JP5602820B2 - Manufacturing method of ZnO sintered body - Google Patents
Manufacturing method of ZnO sintered body Download PDFInfo
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本発明は、太陽電池、タッチパネル等の透明電極に用いられる透明導電膜をスパッタリング法で形成するためのスパッタリングターゲット材料に用いられるＺｎＯ焼結体の製造方法に関するものである。 The present invention relates to a method for producing a ZnO sintered body used for a sputtering target material for forming a transparent conductive film used for transparent electrodes such as solar cells and touch panels by a sputtering method.
近年、低コストで高い透明性、導電性および化学的安定性を有するＺｎＯ透明導電膜が注目されている。ＺｎＯ系の透明導電膜の形成方法としては、緻密で膜質の良い膜が得られやすい、スパッタリング法が最も適していると考えられ、スパッタリングターゲット材料に用いられるＺｎＯ焼結体が種々検討されている。 In recent years, a ZnO transparent conductive film having high transparency, conductivity, and chemical stability at low cost has attracted attention. As a method of forming a ZnO-based transparent conductive film, a sputtering method is considered to be most suitable because a dense and good film quality can be easily obtained, and various ZnO sintered bodies used for sputtering target materials have been studied. .
例えば、特許文献１では、１〜９原子％の硼素を含有し、実質的に亜鉛と硼素の複合酸化物からなることを特徴とするＺｎＯ系焼結体が開示されている。 For example, Patent Document 1 discloses a ZnO-based sintered body characterized by containing 1 to 9 atomic% of boron and substantially consisting of a composite oxide of zinc and boron.
特許文献１によれば、焼結密度が４．８ｇ／ｃｍ３以上であって、亜鉛と硼素の複合酸化物の結晶平均粒径が４〜１５μｍであること、硼素の偏析径が１０μｍ以下であること、焼結体内部に存在する空孔の最大径が５μｍ以下であることを達成することによって、長期的に異常放電の発生が少ない焼結体を得ることができるとされている。 According to Patent Document 1, the sintered density is 4.8 g / cm 3 or more, the crystal average particle diameter of the composite oxide of zinc and boron is 4 to 15 μm, and the segregation diameter of boron is 10 μm or less. In addition, by achieving that the maximum diameter of the pores existing inside the sintered body is 5 μm or less, it is said that a sintered body with less occurrence of abnormal discharge in the long term can be obtained.
しかしながら、このような硼素を添加したＺｎＯ焼結体は、緻密化し難いという問題があった。またスパッタリングターゲットとして用いたときに得られる膜の抵抗のバラツキが大きくなる問題があった。 However, the ZnO sintered body to which such boron is added has a problem that it is difficult to densify. In addition, there is a problem that variation in resistance of a film obtained when used as a sputtering target becomes large.
本発明は、これらの問題に鑑みてなされたものであり、膜特性の均一性に優れた透明導電膜作製用のＺｎＯ焼結体の製造方法を提供するものである。 This invention is made | formed in view of these problems, and provides the manufacturing method of the ZnO sintered compact for transparent conductive film preparation excellent in the uniformity of a film | membrane characteristic.
本発明は、これらの問題を解決するため、以下の（１）〜（３）を提供する。
（１）ＺｎＯ粉末とＢ２Ｏ３粉末とを混合、焼成及び粉砕してＺｎ４Ｂ６Ｏ１３粉末を得る工程と、平均粒径が０．５〜１μｍのＺｎＯ粉末と平均粒径が０．２〜０．５μｍのＺｎ４Ｂ６Ｏ１３粉末とを混合、成形、焼成してＺｎＯ焼結体を得る工程と、を含むＺｎＯ焼結体の製造方法。
（２）ＺｎＯ粉末とＢ２Ｏ３粉末の混合比はｍｏｌ比で４：６〜７：３であり、ＺｎＯ粉末とＢ２Ｏ３粉末とを大気雰囲気中、８００〜１０００℃にて焼成を行う（１）記載のＺｎＯ焼結体の製造方法。
（３）得られたＺｎ４Ｂ６Ｏ１３粉末とＺｎＯ粉末をＢの含有割合がＢ２Ｏ３換算で０．０１〜３．０ｍｏｌ％になるように混合する（１）又は（２）記載のＺｎＯ焼結体の製造方法。
In order to solve these problems, the present invention provides the following (1) to (3).
