JP3501614B2 - ITO sintered body, method of manufacturing the same, and method of forming ITO film using the ITO sintered body - Google Patents
ITO sintered body, method of manufacturing the same, and method of forming ITO film using the ITO sintered bodyInfo
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- JP3501614B2 JP3501614B2 JP05847597A JP5847597A JP3501614B2 JP 3501614 B2 JP3501614 B2 JP 3501614B2 JP 05847597 A JP05847597 A JP 05847597A JP 5847597 A JP5847597 A JP 5847597A JP 3501614 B2 JP3501614 B2 JP 3501614B2
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液晶表示素子等の
透明電極、航空機の窓ガラスやＴＶカメラの防護ガラス
等の防曇あるいは氷結防止のための透明発熱抵抗体、Ｏ
Ａ機器のディスプレー用透明帯電防止膜、太陽光集熱器
用選択透過膜等の成膜に広く用いられるＩＴＯ焼結体お
よびその製造方法ならびに前記ＩＴＯ焼結体を用いたＩ
ＴＯ膜の成膜方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent electrode such as a liquid crystal display device, a transparent heating resistor for preventing fogging or icing of window glass of an aircraft or protective glass of a TV camera, and an O.
An ITO sintered body widely used for forming a transparent antistatic film for a display of a device A, a selective transmission film for a solar heat collector, etc., a method for producing the same, and I using the ITO sintered body.
The present invention relates to a method for forming a TO film.
【０００２】[0002]
【従来の技術】液晶表示素子等の透明電極、航空機の窓
ガラスやＴＶカメラの防護ガラス等の防曇あるいは氷結
防止のための透明発熱抵抗体、ＯＡ機器のディスプレー
用透明帯電防止膜、太陽光集熱器用選択透過膜等に広く
用いられるＩＴＯ膜は、酸化インジウム（Ｉｎ2 Ｏ3 ）
と酸化錫（ＳｎＯ2 ）からなるＩＴＯ焼結体を蒸発源あ
るいはターゲットとする真空蒸着やスパッタリングによ
って成膜される。このようなＩＴＯ膜の透明性、電気伝
導性（導電性）および安定性を向上させるために、従
来、様々な技術が開発されている。2. Description of the Related Art Transparent electrodes for liquid crystal display devices, transparent heat generating resistors for anti-fogging or icing prevention such as aircraft window glass and TV camera protective glass, transparent antistatic film for OA equipment display, sunlight An ITO film that is widely used as a selective transmission film for a heat collector is indium oxide (In 2 O 3 )
The film is formed by vacuum vapor deposition or sputtering using an ITO sintered body made of tin oxide (SnO 2 ) as an evaporation source or a target. In order to improve the transparency, electric conductivity (conductivity) and stability of such an ITO film, various techniques have been conventionally developed.
【０００３】例えば、公知の方法で製作されたＩＴＯ焼
結体を二次焼結させたものを、スパッタリングのターゲ
ットとして用いることで、スパッタリング中の抵抗率の
変化を低減し、透明導電膜の品質を向上させる（特開平
３−４４４６５号公報参照）。For example, by using an ITO sintered body produced by a known method and secondarily sintered as a target for sputtering, the change in resistivity during sputtering is reduced, and the quality of the transparent conductive film is reduced. (See Japanese Patent Laid-Open No. 3-44465).
【０００４】あるいは、酸化インジウムと酸化錫からな
るＩＴＯ原材料にインジウムと錫以外の３価および４価
の酸化物を混合して焼結させたものをスパッタリングの
ターゲットとして用いることで、高密度で均質な透明導
電膜を得る（特開平２−３０４８１５号公報参照）。３
価および４価の酸化物としては、Ａｌ2 Ｏ3 とＳｉＯ 2
が例示されており、これらの、酸化インジウムと酸化錫
の合計重量（ＩＴＯ原材料の重量）に対する混合比は、
０．５〜１％である。Alternatively, it is composed of indium oxide and tin oxide.
Trivalent and tetravalent other than indium and tin for ITO raw material
The oxides of
By using it as a target, high-density and homogeneous transparent conductor
An electric film is obtained (see Japanese Patent Laid-Open No. 2-304815). Three
As the valent and tetravalent oxides, Al2 O3 And SiO 2
Are exemplified, and these indium oxide and tin oxide are
The mixing ratio with respect to the total weight (weight of ITO raw material) is
It is 0.5 to 1%.
【０００５】あるいは、インジウム（Ｉｎ）と錫（Ｓ
ｎ）とケイ素（Ｓｉ）または／およびアルミニウム（Ａ
ｌ）との合金ターゲットあるいはこれらの酸化物ターゲ
ットにおける各原子あるいは各酸化物の配合比を、透明
導電膜中の原子比ａ，ｂが
ａ＝（（Ｓｉ＋Ａｌ）／（Ｉｎ＋Ｓｎ＋Ｓｉ＋Ａｌ））
×１００％
で表わされるＳｉまたは／およびＡｌの原子含量が２％
以上であり、かつ
ｂ＝（（Ｓｎ＋Ｓｉ＋Ａｌ）／（Ｉｎ＋Ｓｎ＋Ｓｉ＋Ａ
ｌ））×１００％
で表わされるＳｎとＳｉまたは／およびＡｌとの合計原
子含量が２０％以下の範囲に入るように適宜設定するこ
とで透明で高抵抗の透明導電膜を得る（特開平４−２０
６４０３号公報参照）。この場合は、透明導電膜の膜中
に酸化シリコンと酸化アルミニウムが含有されておりそ
の含有量は酸化インジウムと酸化錫の合計重量に対して
０．７７％以上という計算値になる。Alternatively, indium (In) and tin (S
n) and silicon (Si) or / and aluminum (A
The atomic ratio a, b in the transparent conductive film is a = ((Si + Al) / (In + Sn + Si + Al)) as the compounding ratio of each atom or each oxide in the alloy target with 1) or these oxide targets.
× 100% Si or / and Al atomic content is 2%
And b = ((Sn + Si + Al) / (In + Sn + Si + A)
l)) × 100%, the total atomic content of Sn and Si or / and Al represented by 20% or less is appropriately set to obtain a transparent and high-resistance transparent conductive film (Japanese Patent Laid-Open No. HEI 4). -20
6403). In this case, the transparent conductive film contains silicon oxide and aluminum oxide, and the content thereof is a calculated value of 0.77% or more based on the total weight of indium oxide and tin oxide.
【０００６】あるいは、スピネル構造のＭｇＡｌ2 Ｏ4
のＭｇ（マグネシウム）をＺｎ、Ｃｄ、Ｉｎ、Ｔｉ、Ｓ
ｎ、ＰＢ、ＳｂおよびＢｉから選ばれる金属元素（Ｍ）
で部分置換し、一般式、ＭｘＭｇ1-x Ａｌ2 Ｏ
4-(1-m/2)xで表わされる膜（ｘは０．０１≦ｘ≦０．２
なる値でｍはＭの酸化数とする）を得ることで、紫外域
で透明かつ高い導電性を有する酸化物膜を実現する（特
開平６−１９１４４号公報参照）。部分置換元素の例と
してはＩｎ2 Ｏ3 とＳｎＯ2 があり、これらの配合比が
ｘ＝０．０５の時の特性が記載されている。すなわちＭ
ｇの割合が０．９５の場合でこれはＭｇに少量のＩｎ2
Ｏ3 またはＳｎＯ2 を添加した格好になっている。Alternatively, MgAl 2 O 4 having a spinel structure
Mg (magnesium) of Zn, Cd, In, Ti, S
Metal element (M) selected from n, PB, Sb and Bi
In partially substituted, general formula, MxMg 1-x Al 2 O
Film represented by 4- (1-m / 2) x (x is 0.01 ≦ x ≦ 0.2
By setting m to be the oxidation number of M), an oxide film that is transparent and has high conductivity in the ultraviolet region is realized (see Japanese Patent Laid-Open No. 6-19144). Examples of the partial substitution element are In 2 O 3 and SnO 2 , and the characteristics when the compounding ratio of these is x = 0.05 are described. Ie M
When the ratio of g is 0.95, this means that a small amount of In 2 is added to Mg.
It is dressed with O 3 or SnO 2 .
【０００７】あるいは、酸化インジウムおよび酸化錫か
らなるＩＴＯ焼結体に亜鉛、銅、アンチモン、チタン、
ツリウム、マグネシウムを１種以上含有させることで密
度が高い焼結体からなるスパッタリングターゲットを用
いて、ターゲットの割れ、ターゲットからの破損微粒物
の飛び散りを改善する（特開平７−５４１３２号公報参
照）。この場合は、亜鉛、銅、アンチモン、チタン、ツ
リウム、マグネシウム元素の総含有量は焼結体全量に対
して５〜５０００ｐｐｍと記載されているので、酸化マ
グネシウムのみ含有した場合でもその総含有量はＩＴＯ
原材料１００％に対し最大０．９５％という計算にな
る。Alternatively, an ITO sintered body composed of indium oxide and tin oxide is used to form zinc, copper, antimony, titanium,
Using a sputtering target made of a sintered body having a high density by containing at least one of thulium and magnesium, it is possible to improve the cracking of the target and the scattering of broken fine particles from the target (see JP-A-7-54132). . In this case, since the total content of zinc, copper, antimony, titanium, thulium, and magnesium elements is described as 5 to 5000 ppm with respect to the total amount of the sintered body, even if only magnesium oxide is contained, the total content is ITO
The maximum calculation is 0.95% for 100% of raw materials.
