲット。   2. The sputtering target for forming a transparent oxide film according to claim 1, wherein the fired body has a thermal conductivity of 7.5 W / m · k or more. 請求項１乃至４のいずれかに記載の透明酸化物膜形成用スパッタリングターゲットの製造方法であって、
ＺｎＯ粉末とＳｉＯ２粉末とをモル比２：１で配合し混合した原料粉末を焼成した後に粉砕して複合酸化物粉末とし、
前記複合酸化物粉末とＡｌ２Ｏ３粉末及びＧａ２Ｏ３粉末のいずれか１種又は２種と、ＺｎＯ粉末とを配合し混合して得られた混合粉末を焼成して焼成体を得ることを特徴とする透明酸化物膜形成用スパッタリングターゲットの製造方法。 It is a manufacturing method of the sputtering target for transparent oxide film formation according to any one of claims 1 to 4,
A raw material powder prepared by mixing and mixing ZnO powder and SiO 2 powder at a molar ratio of 2: 1 is fired and then pulverized to obtain a composite oxide powder.
A mixed powder obtained by blending and mixing any one or two of the composite oxide powder, Al 2 O 3 powder and Ga 2 O 3 powder, and ZnO powder is fired to obtain a fired body. A method for producing a sputtering target for forming a transparent oxide film, comprising: 前記混合粉末は、１１００〜１４５０℃の温度、非酸化性雰囲気で、１〜１０時間を保持して焼成され、
前記焼成体は、冷却速度：３０〜１５０℃／ｈで冷却されることを特徴とする請求項５に記載の透明酸化物膜形成用スパッタリングターゲットの製造方法。 The mixed powder is fired at 1100 to 1450 ° C. in a non-oxidizing atmosphere for 1 to 10 hours,
The method for producing a sputtering target for forming a transparent oxide film according to claim 5, wherein the fired body is cooled at a cooling rate of 30 to 150 ° C./h. 請求項１乃至４のいずれかに記載の透明酸化物膜形成用スパッタリングターゲットの製造方法であって、
平均粒径：０．１〜３．０μｍのＺｎＯ粉末と、平均粒径：０．２〜４．０μｍのＳｉＯ２粉末とＡｌ２Ｏ３粉末及びＧａ２Ｏ３粉末のいずれか１種又は２種とを配合し混合し、１１５０〜１３００℃の温度、１００〜４００ｋｇｆ/ｃｍ２の圧力、非酸化性雰囲気で、１〜１０時間を保持して加圧焼成して焼成体を得ることを特徴とする透明酸化物膜形成用スパッタリングターゲットの製造方法。



It is a manufacturing method of the sputtering target for transparent oxide film formation according to any one of claims 1 to 4,
ZnO powder with an average particle size of 0.1 to 3.0 μm, SiO 2 powder with an average particle size of 0.2 to 4.0 μm, any one of Al 2 O 3 powder and Ga 2 O 3 powder, or 2 It is characterized by blending seeds and mixing them to obtain a fired body by pressurizing and firing at a temperature of 1150 to 1300 ° C., a pressure of 100 to 400 kgf / cm 2 and a non-oxidizing atmosphere for 1 to 10 hours. A method for producing a sputtering target for forming a transparent oxide film.



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