(1) A step of obtaining Zn 4 B 6 O 13 powder by mixing, firing and pulverizing ZnO powder and B 2 O 3 powder, and ZnO powder having an average particle size of 0.5 to 1 μm and an average particle size of 0 A step of mixing, forming and firing a Zn 4 B 6 O 13 powder of 2 to 0.5 μm to obtain a ZnO sintered body.
(2) The mixing ratio of ZnO powder and B 2 O 3 powder is 4: 6 to 7: 3 in terms of molar ratio, and the ZnO powder and B 2 O 3 powder are baked at 800 to 1000 ° C. in an air atmosphere. The manufacturing method of the ZnO sintered compact as described in (1) performed.
(3) The obtained Zn 4 B 6 O 13 powder and ZnO powder are mixed so that the B content is 0.01 to 3.0 mol% in terms of B 2 O 3 (1) or (2) Manufacturing method of ZnO sintered body.
（１）のようにＺｎＯ焼結体のＢ源をＺｎ４Ｂ６Ｏ１３とすれば、Ｂを均一に分散して、Ｂの固溶、置換をし易くして、微細な焼結粒径の組織を持ち、粒径のばらつきが小さい均一化されたＺｎＯ焼結体を得ることができる。 If the B source of the ZnO sintered body is Zn 4 B 6 O 13 as in (1), B is uniformly dispersed to facilitate the solid solution and substitution of B, and the fine sintered particle size A homogenized ZnO sintered body having a structure with a small variation in particle size can be obtained.
さらに、ＺｎＯ粉末の平均粒径が０．５〜１μｍであり、Ｚｎ４Ｂ６Ｏ１３粉末の平均粒径は０．２〜０．５μｍであるので、Ｚｎ４Ｂ６Ｏ１３粉末の平均粒径は主原料ＺｎＯの平均粒径に対して１／２以下となる。そのため、熱処理前の成形体の段階での均一かつ広範囲なＢの分布が得られ、Ｂを均一かつ高い割合でＺｎＯに固溶させることができる。これにより、Ｂの容易に固溶、置換も起きるため、Ｂの固溶と粒径が均一なターゲット用のＺｎＯ焼結体を得ることが可能となる。 Furthermore, since the average particle diameter of the ZnO powder is 0.5-1 μm and the average particle diameter of the Zn 4 B 6 O 13 powder is 0.2-0.5 μm, the average particle diameter of the Zn 4 B 6 O 13 powder The diameter is ½ or less of the average particle diameter of the main raw material ZnO. Therefore, a uniform and wide distribution of B at the stage of the molded body before the heat treatment can be obtained, and B can be dissolved in ZnO at a uniform and high ratio. As a result, since B is easily dissolved and replaced, it is possible to obtain a ZnO sintered body for a target in which the solid solution of B and the particle size are uniform.
（２）の場合、Ｚｎ４Ｂ６Ｏ１３単相の複合酸化物が得られる。なお、Ｚｎ４Ｂ６Ｏ１３粉末には、Ｚｎ３（ＢＯ３）２が微量に含まれていても良い。 In the case of (2), a Zn 4 B 6 O 13 single-phase composite oxide is obtained. The Zn 4 B 6 O 13 powder may contain a trace amount of Zn 3 (BO 3 ) 2 .
（３）の場合、得られたＺｎＯ焼結体を成膜すれば低抵抗な膜を得ることができる。 In the case of (3), a low resistance film can be obtained by depositing the obtained ZnO sintered body.
以下、本発明のＺｎＯ焼結体の製造方法について詳細に説明する。 Hereinafter, the manufacturing method of the ZnO sintered compact of this invention is demonstrated in detail.