【０００８】あるいは、主成分の酸化インジウムと酸化
錫にマグネシウムおよびニッケルよりなる群から選択さ
れる少なくとも一種の金属の酸化物を含む透明導電膜と
することで、膜質を緻密にし、電子移動度を大きくして
湿度と紫外線による抵抗の変化を改善する（特開平７−
１６１２３５号公報参照）。インジウムに対する錫の配
合割合が重量に換算して
Ｓｎ／（Ｓｎ＋Ｉｎ）＝０．０５〜０．２０ｗｔ％
で、インジウムに対するマグネシウム化合物またはニッ
ケル化合物の配合割合がインジウム（Ｉｎ）とマグネシ
ウムおよびニッケル（Ｍ）の比で表わしたときに、
Ｍ／（Ｍ＋Ｉｎ）≦０．０５ｗｔ％
とされており、例として０．００５、０．０２５、０．
０５ｗｔ％の場合が記載されている。これからＩＴＯ膜
中の酸化マグネシウムの配合割合を求めると、酸化イン
ジウムと酸化錫の合計重量すなわち、ＩＴＯ原材料の重
量１００％に対して０．３０〜３．５％の範囲となる。Alternatively, a transparent conductive film containing indium oxide and tin oxide, which are main components, and an oxide of at least one metal selected from the group consisting of magnesium and nickel is used to make the film quality dense and to improve electron mobility. Increase the resistance to improve the resistance change due to humidity and ultraviolet rays (Japanese Patent Laid-Open No. 7-
161235). The compounding ratio of tin to indium is Sn / (Sn + In) = 0.05 to 0.20 wt% in terms of weight, and the compounding ratio of magnesium compound or nickel compound to indium is indium (In) and magnesium and nickel (M). When expressed by the ratio of M / (M + In) ≦ 0.05 wt%, 0.005, 0.025, 0.
The case of 05 wt% is described. When the compounding ratio of magnesium oxide in the ITO film is obtained from this, it is in the range of 0.30 to 3.5% with respect to the total weight of indium oxide and tin oxide, that is, 100% by weight of the ITO raw material.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら上記従来
の技術によれば、真空蒸着の蒸発源あるいはスパッタリ
ングのターゲットとするＩＴＯ焼結体に様々な添加物を
添加することで、ＩＴＯ焼結体から破損微粒子が飛散す
るいわゆるスプラッシュ等を防ぎ、膜厚方向に均一な組
成を有し、かつ、異物の混入やピンホール等の欠陥のな
い良質なＩＴＯ膜を得るように工夫したものであるが、
いずれも、成膜されたＩＴＯ膜のＳｎＯ2含有量と、蒸
発源あるいはターゲットとして用いたＩＴＯ焼結体のＳ
ｎＯ2 含有量が不一致となり、特に、ＩＴＯ膜のＳｎＯ
2 含有量の方がＩＴＯ焼結体のＳｎＯ2 含有量より少な
くなる傾向を有するため、目標とする透明性や導電性を
有するＩＴＯ膜を安定して製作することが難しいという
未解決の課題がある。However, according to the above-mentioned conventional technique, various additives are added to the ITO sintered body which is the evaporation source of the vacuum deposition or the sputtering target, so that the ITO sintered body is damaged. It is devised to prevent a so-called splash or the like in which fine particles are scattered, to have a uniform composition in the film thickness direction, and to obtain a good quality ITO film without defects such as inclusion of foreign matter and pinholes.
In both cases, the SnO 2 content of the formed ITO film and the S content of the ITO sintered body used as the evaporation source or target.
The content of nO 2 is inconsistent, especially SnO of ITO film
Since the 2 content tends to be smaller than the SnO 2 content of the ITO sintered body, there is an unsolved problem that it is difficult to stably manufacture an ITO film having the target transparency and conductivity. is there.
【００１０】また、１００ＭＰａ以上の高いプレス圧力
でＩＴＯ焼結体を焼結させることによって、ＩＴＯ焼結
体を高密度化させれば、スプラッシュの発生やＩＴＯ膜
の組成の変動を防ぐのに有効であることが知られている
が、このような高いプレス圧力で焼結させると、ＩＴＯ
焼結体ごとに密度のバラつきを生じやすく、製品として
のＩＴＯ焼結体に再現性が乏しいために、生産性の低下
を避けることができない。Further, if the ITO sintered body is densified by sintering the ITO sintered body with a high pressing pressure of 100 MPa or more, it is effective to prevent the occurrence of splash and the fluctuation of the composition of the ITO film. It is known that when sintered at such a high pressing pressure, ITO
Since the density of each sintered body tends to vary and the reproducibility of the ITO sintered body as a product is poor, it is unavoidable that the productivity is lowered.
【００１１】本発明は上記従来の技術の有する未解決の
課題に鑑みてなされたものであり、目標とする透明性や
導電性を有し、しかも、スプラッシュ等によるピンホー
ル等の欠陥の無い高品質のＩＴＯ膜を安定して製造でき
る安価なＩＴＯ焼結体およびその製造方法ならびに前記
ＩＴＯ焼結体を用いたＩＴＯ膜の成膜方法を提供するこ
とを目的とするためである。The present invention has been made in view of the above-mentioned unsolved problems of the prior art, and has the desired transparency and conductivity, and is free from defects such as pinholes due to splash or the like. This is to provide an inexpensive ITO sintered body capable of stably producing a high quality ITO film, a method for producing the same, and a method for forming an ITO film using the ITO sintered body.
【００１２】[0012]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明のＩＴＯ焼結体は、酸化インジウムと酸化
錫の割合が重量比９５：５であるＩＴＯ原材料を主成分
とするＩＴＯ膜成膜用のＩＴＯ焼結体であって、前記Ｉ
ＴＯ原材料にＳｉＯ2 およびＭｇＯのみを、前記ＩＴＯ
原材料１００重量部に対してそれぞれ１．０〜２．０重
量部添加したことを特徴とする。In order to achieve the above object, the ITO sintered body of the present invention has an ITO raw material whose main component is an ITO raw material in which the weight ratio of indium oxide to tin oxide is 95: 5. a ITO sintered for film forming, the I
Only SiO 2 and MgO are used as the TO raw material,
1.0 to 2.0 parts each for 100 parts by weight of raw materials
It is characterized in that a part is added.
【００１３】[0013]
【００１４】また、酸化インジウムと酸化錫の割合が重
量比９５：５であるＩＴＯ原材料を主成分とするＩＴＯ
膜成膜用のＩＴＯ焼結体であって、前記ＩＴＯ原材料に
ＳｉＯ2 、ＭｇＯおよびＡｌ2 Ｏ3 を、前記ＩＴＯ原材
料１００重量部に対してそれぞれ０．０５〜０．５重量
部、０．００５〜２．０重量部および１．００〜２．５
重量部添加したことを特徴とするＩＴＯ焼結体であって
もよい。 The proportion of indium oxide and tin oxide is heavy.
ITO whose main component is an ITO raw material with a volume ratio of 95: 5
An ITO sintered body for film formation , wherein the ITO raw material is SiO 2 , MgO and Al 2 O 3 as the ITO raw material
0.05 to 0.5 parts by weight per 100 parts by weight
Parts, 0.005-2.0 parts by weight and 1.00-2.5
It may be an ITO sintered body characterized by adding parts by weight .
【００１５】[0015]
【００１６】本発明のＩＴＯ焼結体の製造方法は、酸化
インジウムと酸化錫の割合が重量比９５：５であるＩＴ
Ｏ原材料に、ＳｉＯ2 およびＭｇＯのみを、前記ＩＴＯ
原材料１００重量部に対してそれぞれ１．０〜２．０重
量部添加したものを、０．２〜２０ＭＰａのプレス圧力
で所定の形状に圧縮成形する工程を有することを特徴と
する。In the method for producing an ITO sintered body of the present invention, IT in which the ratio of indium oxide to tin oxide is 95: 5 by weight.
As the O raw material, only SiO 2 and MgO were added to the ITO
1.0 to 2.0 parts each for 100 parts by weight of raw materials
It is characterized in that it has a step of compression-molding what is added in a predetermined amount with a pressing pressure of 0.2 to 20 MPa.
【００１７】また、酸化インジウムと酸化錫の割合が重
量比９５：５であるＩＴＯ原材料に、ＳｉＯ2 、ＭｇＯ
およびＡｌ2 Ｏ3 を、前記ＩＴＯ原材料１００重量部に
対してそれぞれ０．０５〜０．５重量部、０．００５〜
２．０重量部および１．００〜２．５重量部添加したも
のを、０．２〜２０ＭＰａのプレス圧力で所定の形状に
圧縮成形する工程を有するものでもよい。[0017] In addition, the proportion of indium oxide and tin oxide is heavy
Into the ITO raw material with a volume ratio of 95: 5 , SiO 2 , MgO
And Al 2 O 3 in 100 parts by weight of the ITO raw material
On the other hand , 0.05-0.5 parts by weight, 0.005-
It may have a step of compression-molding what was added 2.0 parts by weight and 1.00 to 2.5 parts by weight to a predetermined shape with a pressing pressure of 0.2 to 20 MPa.