本発明のＺｎＯ焼結体の製造方法で製造されるＺｎＯ焼結体におけるＢ（硼素）の含有割合はＢ２Ｏ３換算で０．０１〜３．０ｍｏｌ％、より好ましくは０．０１〜１．５ｍｏｌ％である。 The content ratio of B (boron) in the ZnO sintered body produced by the method for producing a ZnO sintered body of the present invention is 0.01 to 3.0 mol%, more preferably 0.01 to 1 in terms of B 2 O 3. 0.5 mol%.
Ｂの含有量がＢ２Ｏ３換算で０．０１ｍｏｌ％より少ない場合は、Ｚｎサイトに置換固溶するドーパントのＢの量が少なすぎて、成膜しても低抵抗な膜が得られない。Ｂの含有量がＢ２Ｏ３換算で０．０１ｍｏｌ％以上であることで抵抗を下げることが可能である。一方、３．０ｍｏｌ％を超えると、膜の抵抗には変化がないが、固溶限界を超えた過剰のＢがＺｎＯ焼結体の粒界に多量に残留することで焼結阻害を起こし、焼結体が十分に緻密化しないとか、スパッタリング時に放電を起こす原因となるので好ましくない。このような観点からＢの含有割合は、１．５ｍｏｌ％以下がより好ましい。 When the content of B is less than 0.01 mol% in terms of B 2 O 3, the amount of B, which is a substitutional solid solution at the Zn site, is too small, and a low resistance film cannot be obtained even if the film is formed. . The resistance can be lowered when the B content is 0.01 mol% or more in terms of B 2 O 3 . On the other hand, if it exceeds 3.0 mol%, there is no change in the resistance of the film, but excessive B exceeding the solid solution limit causes sintering inhibition due to a large amount remaining in the grain boundary of the ZnO sintered body, This is not preferable because the sintered body does not become sufficiently dense or causes discharge during sputtering. From such a viewpoint, the content ratio of B is more preferably 1.5 mol% or less.
焼結体を構成するＺｎＯ粒子の平均結晶粒径は、２〜１０μｍであることが好ましい。焼結体の平均結晶粒径が１０μｍ以上になるような焼結条件では粒成長が促進されるので均一な組織を形成するのが難しくなる。 The average crystal grain size of the ZnO particles constituting the sintered body is preferably 2 to 10 μm. Under the sintering conditions in which the average crystal grain size of the sintered body is 10 μm or more, grain growth is promoted, so that it becomes difficult to form a uniform structure.
ＺｎＯ焼結体のＢ源は、Ｚｎ４Ｂ６Ｏ１３である。これは、Ｚｎ４Ｂ６Ｏ１３がＺｎＯ焼結体の組織の均一化に作用するためである。 The B source of the ZnO sintered body is Zn 4 B 6 O 13 . This is because Zn 4 B 6 O 13 acts to make the structure of the ZnO sintered body uniform.
透明導電膜として用いられるスパッタ膜には抵抗均一性が求められているが、Ｂ２Ｏ３を添加したＺｎＯ焼結体をターゲット材としてそれを達成するには、焼結体を構成する粒子の結晶粒径が揃っていることとＺｎＯ中へのＢの固容量が均一であることが望まれる。ＺｎＯは焼結時に活性が非常に高く、低温でも簡単に粒成長を起こす。その際にＢ源としてＢ２Ｏ３で添加すると、Ｂの分布の均一さにより粒成長の度合いが異なり、結晶粒径にバラツキを持った組織のＺｎＯ焼結体ができ易い。つまり、Ｂ２Ｏ３を添加したＺｎＯでは、均一な微構造に制御された焼結体を作るのが難しい。当然、こうした焼結体をターゲット材として使用すると、焼結体を構成する粒子個々へのＢの固溶の程度にばらつきが生じるために抵抗均一性に優れたスパッタ膜を得るのは難しい。 A sputtered film used as a transparent conductive film is required to have resistance uniformity. To achieve this by using a ZnO sintered body to which B 2 O 3 is added as a target material, the particles constituting the sintered body It is desired that the crystal grain size is uniform and that the solid volume of B in ZnO is uniform. ZnO has very high activity during sintering and easily causes grain growth even at low temperatures. In this case, when B 2 O 3 is added as a B source, the degree of grain growth varies depending on the uniformity of the distribution of B, and a ZnO sintered body having a structure with a variation in crystal grain size is easily formed. That is, with ZnO added with B 2 O 3 , it is difficult to produce a sintered body controlled to have a uniform microstructure. Naturally, when such a sintered body is used as a target material, it is difficult to obtain a sputtered film having excellent resistance uniformity because the degree of solid solution of B in each particle constituting the sintered body varies.