【００１８】[0018]
【作用】本発明によれば、成膜中の蒸発源やターゲット
のスプラッシュ等が抑制され、しかも、ＩＴＯ焼結体と
同じ含有量の錫を含有するＩＴＯ膜を得ることができ
る。ＩＴＯ膜の錫の含有量は、ＩＴＯ膜の導電性と透明
性を大きく左右するものであるから、ＩＴＯ焼結体と錫
の含有量が同じであるＩＴＯ膜を成膜できれば、目標と
する透明性や導電性を有するＩＴＯ膜を安定して製造で
きる。 According to the present invention, it is possible to obtain an ITO film in which the evaporation source and the splash of the target during film formation are suppressed, and moreover, the ITO film contains tin in the same amount as that of the ITO sintered body. Since the tin content of the ITO film greatly affects the conductivity and transparency of the ITO film, if the ITO film having the same tin content as that of the ITO sintered body can be formed, the target transparency can be obtained. It is possible to stably manufacture an ITO film having properties and conductivity.
【００１９】すなわち、目標通りの透明性や導電性を有
し、しかもスプラッシュ等によるピンホール等の欠陥の
ない高品質なＩＴＯ膜を高い生産性で、従って安価に製
造できる。That is, a high-quality ITO film having the desired transparency and conductivity and having no defects such as pinholes due to splash or the like can be manufactured with high productivity and at low cost.
【００２０】さらに、ＩＴＯ焼結体を圧縮成形する工程
で高いプレス圧力を必要とせず、ＩＴＯ焼結体ごとに密
度がバラつくのを回避できる。これによってＩＴＯ焼結
体の生産性を大きく向上させ、ＩＴＯ膜の製造コストを
より一層低減できる。Further, it is possible to avoid a variation in the density of each ITO sintered body without requiring a high pressing pressure in the step of compression-molding the ITO sintered body. This can greatly improve the productivity of the ITO sintered body and further reduce the manufacturing cost of the ITO film.
【００２１】[0021]
【発明の実施の形態】本発明の実施の形態を説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described.
【００２２】本発明の第１の実施の形態によれば、ＩＴ
Ｏ焼結体の主成分である酸化インジウムと酸化錫の重量
比を９５：５とする原材料（ＩＴＯ原材料）１００重量
部にＳｉＯ2 を１．０〜２．０重量部、ＭｇＯを１．０
〜２．０重量部添加し、ボール・ミル等を使って充分に
細かい粒状混合物を得る。得られた粒状混合物を、プレ
ス圧力０．２〜２０ＭＰａでペレット状に圧縮成形し、
大気中で所定の温度で加熱、焼結させ、ＩＴＯ焼結体を
製作する。According to the first embodiment of the present invention, IT
1.0 to 2.0 parts by weight of SiO 2 and 1.0 parts by weight of MgO are added to 100 parts by weight of a raw material (ITO raw material) having a weight ratio of indium oxide and tin oxide of 95: 5 which are main components of the O sintered body.
~ 2.0 parts by weight is added and a sufficiently fine granular mixture is obtained using a ball mill or the like. The obtained granular mixture is compression molded into pellets at a pressing pressure of 0.2 to 20 MPa,
An ITO sintered body is manufactured by heating and sintering in air at a predetermined temperature.
【００２３】このようにして製作したＩＴＯ焼結体を電
子ビーム蒸発源とする真空蒸着によって、ガラス基板等
にＩＴＯ膜を成膜すると、透明性、導電性ともに良好
で、ピンホール等の欠陥のない良質のＩＴＯ膜を得るこ
とができる。成膜中のＩＴＯ焼結体の針立ちはほとんど
観察されず、スプラッシュが抑制されていると推測され
る。また、成膜後のＩＴＯ膜の酸化錫の含有量を調べた
ところ、ＩＴＯ焼結体の酸化錫の含有量と同じであり、
ＩＴＯ膜中へのＳｉＯ2 、ＭｇＯの混入量も極く微量で
あった。When an ITO film is formed on a glass substrate or the like by vacuum vapor deposition using the ITO sintered body thus produced as an electron beam evaporation source, both transparency and conductivity are good, and defects such as pinholes are generated. It is possible to obtain a good quality ITO film. Spikes of the ITO sintered body during film formation were hardly observed, and it is presumed that splash is suppressed. Further, when the content of tin oxide in the ITO film after film formation was examined, it was the same as the content of tin oxide in the ITO sintered body,
The amounts of SiO 2 and MgO mixed in the ITO film were very small.
【００２４】すなわち、上記のＩＴＯ焼結体を真空蒸着
の蒸発源として用いることで、透明性、導電性ともに良
好でピンホール等の欠陥のない良質のＩＴＯ膜を製作で
きる。That is, by using the above ITO sintered body as an evaporation source for vacuum vapor deposition, a high quality ITO film having both excellent transparency and conductivity and no defects such as pinholes can be manufactured.
【００２５】また、ＩＴＯ焼結体を成形するときのプレ
ス圧力も２０ＭＰａ以下であるから、ＩＴＯ焼結体ごと
に密度のバラつきを生じるおそれもなく、製品としてＩ
ＴＯ焼結体の再現性にすぐれており、高い生産性を期待
できる。Further, since the pressing pressure at the time of molding the ITO sintered body is 20 MPa or less, there is no possibility that the density of each ITO sintered body will vary, and the product I
The TO sintered product has excellent reproducibility and high productivity can be expected.
【００２６】（実施例１）ＩＴＯ焼結体の主成分である
酸化インジウムと酸化錫の割合が重量比９５：５である
ＩＴＯ原材料に、添加物として重量比でＩＴＯ原材料１
００重量部に対してＳｉＯ2 を１．０重量部、ＭｇＯを
１．０重量部それぞれ加える。この混合物をボール・ミ
ルを使って充分に細かい粒状形状にしながら混ぜ合わせ
る。(Example 1) ITO raw material 1 in which the ratio of indium oxide to tin oxide, which is the main component of the ITO sintered body, was 95: 5 by weight, and ITO raw material 1 was added as a weight ratio.
1.0 part by weight of SiO 2 and 1.0 part by weight of MgO are added to each of 00 parts by weight. The mixture is blended using a ball mill in a finely pulverized form.
【００２７】その後プレス圧力１３ＭＰａで大きさが１
０×１０×７（ｍｍ）のペレット形状に成形する。プレ
ス後大気中にて温度１６００℃で加熱しＩＴＯ焼結体を
得る。Thereafter, the press pressure is 13 MPa and the size is 1
It is molded into a pellet shape of 0 × 10 × 7 (mm). After pressing, it is heated in the atmosphere at a temperature of 1600 ° C. to obtain an ITO sintered body.
【００２８】このようにして作製したＩＴＯ焼結体の密
度は、理論密度７．１５ｇ／ｃｍ3の８４％である６．
０４ｇ／ｃｍ3 であった。通常の真空蒸着装置の電子ビ
ーム蒸発源にこのＩＴＯ焼結体を設置し、酸素ガス圧４
×１０-2Ｐａ、基板温度３００℃の雰囲気において成膜
速度０．３ｎｍ／ｓｅｃでガラス基板上にＩＴＯ膜を成
膜した。The density of the ITO sintered body thus produced is 84% of the theoretical density of 7.15 g / cm 3 .
It was 04 g / cm 3 . This ITO sintered body was installed in the electron beam evaporation source of a normal vacuum vapor deposition apparatus, and the oxygen gas pressure was set to 4
An ITO film was formed on a glass substrate at a film forming rate of 0.3 nm / sec in an atmosphere of × 10 -2 Pa and substrate temperature of 300 ° C.
【００２９】得られたＩＴＯ膜の透過率は波長５５０ｎ
ｍにて８７％、抵抗値は２０Ω／ｃｍであった。The transmittance of the obtained ITO film has a wavelength of 550n.
It was 87% in m and the resistance value was 20 Ω / cm.
【００３０】誘導結合プラズマ分析（以下Ｉ．Ｃ．Ｐ発
光分析と略す）にてＩＴＯ焼結体中の酸化錫の含有量と
ＩＴＯ膜中の酸化錫の含有量を測定したところどちらか
らも４．８％のＳｎＯ2 濃度値を得た。また、ＩＴＯ膜
中へのＳｉＯ2 、ＭｇＯの混入量は検出限界値に近い極
くわずかなものであり、ＩＴＯ膜が酸化インジウムと酸
化錫から構成されていることが確かめられた。The content of tin oxide in the ITO sintered body and the content of tin oxide in the ITO film were measured by inductively coupled plasma analysis (hereinafter referred to as ICP emission analysis). A SnO 2 concentration value of 0.8% was obtained. Further, the amounts of SiO 2 and MgO mixed in the ITO film were very small, close to the detection limit value, and it was confirmed that the ITO film was composed of indium oxide and tin oxide.
【００３１】本実施例にて得られたＩＴＯ焼結体とＩＴ
Ｏ膜をサンプルＡとして物性値を表１に示す。The ITO sintered body and IT obtained in this example
The physical properties of the O film as sample A are shown in Table 1.