したがって、Ｂの分散を均一にして、Ｂの固溶、置換をし易くして、ＺｎＯは微細な焼結粒径の組織を持ち、粒径のばらつきが小さい、ＺｎＯ焼結体とすることが有効である。このような知見のもと、ＢはＺｎ４Ｂ６Ｏ１３化合物の形で添加するのが好ましいという結論に至った。 Accordingly, the dispersion of B should be made uniform to facilitate the solid solution and substitution of B, and ZnO should have a fine sintered grain size structure with a small variation in grain size. It is valid. Based on these findings, it was concluded that B is preferably added in the form of a Zn 4 B 6 O 13 compound.
Ｚｎ４Ｂ６Ｏ１３をＢ源として添加するのは、Ｚｎ４Ｂ６Ｏ１３がＢの固溶源として働く他に一部がそのピン止め効果により粒成長を抑制する効果が極めて大きいためである。ＺｎＯとＢ２Ｏ３の混合粉末を仮焼して容易に得られるのはＺｎＢ２Ｏ４、Ｚｎ３Ｂ２Ｏ６とＺｎ４Ｂ６Ｏ１３の３つの複合酸化物であるが、ＺｎＢ２Ｏ４とＺｎ３Ｂ２Ｏ６は低融点が原因と考えられる溶出を焼結時に起こし易く、ＺｎＯを十分に緻密化させることが難しいためである。 Zn 4 B 6 O 13 is added as a B source because Zn 4 B 6 O 13 works as a solid solution source of B and a part thereof has an extremely large effect of suppressing grain growth due to its pinning effect. is there. Although the obtained easily by calcining a mixed powder of ZnO and B 2 O 3 is 3 composite oxide ZnB 2 O 4, Zn 3 B 2 O 6 and Zn 4 B 6 O 13, ZnB 2 This is because O 4 and Zn 3 B 2 O 6 tend to cause elution, which is considered to be caused by a low melting point, during sintering, and it is difficult to sufficiently densify ZnO.
また、本発明では、Ｚｎ４Ｂ６Ｏ１３のＢがＺｎＯに固溶する結果、ＺｎＯ焼結体をＸ線回折測定したときに、複合酸化物が検出されないことが好ましい。上述のように、固溶限界を超えた過剰のＢがＺｎＯ焼結体の粒界に多量に残留することで焼結阻害を起こし、焼結体が十分に緻密化しなかったり、スパッタリング時に放電を起こしたりする原因となるので好ましくない。 In the present invention, as a result of B in Zn 4 B 6 O 13 being dissolved in ZnO, it is preferable that no complex oxide is detected when the ZnO sintered body is measured by X-ray diffraction. As described above, excessive B exceeding the solid solution limit remains in a large amount at the grain boundary of the ZnO sintered body, causing sintering inhibition, and the sintered body is not sufficiently densified, or discharge is generated during sputtering. This is not preferable because it may cause
次に本発明のＺｎＯ焼結体の製造方法について説明する。 Next, the manufacturing method of the ZnO sintered compact of this invention is demonstrated.