【００３２】本実施例のＩＴＯ焼結体には電子ビーム加
熱方式を用いる真空蒸着法で従来見られたＩＴＯ焼結体
の針立ちが無くなった。また、それによる影響のものと
思われる破損微粒物の飛散（スプラッシュ）が抑制され
た。その結果、可視域において良好な透明性と高導電性
を有するピンホールの無い無欠陥膜が作製されたものと
推測される。In the ITO sintered body of this example, the needle-pointing of the ITO sintered body which has been conventionally observed by the vacuum deposition method using the electron beam heating system is eliminated. Moreover, the scattering (splash) of broken fine particles, which is considered to be caused by the influence, was suppressed. As a result, it is speculated that a defect-free film having good transparency and high conductivity in the visible region and having no pinhole was produced.
【００３３】なお、ＳｉＯ2 とＭｇＯの添加量をそれぞ
れ１．０〜２．０重量部の範囲で変化させ、かつ、プレ
ス圧力も０．２〜２０ＭＰａの範囲で変化させて、上記
と同様の実験を行なったところ、本実施例と同様の効果
があることを確認した。The amounts of SiO 2 and MgO added were each changed in the range of 1.0 to 2.0 parts by weight, and the pressing pressure was also changed in the range of 0.2 to 20 MPa. As a result of experiments, it was confirmed that the same effect as that of this example was obtained.
【００３４】次に本実施例の比較例を説明する。Next, a comparative example of this embodiment will be described.
【００３５】（実施例１の比較例１）ＩＴＯ焼結体の主
成分である酸化インジウムと酸化錫の割合が重量比９
５：５であるＩＴＯ原材料に、添加物として重量比でＩ
ＴＯ原材料１００重量部に対してＭｇＯのみを１．０重
量部加える。(Comparative Example 1 of Example 1) The weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 9%.
The ITO raw material of 5: 5 is added with I as a weight ratio as an additive.
Only 1.0 part by weight of MgO is added to 100 parts by weight of the TO raw material.
【００３６】それ以外は実施例１と同様にＩＴＯ焼結体
を製作し、ＩＴＯ膜を成膜した。Other than that, an ITO sintered body was manufactured in the same manner as in Example 1 to form an ITO film.
【００３７】ＩＴＯ焼結体の密度は、理論密度７．１５
ｇ／ｃｍ3 の５２％である３．７ｇ／ｃｍ3 であった。The density of the ITO sintered body is a theoretical density of 7.15.
It was 3.7 g / cm 3 is 52% of the g / cm 3.
【００３８】また、得られたＩＴＯ膜の透過率は波長５
５０ｎｍにて８５％、抵抗値は２２Ω／ｃｍであった。The transmittance of the obtained ITO film has a wavelength of 5
It was 85% at 50 nm and the resistance value was 22 Ω / cm.
【００３９】Ｉ．Ｃ．Ｐ発光分析にてＩＴＯ焼結体中の
酸化錫の含有量とＩＴＯ膜中の酸化錫の含有量を測定し
たところ、ＩＴＯ焼結体からは４．９％のＳｎＯ2 濃度
値を得たのに対しＩＴＯ膜からは４．４％のＳｎＯ2 濃
度値を得た。I. C. When the content of tin oxide in the ITO sintered body and the content of tin oxide in the ITO film were measured by P emission analysis, a SnO 2 concentration value of 4.9% was obtained from the ITO sintered body. On the other hand, an SnO 2 concentration value of 4.4% was obtained from the ITO film.
【００４０】本比較例にて得られたＩＴＯ焼結体とＩＴ
Ｏ膜をサンプルＢとして物性値を表１に示す。ITO sintered body and IT obtained in this comparative example
Table 1 shows the physical properties of the O film as Sample B.
【００４１】本比較例のＩＴＯ焼結体には電子ビーム加
熱方式を用いる真空蒸着法で従来見られたＩＴＯ焼結体
の針立ちが無くなった。しかし針立ちによる影響のもの
と思われる破損微粒物の飛散（スプラッシュ）は真空蒸
着中にわずかだがあった。このため可視域における透明
性と導電性は充分であるがピンホール等の欠陥を有する
膜が作製されていた。In the ITO sintered body of this comparative example, the needle-pointing of the ITO sintered body which has been conventionally observed by the vacuum deposition method using the electron beam heating system is eliminated. However, there was a slight splash (splash) of broken fine particles, which is considered to be caused by the stapling, during the vacuum deposition. For this reason, a film having sufficient transparency and conductivity in the visible region but having defects such as pinholes has been prepared.
【００４２】添加物がＭｇＯのみであるために、スプラ
ッシュの発生を回避できなかったものと推測される。It is speculated that the occurrence of splash could not be avoided because the additive was only MgO.
【００４３】（実施例１の比較例２）ＩＴＯ焼結体の主
成分である酸化インジウムと酸化錫の割合が重量比９
５：５であるＩＴＯ原材料に、添加物として重量比でＩ
ＴＯ原材料１００重量部に対しＳｉＯ2 とＭｇＯをそれ
ぞれ０．５重量部加える。(Comparative Example 2 of Example 1) The weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 9 in weight.
The ITO raw material of 5: 5 is added with I as a weight ratio as an additive.
0.5 parts by weight of each of SiO 2 and MgO is added to 100 parts by weight of the TO raw material.
【００４４】それ以外は実施例１と同様にＩＴＯ焼結体
を製作し、ＩＴＯ膜を成膜した。Other than that, an ITO sintered body was manufactured and an ITO film was formed in the same manner as in Example 1.
【００４５】得られたＩＴＯ焼結体とＩＴＯ膜をサンプ
ルＣとして物性値を表１に示す。Table 1 shows the physical properties of the obtained ITO sintered body and ITO film as sample C.
【００４６】ＳｉＯ2 とＭｇＯとがそれぞれ１重量部未
満であるから、添加効果が現われず、ＩＴＯ膜中のＳｎ
Ｏ2 濃度値はＩＴＯ焼結体中のＳｎＯ2 濃度値である５
％より少なく、また、スプラッシュによるものと思われ
る膜欠陥が多数見られた。Since each of SiO 2 and MgO is less than 1 part by weight, the effect of addition does not appear, and Sn in the ITO film does not appear.
The O 2 concentration value is the SnO 2 concentration value in the ITO sintered body. 5
%, And a large number of film defects which were considered to be caused by splash were observed.
【００４７】（実施例１の比較例３）ＩＴＯ焼結体の主
成分である酸化インジウムと酸化錫の割合が重量比９
５：５であるＩＴＯ原材料に、添加物として重量比でＩ
ＴＯ原材料１００重量部に対してＳｉＯ2 とＭｇＯをそ
れぞれ３．０重量部加える。(Comparative Example 3 of Example 1) The ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 9 by weight.
The ITO raw material of 5: 5 is added with I as a weight ratio as an additive.
Add 3.0 parts by weight of SiO 2 and MgO to 100 parts by weight of the TO raw material.
【００４８】それ以外は実施例１と同様にＩＴＯ焼結体
を製作し、ＩＴＯ膜を成膜した。Other than that, an ITO sintered body was manufactured in the same manner as in Example 1, and an ITO film was formed.
【００４９】得られたＩＴＯ焼結体とＩＴＯ膜をサンプ
ルＤとして物性値を表１に示す。Table 1 shows the physical properties of the obtained ITO sintered body and ITO film as sample D.
【００５０】ＳｉＯ2 とＭｇＯとがそれぞれ２重量部を
超えているため、ＩＴＯ膜中の添加物であるＳｉＯ2 ま
たはＭｇＯの混入が膜厚方向で不均一になり良好なる導
電性を示さないＩＴＯ膜が成膜された。Since each of SiO 2 and MgO exceeds 2 parts by weight, mixing of SiO 2 or MgO, which is an additive in the ITO film, becomes non-uniform in the film thickness direction, and ITO does not exhibit good conductivity. A film was deposited.
【００５１】次に、本発明の第２の実施の形態を説明す
る。これは、ＩＴＯ焼結体の主成分である酸化インジウ
ムと酸化錫の重量比を９５：５とする原材料（ＩＴＯ原
材料）１００重量部に、ＳｉＯ2 を０．０５〜０．５重
量部、ＭｇＯを０．００５〜２．０重量部、Ａｌ2 Ｏ3
を１．００〜２．５重量部添加し、ボール・ミル等を使
って充分に細かい粒状混合物を得るものである。なお、
各添加物の添加量は、ＳｉＯ2 が０．１０〜０．１５重
量部、ＭｇＯが０．００５〜０．０５重量部、Ａｌ2 Ｏ
3 が１．００〜２．５重量部であるのがより一層望まし
い。得られた粒状混合物を、プレス圧力０．２〜２０Ｍ
Ｐａでペレット状に圧縮成形し、大気中で所定の温度で
加熱、焼結させ、ＩＴＯ焼結体を製作する。Next, a second embodiment of the present invention will be described. This is based on 100 parts by weight of a raw material (ITO raw material) in which the weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, is 95: 5, 0.05 to 0.5 parts by weight of SiO 2 , and MgO. 0.005 to 2.0 parts by weight, Al 2 O 3
1.00 to 2.5 parts by weight is added and a sufficiently fine granular mixture is obtained using a ball mill or the like. In addition,
The amount of each additive added is 0.10 to 0.15 parts by weight of SiO 2 , 0.005 to 0.05 parts by weight of MgO, and Al 2 O.
It is even more desirable that 3 be 1.00 to 2.5 parts by weight. The obtained granular mixture is pressed at a pressure of 0.2 to 20M.
The ITO sintered body is manufactured by compression-molding into a pellet shape with Pa and heating and sintering at a predetermined temperature in the atmosphere.
【００５２】このようにして製作したＩＴＯ焼結体を電
子ビーム蒸発源とする真空蒸着によってガラス基板等に
ＩＴＯ膜を成膜すると、透明性、導電性ともに良好で、
ピンホール等の欠陥のない良質のＩＴＯ膜を得ることが
できる。成膜中のＩＴＯ焼結体の針立ちはほとんど観察
されず、スプラッシュが抑制されていると推測される。
また、成膜後のＩＴＯ膜の酸化錫の含有量を調べたとこ
ろ、ＩＴＯ焼結体の酸化錫の含有量と同じであり、ＩＴ
Ｏ膜中へのＡｌ2 Ｏ3 、ＳｉＯ2 、ＭｇＯの混入量も極
く微量であった。When an ITO film is formed on a glass substrate or the like by vacuum vapor deposition using the ITO sintered body thus produced as an electron beam evaporation source, both transparency and conductivity are excellent,
It is possible to obtain a good quality ITO film without defects such as pinholes. Spikes of the ITO sintered body during film formation were hardly observed, and it is presumed that splash is suppressed.
Further, when the content of tin oxide in the ITO film after film formation was examined, it was found to be the same as the content of tin oxide in the ITO sintered body.
The amount of Al 2 O 3 , SiO 2 , and MgO mixed in the O film was also extremely small.
【００５３】すなわち、上記のＩＴＯ焼結体を真空蒸着
の蒸発源として用いることで、透明性、導電性ともに良
好でピンホール等の欠陥のない良質のＩＴＯ膜を製作で
きる。That is, by using the above ITO sintered body as an evaporation source for vacuum vapor deposition, a good quality ITO film having both excellent transparency and conductivity and no defects such as pinholes can be manufactured.
【００５４】また、ＩＴＯ焼結体を成形するときのプレ
ス圧力も２０ＭＰａ以下であるから、ＩＴＯ焼結体ごと
に密度のバラつきを生じるおそれもなく、製品としてＩ
ＴＯ焼結体の再現性にすぐれており、高い生産性を期待
できる。Further, since the pressing pressure at the time of molding the ITO sintered body is 20 MPa or less, there is no possibility that the density of each ITO sintered body will vary, and the product I
The TO sintered product has excellent reproducibility and high productivity can be expected.
【００５５】（実施例２）ＩＴＯ焼結体の主成分である
酸化インジウムと酸化錫の割合が重量比９５：５である
ＩＴＯ原材料に、添加物として重量比でＩＴＯ原材料１
００重量部に対してＳｉＯ2 を０．１１重量部、ＭｇＯ
を０．０２重量部、Ａｌ2 Ｏ3 を１．６１重量部それぞ
れ加える。この混合物をボール・ミルを使って充分に細
かい粒状形状にしながら混ぜ合わせる。(Example 2) ITO raw material 1 in which the ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 95: 5 by weight, and ITO raw material 1 was added as a weight ratio.
0.1 parts by weight of SiO 2 and MgO with respect to 00 parts by weight
Is added in an amount of 0.02 parts by weight and Al 2 O 3 is added in an amount of 1.61 parts by weight. The mixture is blended using a ball mill in a finely pulverized form.
【００５６】その後プレス圧力１３ＭＰａで大きさが１
０×１０×７（ｍｍ）のペレット形状に成形する。プレ
ス後大気中にて温度１６００℃で加熱しＩＴＯ焼結体を
得る。Thereafter, the size is 1 at a pressing pressure of 13 MPa.
It is molded into a pellet shape of 0 × 10 × 7 (mm). After pressing, it is heated in the atmosphere at a temperature of 1600 ° C. to obtain an ITO sintered body.
【００５７】このようにして作製したＩＴＯ焼結体の密
度は、理論密度７．１５ｇ／ｃｍ3の９６％である６．
８６ｇ／ｃｍ3 であった。通常の真空蒸着装置の電子ビ
ーム蒸発源にこのＩＴＯ焼結体を設置し、実施例１と同
様の成膜方法でガラス基板上にＩＴＯ膜を成膜した。The density of the ITO sintered body thus produced is 96% of the theoretical density of 7.15 g / cm 3 .
It was 86 g / cm 3 . This ITO sintered body was installed in an electron beam evaporation source of a usual vacuum vapor deposition apparatus, and an ITO film was formed on a glass substrate by the same film forming method as in Example 1.
【００５８】得られたＩＴＯ膜の透過率は波長５５０ｎ
ｍにて８８％、抵抗値は２１Ω／ｃｍであった。The transmittance of the obtained ITO film has a wavelength of 550 n.
It was 88% in m and the resistance value was 21 Ω / cm.
【００５９】Ｉ．Ｃ．Ｐ発光分析にてＩＴＯ焼結体中の
酸化錫の含有量とＩＴＯ膜中の酸化錫の含有量を測定し
たところ、どちらからも４．８％のＳｎＯ2 濃度値を得
た。また、ＩＴＯ膜中へのＳｉＯ2 、ＭｇＯ、Ａｌ2 Ｏ
3 の混入量は検出限界値に近い極わずかなものでありＩ
ＴＯ膜が酸化インジウムと酸化錫から構成されているこ
とが確かめられた。I. C. When the content of tin oxide in the ITO sintered body and the content of tin oxide in the ITO film were measured by P emission analysis, a SnO 2 concentration value of 4.8% was obtained from both. In addition, SiO 2 , MgO, Al 2 O in the ITO film
The mixing amount of 3 is a very small amount close to the detection limit value.
It was confirmed that the TO film was composed of indium oxide and tin oxide.
【００６０】本実施例にて得られたＩＴＯ焼結体とＩＴ
Ｏ膜をサンプルＥとして物性値を表１に示す。ITO sintered body and IT obtained in this example
Table 1 shows the physical properties of the O film as sample E.
【００６１】本実施例のＩＴＯ焼結体には電子ビーム加
熱方式を用いる真空蒸着法で従来見られたＩＴＯ焼結体
の針立ちが無くなった。また、それによる影響のものと
思われる破損微粒物の飛散（スプラッシュ）が抑制され
た。その結果、可視域において良好な透明性と高導電性
を有するピンホールの無い無欠陥膜が作製されたものと
推測される。In the ITO sintered body of this example, the needle-pointing of the ITO sintered body which has been conventionally observed by the vacuum deposition method using the electron beam heating system is eliminated. Moreover, the scattering (splash) of broken fine particles, which is considered to be caused by the influence, was suppressed. As a result, it is speculated that a defect-free film having good transparency and high conductivity in the visible region and having no pinhole was produced.
【００６２】なお、ＳｉＯ2 とＭｇＯとＡｌ2 Ｏ3 の添
加量をそれぞれ０．０５〜０．５重量部、０．０５〜
２．０重量部、１．００〜２．５重量部の範囲で変化さ
せ、かつ、プレス圧力も０．２〜２０ＭＰａの範囲で変
化させて、上記と同様の実験を行なったところ、本実施
例と同様の効果があることを確認した。The amounts of SiO 2 , MgO, and Al 2 O 3 added were 0.05 to 0.5 parts by weight and 0.05 to 0.5 parts by weight, respectively.
An experiment similar to the above was conducted by changing the pressure in the range of 2.0 parts by weight and 1.00 to 2.5 parts by weight, and the pressing pressure in the range of 0.2 to 20 MPa. It was confirmed that the same effect as the example was obtained.
【００６３】次に本実施例の比較例を説明する。Next, a comparative example of this embodiment will be described.
【００６４】（実施例２の比較例１）ＩＴＯ焼結体の主
成分である酸化インジウムと酸化錫の割合が重量比９
５：５であるＩＴＯ原材料に、添加物として重量比でＩ
ＴＯ原材料１００重量部に対してＳｉＯ2 とＡｌ2 Ｏ3
をそれぞれ１．０重量部加える。(Comparative Example 1 of Example 2) The ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 9 by weight.
The ITO raw material of 5: 5 is added with I as a weight ratio as an additive.
SiO 2 and Al 2 O 3 for 100 parts by weight of TO raw material
1.0 part by weight each.
【００６５】それ以外は実施例２と同様にＩＴＯ焼結体
を製作し、ＩＴＯ膜を成膜した。Other than that, an ITO sintered body was manufactured in the same manner as in Example 2, and an ITO film was formed.
【００６６】ＩＴＯ焼結体の密度は、理論密度７．１５
ｇ／ｃｍ3 の８７％である６．２５ｇ／ｃｍ3 であっ
た。The density of the ITO sintered body has a theoretical density of 7.15.
was 6.25 g / cm 3 which is 87% of the g / cm 3.
【００６７】また、得られたＩＴＯ膜の透過率は波長５
５０ｎｍにて８０％、抵抗値は７２Ω／ｃｍであった。The transmittance of the obtained ITO film has a wavelength of 5
80% at 50 nm and a resistance value of 72 Ω / cm.
【００６８】Ｉ．Ｃ．Ｐ発光分析にてＩＴＯ焼結体中の
酸化錫の含有量とＩＴＯ膜中の酸化錫の含有量を測定し
たところ、ＩＴＯ焼結体からは４．９％のＳｎＯ2 濃度
値を得たのに対しＩＴＯ膜からは４．１％のＳｎＯ2 濃
度値であった。I. C. When the content of tin oxide in the ITO sintered body and the content of tin oxide in the ITO film were measured by P emission analysis, a SnO 2 concentration value of 4.9% was obtained from the ITO sintered body. On the other hand, from the ITO film, the SnO 2 concentration value was 4.1%.