Ｂ源のＺｎ４Ｂ６Ｏ１３粉末は、ＺｎＯ粉末とＢ２Ｏ３粉末とを混合、焼成及び粉砕して得られる。ここで用いられるＺｎ４Ｂ６Ｏ１３粉末作製用のＺｎＯ粉末は、平均粒径０．５〜１．０μｍのものを用いることが好ましい。また、高純度のものを用いることが好ましく、その純度は９９％以上、より好ましくは９９．８％以上の原料粉末を用いることが望ましい。Ｂ２Ｏ３粉末としては、平均粒径０．５〜２．０μｍのものを用いることが好ましい。また、上記ＺｎＯ粉末同様、高純度のものを用いることが好ましく、その純度は９９％以上、より好ましくは９９．８％以上の原料粉末を用いることが望ましい。 The Zn 4 B 6 O 13 powder of the B source is obtained by mixing, firing and pulverizing ZnO powder and B 2 O 3 powder. The ZnO powder for producing Zn 4 B 6 O 13 powder used here is preferably one having an average particle diameter of 0.5 to 1.0 μm. Moreover, it is preferable to use a high-purity one, and it is desirable to use a raw material powder having a purity of 99% or more, more preferably 99.8% or more. As the B 2 O 3 powder, one having an average particle diameter of 0.5 to 2.0 μm is preferably used. Further, like the ZnO powder, it is preferable to use a high-purity one, and it is desirable to use a raw material powder having a purity of 99% or more, more preferably 99.8% or more.
ＺｎＯ粉末とＢ２Ｏ３粉末の混合比は、ｍｏｌ比で４：６〜７：３とすることができる。このような混合比とし、焼成条件を適切に制御すれば、Ｚｎ４Ｂ６Ｏ１３単相の複合酸化物が得られる。なお、Ｚｎ４Ｂ６Ｏ１３粉末には、Ｚｎ３（ＢＯ３）２が微量に含まれていても良い。 The mixing ratio of the ZnO powder and the B 2 O 3 powder can be 4: 6 to 7: 3 in terms of a molar ratio. When such a mixing ratio is used and the firing conditions are appropriately controlled, a Zn 4 B 6 O 13 single-phase composite oxide can be obtained. The Zn 4 B 6 O 13 powder may contain a trace amount of Zn 3 (BO 3 ) 2 .
原料粉末の混合方法は特に限定されず、湿式及び乾式のボールミル、振動ミル等を用いることができる。 The mixing method of the raw material powder is not particularly limited, and wet and dry ball mills, vibration mills, and the like can be used.
焼成は、大気雰囲気中、８００〜１０００℃にて行うことができる。以上の作製条件によりＺｎ４Ｂ６Ｏ１３単相の複合酸化物が得られる。 Firing can be performed at 800 to 1000 ° C. in an air atmosphere. A Zn 4 B 6 O 13 single-phase composite oxide is obtained under the above manufacturing conditions.
アルミナボール等を媒体としてこの粉末をミル粉砕することで、添加物用として所望の粒度分布を持つＺｎ４Ｂ６Ｏ１３粉末が得られる。効果的にＺｎ４Ｂ６Ｏ１３のピン止め効果を発揮させるためには、添加するＺｎ４Ｂ６Ｏ１３粉末の粒径が小さく、かつ狭い粒度分布を持つことが好ましい。Ｚｎ４Ｂ６Ｏ１３粉末の平均粒径は、０．２〜０．５μｍに制御する。これは、Ｂを均一かつ高い割合でＺｎＯに固溶させるには、熱処理前の成形体の段階での均一かつ広範囲なＢの分布が必要で、そのためにはＺｎ４Ｂ６Ｏ１３粉末の平均粒径は主原料ＺｎＯの平均粒径に対して１／２以下であることが好ましいためである。こうすることで容易に固溶置換も起きるために、Ｂの固溶と粒径が均一なターゲット用のＺｎＯ焼結体を得ることが可能となる。 By milling the powder using alumina balls or the like as a medium, Zn 4 B 6 O 13 powder having a desired particle size distribution can be obtained for the additive. In order to effectively exert the pinning effect of Zn 4 B 6 O 13 is, Zn 4 B 6 O 13 particle size of the powder is smaller to be added, and preferably has a narrow particle size distribution. The average particle size of the Zn 4 B 6 O 13 powder is controlled to 0.2 to 0.5 μm. This is because, in order to dissolve B in a uniform and high proportion in ZnO, a uniform and wide distribution of B at the stage of the molded body before the heat treatment is required. For this purpose, the average of Zn 4 B 6 O 13 powder This is because the particle size is preferably ½ or less of the average particle size of the main raw material ZnO. By doing so, solid solution substitution easily occurs, so that it becomes possible to obtain a ZnO sintered body for a target in which the solid solution of B and the particle size are uniform.