【００６９】本比較例にて得られたＩＴＯ焼結体とＩＴ
Ｏ膜をサンプルＦとして物性値を表１に示す。ITO sintered body and IT obtained in this comparative example
The physical properties of the O film as sample F are shown in Table 1.
【００７０】本比較例のＩＴＯ焼結体には電子ビーム加
熱方式を用いる真空蒸着法で従来見られたＩＴＯ焼結体
の針立ちが無くなった。しかし針立ちによる影響のもの
と思われる破損微粒物の飛散（スプラッシュ）は真空蒸
着中にわずかだがあった。その結果、可視域における透
明性と導電性は充分であるがピンホール等の欠陥を有す
る膜が作製されていた。In the ITO sintered body of this comparative example, the needle-pointing of the ITO sintered body which has been conventionally observed by the vacuum deposition method using the electron beam heating system is eliminated. However, there was a slight splash (splash) of broken fine particles, which is considered to be caused by the stapling, during the vacuum deposition. As a result, a film having sufficient transparency and conductivity in the visible region but having defects such as pinholes was produced.
【００７１】これは、各添加物の添加量が適切でないた
めと推測される。It is speculated that this is because the amount of each additive added is not appropriate.
【００７２】（実施例２の比較例２）ＩＴＯ焼結体の主
成分である酸化インジウムと酸化錫の割合が重量比９
５：５であるＩＴＯ原材料に、添加物として重量比でＩ
ＴＯ原材料１００重量部に対しＳｉＯ2 とＭｇＯをそれ
ぞれ０．０５重量部未満の０．０２重量部、Ａｌ2 Ｏ3
を１．００重量部未満の０．５重量部加える。(Comparative Example 2 of Example 2) The weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 9%.
The ITO raw material of 5: 5 is added with I as a weight ratio as an additive.
0.02 parts by weight of each less than 0.05 part by weight SiO 2 and MgO to respect TO raw material 100 parts by weight, Al 2 O 3
0.5 parts by weight less than 1.00 parts by weight.
【００７３】それ以外は実施例２と同様にＩＴＯ焼結体
を製作し、ＩＴＯ膜を成膜した。Other than that, an ITO sintered body was manufactured in the same manner as in Example 2 to form an ITO film.
【００７４】得られたＩＴＯ焼結体とＩＴＯ膜をサンプ
ルＧとして物性値を表１に示す。Table 1 shows the physical properties of the obtained ITO sintered body and ITO film as sample G.
【００７５】ＳｉＯ2 とＭｇＯとがそれぞれ０．０５重
量部未満で、Ａｌ2 Ｏ3 も０．１重量部未満であるか
ら、添加効果が現われず、ＩＴＯ膜中のＳｎＯ2 濃度値
はＩＴＯ焼結体中のＳｎＯ2 濃度値である５％より少な
く、また、スプラッシュによるものと思われる膜欠陥が
多数見られた。Since each of SiO 2 and MgO is less than 0.05 parts by weight and Al 2 O 3 is also less than 0.1 parts by weight, the effect of addition does not appear, and the SnO 2 concentration value in the ITO film is the The SnO 2 concentration value in the aggregate was less than 5%, and many film defects that were considered to be due to splash were observed.
【００７６】（実施例２の比較例３）ＩＴＯ焼結体の主
成分である酸化インジウムと酸化錫の割合が重量比９
５：５であるＩＴＯ原材料に、添加物として重量比でＩ
ＴＯ原材料１００重量部に対してＳｉＯ2 を０．５重量
部以上の０．７重量部、ＭｇＯを０．０５重量部、Ａｌ
2 Ｏ3 を１．５０重量部加える。(Comparative Example 3 of Example 2) The weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, was 9%.
The ITO raw material of 5: 5 is added with I as a weight ratio as an additive.
To 100 parts by weight of TO raw material, 0.7 parts by weight of SiO 2 of 0.5 parts by weight or more, 0.05 parts by weight of MgO, Al
The 2 O 3 is added 1.50 parts by weight.
【００７７】それ以外は実施例２と同様にＩＴＯ焼結体
を製作し、ＩＴＯ膜を成膜した。Other than that, an ITO sintered body was manufactured in the same manner as in Example 2, and an ITO film was formed.
【００７８】得られたＩＴＯ焼結体とＩＴＯ膜をサンプ
ルＨとして物性値を表１に示す。Table 1 shows the physical properties of the obtained ITO sintered body and ITO film as sample H.
【００７９】ＳｉＯ2 が０．５重量部を超えているた
め、ＩＴＯ膜中の添加物の混入が膜厚方向で不均一にな
り良好なる導電性を示さないＩＴＯ膜が成膜された。特
に、ＩＴＯ膜の抵抗値は８３Ω／ｃｍと高く、これは、
ＳｉＯ2 が０．５重量部を超えているためと推測され
る。Since the amount of SiO 2 was more than 0.5 part by weight, the mixture of additives in the ITO film became non-uniform in the film thickness direction, and an ITO film which did not show good conductivity was formed. In particular, the ITO film has a high resistance value of 83 Ω / cm, which is
It is presumed that the amount of SiO 2 exceeds 0.5 parts by weight.
【００８０】次に、本発明の第３の実施の形態を説明す
る。これは、ＩＴＯ焼結体の主成分である酸化インジウ
ムと酸化錫の重量比を９５：５とする原材料（ＩＴＯ原
材料）１００重量部にＳｉＯ2 を１．０〜２．０重量
部、ＭｇＯを１．０〜２．０重量部添加し、ボール・ミ
ル等を使って充分に細かい粒状混合物を得る。得られた
粒状混合物を、プレス圧力０．２〜２０ＭＰａでターゲ
ット状に圧縮成形し、大気中で所定の温度で加熱、焼結
させ、ＩＴＯ焼結体を製作する。Next, a third embodiment of the present invention will be described. This is because 1.0 to 2.0 parts by weight of SiO 2 and MgO are added to 100 parts by weight of a raw material (ITO raw material) having a weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, of 95: 5. Add 1.0 to 2.0 parts by weight and use a ball mill or the like to obtain a sufficiently fine granular mixture. The obtained granular mixture is compression-molded into a target with a pressing pressure of 0.2 to 20 MPa and heated and sintered at a predetermined temperature in the atmosphere to produce an ITO sintered body.
【００８１】このようにして製作したＩＴＯ焼結体をタ
ーゲットとする真空マグネトロンスパッタリングによっ
てガラス基板上にＩＴＯ膜を成膜すると、透明性、導電
性ともに良好で、ピンホール等の欠陥のない良質のＩＴ
Ｏ膜を得ることができる。成膜中のＩＴＯ焼結体のスプ
ラッシュはほとんど観察されず、また、成膜後のＩＴＯ
膜の酸化錫の含有量を調べたところ、ＩＴＯ焼結体の酸
化錫の含有量と同じであり、ＩＴＯ膜中へのＳｉＯ2 、
ＭｇＯの混入量も極く微量であった。When an ITO film is formed on a glass substrate by vacuum magnetron sputtering targeting the ITO sintered body produced in this way, the transparency and conductivity are good, and there are no defects such as pinholes. IT
An O film can be obtained. Almost no splash of ITO sintered body was observed during film formation, and ITO after film formation
When the content of tin oxide in the film was examined, it was found to be the same as the content of tin oxide in the ITO sintered body, and SiO 2 in the ITO film,
The amount of MgO mixed was extremely small.
【００８２】すなわち、上記のＩＴＯ焼結体を真空マグ
ネトロンスパッタリングのターゲットとして用いること
で、透明性、導電性ともに良好でピンホール等の欠陥の
ない良質のＩＴＯ膜を製作できる。That is, by using the above ITO sintered body as a target for vacuum magnetron sputtering, a high quality ITO film having both excellent transparency and conductivity and no defects such as pinholes can be manufactured.
【００８３】また、ＩＴＯ焼結体を成形するときのプレ
ス圧力も２０ＭＰａ以下であるから、ＩＴＯ焼結体ごと
に密度のバラつきを生じるおそれもなく、製品としてＩ
ＴＯ焼結体の再現性にすぐれており、高い生産性を期待
できる。Further, since the pressing pressure at the time of molding the ITO sintered body is 20 MPa or less, there is no possibility that the density of each ITO sintered body will vary, and the product I
The TO sintered product has excellent reproducibility and high productivity can be expected.
【００８４】（実施例３）ＩＴＯ焼結体の主成分である
酸化インジウムと酸化錫の割合が重量比９５：５である
ＩＴＯ原材料に添加物として重量比でＩＴＯ原材料１０
０重量部％に対してＳｉＯ2 を１．０重量部、ＭｇＯを
１．０重量部それぞれ加える。この混合物をボール・ミ
ルを使って充分に細かい粒状形状にしながら混ぜ合わせ
る。Example 3 The ITO raw material 10 was added by weight as an additive to the ITO raw material in which the ratio of indium oxide and tin oxide as the main components of the ITO sintered body was 95: 5.
1.0 part by weight of SiO 2 and 1.0 part by weight of MgO are added to 0 part by weight. The mixture is blended using a ball mill in a finely pulverized form.