また、Ｚｎ４Ｂ６Ｏ１３粉末の粒度分布は、レーザー回折式粒度分布測定におけるＤ１０の粒径とＤ９０の粒径の比Ｄ９０／Ｄ１０が２０以下、より好ましくは１０以下とすることが望ましい。なお、明細書において平均粒径とは、レーザー回折式粒度分布測定におけるメディアン径（Ｄ５０）である。 The particle size distribution of the Zn 4 B 6 O 13 powder is preferably such that the ratio D90 / D10 of the particle size of D10 to the particle size of D90 in laser diffraction particle size distribution measurement is 20 or less, more preferably 10 or less. In the specification, the average particle diameter is a median diameter (D50) in laser diffraction particle size distribution measurement.
次に、こうして得られたＺｎ４Ｂ６Ｏ１３粉末とＺｎＯ粉末を、Ｂの含有割合がＢ２Ｏ３換算で０．０１〜３．０ｍｏｌ％になるように秤量、混合した後、プレス成形等で粉末成形体を作製して、大気雰囲気等で焼成することでＺｎＯ焼結体が得られる。 Next, the thus obtained Zn 4 B 6 O 13 powder and ZnO powder are weighed and mixed so that the B content is 0.01 to 3.0 mol% in terms of B 2 O 3 , and then press-molded. A ZnO sintered body can be obtained by preparing a powder compact with the above and firing it in an air atmosphere or the like.
焼結体を得るためのＺｎＯ粉末は、平均粒径０．５〜１．０μｍのものを用いる。また、高純度のものを用いることが好ましく、その純度は９９％以上、より好ましくは９９．８％以上の原料粉末を用いることが望ましい。 As the ZnO powder for obtaining a sintered body, one having an average particle diameter of 0.5 to 1.0 μm is used. Moreover, it is preferable to use a high-purity one, and it is desirable to use a raw material powder having a purity of 99% or more, more preferably 99.8% or more.
焼結温度は１１００〜１５００℃であることが好ましい。１１００℃未満で焼結した場合、ＺｎＯは緻密化するもののＺｎＯ中へのＢの固溶が十分に進まないために低抵抗化しないおそれがあるので好ましくない。１５００℃より高いとＺｎＯの分解が顕著になり密度低下を引き起こす可能性があるので好ましくない。 The sintering temperature is preferably 1100 to 1500 ° C. When sintered at a temperature lower than 1100 ° C., ZnO becomes dense, but the solid solution of B in ZnO does not advance sufficiently, so that there is a possibility that the resistance will not be lowered. A temperature higher than 1500 ° C. is not preferable because ZnO is significantly decomposed and may cause a decrease in density.
保持時間は２〜２０時間であることが好ましい。２時間より短いと、十分に緻密化しないおそれがあるために好ましくない。２０時間を越えると、長時間化による粒成長が著しくなる場合があるために好ましくない。焼結雰囲気は特に限定されないが、例えば大気中、酸素中、不活性ガス雰囲気中での焼成とすることができる。特に焼結中に酸化物の蒸発による重量減少、組成ずれの低減のためには大気中等の酸化雰囲気での焼結が好適である。また焼結雰囲気の圧力は限定されず、減圧、常圧から数気圧の加圧まで任意に適用できる。 The holding time is preferably 2 to 20 hours. If it is shorter than 2 hours, it may not be sufficiently densified, which is not preferable. Exceeding 20 hours is not preferable because grain growth due to longer time may become remarkable. Although the sintering atmosphere is not particularly limited, for example, the firing can be performed in air, oxygen, or an inert gas atmosphere. In particular, sintering in an oxidizing atmosphere such as in the air is suitable for reducing weight loss due to evaporation of oxide and reducing composition deviation during sintering. The pressure of the sintering atmosphere is not limited, and any pressure can be applied from reduced pressure, normal pressure to several atmospheric pressure.