【００８５】その後プレス圧力６ＭＰａで大きさが直径
１２７×５（ｍｍ）のターゲット形状に成形する。プレ
ス後大気中にて温度１４５０℃で加熱しＩＴＯ焼結体を
得る。After that, it is molded into a target shape having a diameter of 127 × 5 (mm) with a pressing pressure of 6 MPa. After pressing, it is heated in the atmosphere at a temperature of 1450 ° C. to obtain an ITO sintered body.
【００８６】このようにして作製したＩＴＯ焼結体の密
度は、理論密度７．１５ｇ／ｃｍ3の９０％である６．
４ｇ／ｃｍ3 であった。通常の真空マグネトロンスパッ
タリング装置のターゲットとして、銅のバッキングプレ
ートにこのＩＴＯ焼結体を貼り付けたものを用いて、酸
素ガスとアルゴンガスを導入し、圧力を０．４Ｐａに制
御して、基板温度３００℃の雰囲気において成膜速度
１．６ｎｍ／ｓｅｃでガラス基板上にＩＴＯ膜を成膜し
た。The density of the ITO sintered body thus produced is 90% of the theoretical density of 7.15 g / cm 3 .
It was 4 g / cm 3 . As a target of a normal vacuum magnetron sputtering device, a copper backing plate having the ITO sintered body attached thereto was used, oxygen gas and argon gas were introduced, the pressure was controlled to 0.4 Pa, and the substrate temperature was adjusted. An ITO film was formed on a glass substrate at a film forming rate of 1.6 nm / sec in an atmosphere of 300 ° C.
【００８７】得られたＩＴＯ膜の透過率は波長５５０ｎ
ｍにて８６％、抵抗値は１９Ω／ｃｍであった。The transmittance of the obtained ITO film has a wavelength of 550 n.
It was 86% in m and the resistance value was 19 Ω / cm.
【００８８】Ｉ．Ｃ．Ｐ発光分析にてＩＴＯ焼結体中の
酸化錫の含有量とＩＴＯ膜中の酸化錫の含有量を測定し
たところ、どちらからも４．９％のＳｎＯ2 濃度値を得
た。また、ＩＴＯ膜中へのＳｎＯ2 、ＭｇＯの混入量は
検出限界値に近い極わずかなものでありＩＴＯ膜が酸化
インジウムと酸化錫から構成されていることが確かめら
れた。I. C. When the content of tin oxide in the ITO sintered body and the content of tin oxide in the ITO film were measured by P emission analysis, a SnO 2 concentration value of 4.9% was obtained from both. Further, the amounts of SnO 2 and MgO mixed in the ITO film were very small close to the detection limit value, and it was confirmed that the ITO film was composed of indium oxide and tin oxide.
【００８９】本実施例にて得られたＩＴＯ焼結体とＩＴ
Ｏ膜をサンプルＩとして物性値を表１に示す。The ITO sintered body and IT obtained in this example
Table 1 shows the physical properties of the O film as sample I.
【００９０】また、成膜中ＩＴＯ焼結体からの破損微粒
物の飛散（スプラッシュ）が抑制され、その結果、可視
域において良好な透明性と高導電性を有するピンホール
の無い無欠陥膜が作製されたものと推測される。Further, scattering (splash) of broken fine particles from the ITO sintered body during film formation is suppressed, and as a result, a pinhole-free defect-free film having good transparency and high conductivity in the visible region is obtained. It is assumed that it was created.
【００９１】なお、ＳｉＯ2 とＭｇＯの添加量をそれぞ
れ１．０〜２．０重量部の範囲で変化させ、かつ、プレ
ス圧力も０．２〜２０ＭＰａの範囲で変化させて、上記
と同様の実験を行なったところ、本実施例と同様の効果
があることを確認した。The amounts of SiO 2 and MgO added were each changed in the range of 1.0 to 2.0 parts by weight, and the pressing pressure was also changed in the range of 0.2 to 20 MPa. As a result of experiments, it was confirmed that the same effect as that of this example was obtained.
【００９２】次に、本発明の第４の実施の形態を説明す
る。これは、ＩＴＯ焼結体の主成分である酸化インジウ
ムと酸化錫の重量比を９５：５とする原材料（ＩＴＯ原
材料）１００重量部にＳｉＯ2 を０．０５〜０．５重量
部、ＭｇＯを０．００５〜２．０重量部、Ａｌ2 Ｏ3 を
１．００〜２．５重量部それぞれ添加し、ボール・ミル
等を使って充分に細かい粒状混合物を得る。なお、各添
加物の添加量は、ＳｉＯ2 が０．１０〜０．１５重量
部、ＭｇＯが０．００５〜０．０５重量部、Ａｌ2 Ｏ3
が１．００〜２．５重量部であるのがより一層望まし
い。得られた粒状混合物を、プレス圧力０．２〜２０Ｍ
Ｐａでペレット状に圧縮成形し、大気中で所定の温度で
加熱、焼結させ、ＩＴＯ焼結体を製作する。Next explained is the fourth embodiment of the invention. This is because 0.05 to 0.5 parts by weight of SiO 2 and MgO are added to 100 parts by weight of a raw material (ITO raw material) having a weight ratio of indium oxide and tin oxide, which are the main components of the ITO sintered body, of 95: 5. 0.005 to 2.0 parts by weight and 1.00 to 2.5 parts by weight of Al 2 O 3 are added, and a sufficiently fine granular mixture is obtained using a ball mill or the like. The amount of each additive added was 0.10 to 0.15 parts by weight of SiO 2 , 0.005 to 0.05 parts by weight of MgO, and Al 2 O 3
Is more preferably 1.00 to 2.5 parts by weight. The obtained granular mixture is pressed at a pressure of 0.2 to 20M.
The ITO sintered body is manufactured by compression-molding into a pellet shape with Pa and heating and sintering at a predetermined temperature in the atmosphere.
【００９３】このようにして製作したＩＴＯ焼結体をタ
ーゲットとする真空マグネトロンスパッタリングによっ
てガラス基板等にＩＴＯ膜を成膜すると、透明性、導電
性ともに良好で、ピンホール等の欠陥のない良質のＩＴ
Ｏ膜を得ることができる。成膜中のＩＴＯ焼結体のスプ
ラッシュは抑制されていると推測される。また、成膜後
のＩＴＯ膜の酸化錫の含有量を調べたところ、ＩＴＯ焼
結体の酸化錫の含有量と同じであり、ＩＴＯ膜中へのＡ
ｌ2 Ｏ3 ，ＳｉＯ2 、ＭｇＯの混入量も極く微量であっ
た。When an ITO film is formed on a glass substrate or the like by vacuum magnetron sputtering targeting the ITO sintered body produced in this way, the transparency and the conductivity are good, and there are no defects such as pinholes. IT
An O film can be obtained. It is speculated that the splash of the ITO sintered body during film formation is suppressed. Further, when the content of tin oxide in the ITO film after film formation was examined, it was found to be the same as the content of tin oxide in the ITO sintered body.
The amount of 1 2 O 3 , SiO 2 , and MgO mixed was extremely small.
【００９４】すなわち、上記のＩＴＯ焼結体を真空マグ
ネトロンスパッタリングのターゲットとして用いること
で、透明性、導電性ともに良好でピンホール等の欠陥の
ない良質のＩＴＯ膜を製作できる。That is, by using the above ITO sintered body as a target for vacuum magnetron sputtering, a good quality ITO film having both excellent transparency and conductivity and no defects such as pinholes can be manufactured.
【００９５】また、ＩＴＯ焼結体を成形するときのプレ
ス圧力も２０ＭＰａ以下であるから、ＩＴＯ焼結体ごと
に密度のバラつきを生じるおそれもなく、製品としてＩ
ＴＯ焼結体の再現性にすぐれており、高い生産性を期待
できる。Further, since the pressing pressure at the time of molding the ITO sintered body is 20 MPa or less, there is no possibility that the density of the ITO sintered body will vary, and the product I
The TO sintered product has excellent reproducibility and high productivity can be expected.
【００９６】（実施例４）ＩＴＯ焼結体の主成分である
酸化インジウムと酸化錫の割合が重量比９５：５である
ＩＴＯ原材料に添加物として重量比でＩＴＯ原材料１０
０重量部に対してＳｉＯ2 を０．１１重量部、ＭｇＯを
０．０２重量部、Ａｌ2 Ｏ3 を１．６１重量部加える。
この混合物をボール・ミルを使って充分に細かい粒状形
状にしながら混ぜ合わせる。Example 4 The ITO raw material 10 was added by weight as an additive to the ITO raw material in which the ratio of indium oxide and tin oxide as the main components of the ITO sintered body was 95: 5 by weight.
0.10 parts by weight of SiO 2 , 0.02 parts by weight of MgO and 1.61 parts by weight of Al 2 O 3 are added to 0 parts by weight.
The mixture is blended using a ball mill in a finely pulverized form.
【００９７】実施例３と同様の方法でＩＴＯ焼結体を得
て、ＩＴＯ膜を成膜する。An ITO sintered body is obtained in the same manner as in Example 3, and an ITO film is formed.
【００９８】ＩＴＯ焼結体の密度は、理論密度７．１５
ｇ／ｃｍ3 の９７％である６．９４ｇ／ｃｍ3 であっ
た。The density of the ITO sintered body is the theoretical density of 7.15.
was a 6.94 g / cm 3 is 97% g / cm 3.