ＺｎＯ焼結体は、スパッタリングターゲット材としてバッキングプレートに接合される前に、研削加工が施される。このとき、研削歪みが生じることから、歪みを除去するために、研削加工後に仮焼することが好ましい。仮焼は、６００〜８００℃で行うことができる。このような温度範囲であれば、十分に歪みが除去でき、焼結体の粒成長等も起きないので好ましい。 The ZnO sintered body is subjected to grinding before being joined to the backing plate as a sputtering target material. At this time, since grinding distortion occurs, it is preferable to calcine after grinding in order to remove the distortion. Calcination can be performed at 600 to 800 ° C. Such a temperature range is preferable because distortion can be sufficiently removed and grain growth of the sintered body does not occur.
以下、本発明の実施例を比較例とともに具体的に挙げ、本発明をより詳細に説明する。 EXAMPLES Hereinafter, the Example of this invention is specifically given with a comparative example, and this invention is demonstrated in detail.
［実施例１］
ＺｎＯ粉末（純度９９．８％、平均粒径０．７μｍ）とＢ２Ｏ３粉末（純度９９．９％、平均粒径０．５μｍ）とをｍｏｌ比で６：４の割合で秤量、混合した後、大気雰囲気中、９００℃で焼成することで、Ｚｎ４Ｂ６Ｏ１３単相の複合酸化物を得た。これを、アルミナボールを媒体として２４時間ボールミル粉砕した。得られた粉末の平均粒径をレーザー回折式粒度分布測定したところ０．４μｍであり、これを添加物用のＺｎ４Ｂ６Ｏ１３粉末とした。
[Example 1]
ZnO powder (purity 99.8%, average particle size 0.7 μm) and B 2 O 3 powder (purity 99.9%, average particle size 0.5 μm) were weighed and mixed at a molar ratio of 6: 4. After that, it was fired at 900 ° C. in an air atmosphere to obtain a Zn 4 B 6 O 13 single-phase composite oxide. This was ball milled for 24 hours using alumina balls as a medium. When the average particle size of the obtained powder was measured by laser diffraction particle size distribution, it was 0.4 μm, which was designated as Zn 4 B 6 O 13 powder for additives.
このＺｎ４Ｂ６Ｏ１３粉末とＺｎＯ粉末（純度９９．８％、平均粒径０．７μｍ）を、Ｂの含有割合がＢ２Ｏ３換算で２．０ｍｏｌ％になるように秤量、混合した後、プレス成形により直径１００ｍｍ、厚さ６ｍｍの粉末成形体を作製した。これを大気雰囲気中、１３５０℃、１０時間焼成して、ＺｎＯ焼結体を得た。焼結体の平均結晶粒径を、焼結体表面を鏡面研磨後、研磨面を熱腐食したあとにＳＥＭ観察し、線インターセプト法によって求めたところ、７μｍであった。また、焼結体の密度をアルキメデス法により測定したところ５．４ｇ／ｃｍ３であった。 This Zn 4 B 6 O 13 powder and ZnO powder (purity 99.8%, average particle size 0.7 μm) were weighed and mixed so that the B content was 2.0 mol% in terms of B 2 O 3 . Thereafter, a powder compact having a diameter of 100 mm and a thickness of 6 mm was produced by press molding. This was fired in air at 1350 ° C. for 10 hours to obtain a ZnO sintered body. The average crystal grain size of the sintered body was 7 μm when the surface of the sintered body was mirror-polished and the polished surface was thermally corroded and then observed by SEM and determined by the line intercept method. Moreover, it was 5.4 g / cm < 3 > when the density of the sintered compact was measured by the Archimedes method.
得られたＺｎＯ焼結体を直径６０ｍｍ、厚さ４ｍｍの円盤状に加工した後、７００℃にて仮焼してスパッタリングターゲットを作製した。このスパッタリングターゲットを用いてＤＣマグネトロンスパッタリング法によって膜厚３００ｎｍの成膜を行った。スパッタリング条件は、投入電力２００Ｗ、Ａｒガス圧０．３Ｐａとした。 The obtained ZnO sintered body was processed into a disk shape having a diameter of 60 mm and a thickness of 4 mm, and then calcined at 700 ° C. to prepare a sputtering target. Using this sputtering target, a film having a thickness of 300 nm was formed by DC magnetron sputtering. The sputtering conditions were an input power of 200 W and an Ar gas pressure of 0.3 Pa.
成膜後、ＺｎＯ膜の１０ヶ所について、膜抵抗率を４端子法によって測定した。結果を表１に示す。１０ヶ所の膜抵抗は平均が２.５ ×１０−３Ω・ｃｍに対して最大が２.６×１０−３Ω・ｃｍ、最小が２.３×１０−３Ω・ｃｍと、バラツキの小さい良好なＺｎＯ膜が得られた。 After the film formation, the film resistivity was measured at 10 points of the ZnO film by the 4-terminal method. The results are shown in Table 1. The film resistance at 10 locations averages 2.5 × 10 −3 Ω · cm, the maximum is 2.6 × 10 −3 Ω · cm, and the minimum is 2.3 × 10 −3 Ω · cm, which varies widely. A small and good ZnO film was obtained.
［実施例２〜５］
同様にして表１に示すようにＺｎＯ粉末とＺｎ４Ｂ６Ｏ１３粉末の粒径、Ｂの含有割合（Ｂ２Ｏ３換算量ｍｏｌ％）を変化させてＺｎＯ焼結体を作製し、実施例１と同じ評価をした。いずれの場合とも膜抵抗のバラツキは１０％以内と良好なＺｎＯ膜が得られた。
[Examples 2 to 5]
Similarly, as shown in Table 1, ZnO powder and Zn 4 B 6 O 13 powder were changed in particle size and B content ratio (B 2 O 3 equivalent mol%) to produce a ZnO sintered body, The same evaluation as in Example 1 was performed. In either case, the film resistance variation was within 10%, and a good ZnO film was obtained.
［比較例１〜３］
同様にして表１に示すようにＺｎＯ粉末とＺｎ４Ｂ６Ｏ１３粉末の粒径、複合酸化物の種類を変化させて焼結体を作製し、実施例１と同じ評価をした。比較例１については、低抵抗化は示したものの膜抵抗のバラツキが大きくなった。比較例２、３については、複合酸化物の低融点化によりＺｎＯが十分に緻密化しなかったために、得られた膜も低抵抗にならなかった。
[Comparative Examples 1-3]
Similarly, as shown in Table 1, sintered bodies were produced by changing the particle sizes of ZnO powder and Zn 4 B 6 O 13 powder and the type of composite oxide, and the same evaluation as in Example 1 was performed. As for Comparative Example 1, although the reduction in resistance was shown, the variation in film resistance increased. In Comparative Examples 2 and 3, since the ZnO was not sufficiently densified due to the low melting point of the composite oxide, the obtained film did not have a low resistance.
なお、実施例のＺｎＯ焼結体についてＢの複合酸化物の有無を調べるためにＸ線回折測定（リガク社製Ｘ線回折装置ＭｕｌｔｉＦｌｅｘを使用。ＣｕＫα線源、加速電圧４０ｋＶ、４０ｍＡ）を行ったが、ＺｎＯ以外は検出されなかった。また、ＺｎＯへのＢの固溶がＸ線回折ピークのピークシフトにより確認された。 In addition, in order to investigate the presence or absence of the complex oxide of B for the ZnO sintered body of the example, an X-ray diffraction measurement (using an X-ray diffractometer MultiFlex manufactured by Rigaku Corporation. CuKα radiation source, acceleration voltage 40 kV, 40 mA) was performed. However, other than ZnO was not detected. Moreover, the solid solution of B in ZnO was confirmed by the peak shift of the X-ray diffraction peak.
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