【００９９】得られたＩＴＯ膜の透過率は波長５５０ｎ
ｍにて８７％、抵抗値は２１Ω／ｃｍであった。The transmittance of the obtained ITO film has a wavelength of 550 n.
It was 87% in m and the resistance value was 21 Ω / cm.
【０１００】また、Ｉ．Ｃ．Ｐ発光分析にてＩＴＯ焼結
体中の酸化錫の含有量とＩＴＯ膜中の酸化錫の含有量を
測定したところ、どちらからも４．９％のＳｎＯ2 濃度
値を得た。また、ＩＴＯ膜中へのＳｉＯ2 、ＭｇＯ、Ａ
ｌ2 Ｏ3 の混入量は検出限界値に近い極わずかなもので
ありＩＴＯ膜が酸化インジウムと酸化錫から構成されて
いることが確かめられた。In addition, I.D. C. When the content of tin oxide in the ITO sintered body and the content of tin oxide in the ITO film were measured by P emission analysis, a SnO 2 concentration value of 4.9% was obtained from both. In addition, SiO 2 , MgO, A in the ITO film
The amount of l 2 O 3 mixed in was extremely small close to the detection limit value, and it was confirmed that the ITO film was composed of indium oxide and tin oxide.
【０１０１】本実施例にて得られたＩＴＯ焼結体とＩＴ
Ｏ膜をサンプルＪとして物性値を表１に示す。ITO sintered body and IT obtained in this example
The physical properties of the O film as sample J are shown in Table 1.
【０１０２】また成膜中ＩＴＯ焼結体からの破損微粒物
の飛散（スプラッシュ）は抑制された。その結果、可視
域において良好な透明性と高導電性を有するピンホール
の無い無欠陥膜が作製されたものと推測される。Further, scattering (splash) of broken fine particles from the ITO sintered body during film formation was suppressed. As a result, it is speculated that a defect-free film having good transparency and high conductivity in the visible region and having no pinhole was produced.
【０１０３】なお、ＳｉＯ2 とＭｇＯとＡｌ2 Ｏ3 の添
加量をそれぞれ０．０５〜０．５重量部、０．０５〜
２．０重量部、１．００〜２．５重量部の範囲で変化さ
せ、かつ、プレス圧力も０．２〜２０ＭＰａの範囲で変
化させて、上記と同様の実験を行なったところ、本実施
例と同様の効果があることを確認した。The addition amounts of SiO 2 , MgO and Al 2 O 3 were 0.05 to 0.5 parts by weight and 0.05 to 0.5 parts by weight, respectively.
An experiment similar to the above was conducted by changing the pressure in the range of 2.0 parts by weight and 1.00 to 2.5 parts by weight, and the pressing pressure in the range of 0.2 to 20 MPa. It was confirmed that the same effect as the example was obtained.
【０１０４】[0104]
【表１】 [Table 1]
【０１０５】[0105]
【発明の効果】本発明は上述のように構成されているの
で、以下に記載するような効果を奏する。Since the present invention is constructed as described above, it has the following effects.
【０１０６】目標通りの透明性や導電性を有し、しかも
ピンホール等の欠陥のない高品質なＩＴＯ膜を安定して
製造できる。また、ＩＴＯ焼結体を圧縮成形する工程で
高いプレス加工を必要とせず、ＩＴＯ焼結体の生産性を
向上させてＩＴＯ膜の低価格化を促進できる。It is possible to stably manufacture a high-quality ITO film having the desired transparency and conductivity and having no defects such as pinholes. Further, it is possible to improve the productivity of the ITO sintered body and promote the cost reduction of the ITO film without requiring high press working in the step of compression-molding the ITO sintered body.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 橋本 茂 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (56)参考文献 特開 平８−264022（ＪＰ，Ａ) 特開 平８−264023（ＪＰ，Ａ) 特開 平７−54132（ＪＰ，Ａ) 実開 平６−349338（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 14/00 - 14/58 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shigeru Hashimoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-8-264022 (JP, A) JP-A-8 -264023 (JP, A) JP-A-7-54132 (JP, A) Actual development: 6-349338 (JP, U) (58) Fields investigated (Int.Cl. 7 , DB name) C23C 14/00- 14/58
Claims (6)
９５：５であるＩＴＯ原材料を主成分とするＩＴＯ膜成
膜用のＩＴＯ焼結体であって、前記ＩＴＯ原材料にＳｉ
Ｏ2 およびＭｇＯのみを、前記ＩＴＯ原材料１００重量
部に対してそれぞれ１．０〜２．０重量部添加したこと
を特徴とするＩＴＯ焼結体。1. The weight ratio of indium oxide to tin oxide
95: The ITO raw material is 5 a ITO sintered for ITO film forming mainly, Si in the ITO raw material
O 2 and MgO only, 100 wt% of the ITO raw material
1.0 to 2.0 parts by weight to each part of the ITO sintered body.
９５：５であるＩＴＯ原材料を主成分とするＩＴＯ膜成
膜用のＩＴＯ焼結体であって、前記ＩＴＯ原材料にＳｉ
Ｏ 2 、ＭｇＯおよびＡｌ 2 Ｏ 3 を、前記ＩＴＯ原材料１
００重量部に対してそれぞれ０．０５〜０．５重量部、
０．００５〜２．０重量部および１．００〜２．５重量
部添加したことを特徴とするＩＴＯ焼結体。2. The weight ratio of indium oxide to tin oxide
ITO film formation mainly composed of 95: 5 ITO raw material
An ITO sintered body for a film, wherein the ITO raw material contains Si
O 2 , MgO and Al 2 O 3 are added to the ITO raw material 1
0.05 to 0.5 parts by weight per 100 parts by weight,
0.005-2.0 parts by weight and 1.00-2.5 parts by weight
Parts added ITO sintered you, characterized in that the.
蒸発源として真空蒸着によってＩＴＯ膜を成膜する工程
を有するＩＴＯ膜の成膜方法。 3. The ITO sintered body according to claim 1 or 2.
Step of forming an ITO film by vacuum evaporation as an evaporation source
A method for forming an ITO film having:
ターゲットとしてスパッタリングによってＩＴＯ膜を成
膜する工程を有するＩＴＯ膜の成膜方法。 4. The ITO sintered body according to claim 1 or 2.
An ITO film is formed as a target by sputtering.
A method for forming an ITO film having a film forming step.
９５：５であるＩＴＯ原材料に、ＳｉＯ2 およびＭｇＯ
のみを、前記ＩＴＯ原材料１００重量部に対してそれぞ
れ１．０〜２．０重量部添加したものを、０．２〜２０
ＭＰａのプレス圧力で所定の形状に圧縮成形する工程を
有するＩＴＯ焼結体の製造方法。5. The weight ratio of indium oxide to tin oxide is
95: 5 ITO raw material with SiO 2 and MgO
Only for 100 parts by weight of the ITO raw material
1.0 to 2.0 parts by weight is added to 0.2 to 20
A method for manufacturing an ITO sintered body, comprising a step of compression-molding into a predetermined shape with a pressing pressure of MPa.
９５：５であるＩＴＯ原材料に、ＳｉＯ2 、ＭｇＯおよ
びＡｌ2 Ｏ3 を、前記ＩＴＯ原材料１００重量部に対し
てそれぞれ０．０５〜０．５重量部、０．００５〜２．
０重量部および１．００〜２．５重量部添加したもの
を、０．２〜２０ＭＰａのプレス圧力で所定の形状に圧
縮成形する工程を有するＩＴＯ焼結体の製造方法。6. The weight ratio of indium oxide to tin oxide is
95: 5 ITO raw material, SiO 2 , MgO and
And Al 2 O 3 to 100 parts by weight of the ITO raw material
Each Te 0.05 to 0.5 parts by weight, 0.005.
A method for producing an ITO sintered body, comprising a step of compression-molding a mixture of 0 part by weight and 1.00 to 2.5 parts by weight with a pressing pressure of 0.2 to 20 MPa.
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|---|---|---|---|
| JP05847597A JP3501614B2 (en) | 1997-02-26 | 1997-02-26 | ITO sintered body, method of manufacturing the same, and method of forming ITO film using the ITO sintered body |
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|---|---|---|---|
| JP05847597A JP3501614B2 (en) | 1997-02-26 | 1997-02-26 | ITO sintered body, method of manufacturing the same, and method of forming ITO film using the ITO sintered body |
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| Publication Number | Publication Date |
|---|---|
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| JP3501614B2 true JP3501614B2 (en) | 2004-03-02 |
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| JP2007176706A (en) | 2005-12-26 | 2007-07-12 | Mitsui Mining & Smelting Co Ltd | Oxide sintered compact, its production method, sputtering target and transparent electrically conductive film |
| ES2663895T3 (en) * | 2006-05-18 | 2018-04-17 | Hydro-Quebec | Procedure for preparing ceramics, ceramics obtained in this way and their uses specifically as a target for sputtering |
| CN102666909B (en) * | 2009-11-19 | 2016-06-22 | 株式会社爱发科 | The manufacture method of nesa coating, the manufacture device of nesa coating, sputtering target and nesa coating |
| KR102003077B1 (en) * | 2011-06-15 | 2019-07-23 | 스미토모덴키고교가부시키가이샤 | Electrically conductive oxide and method for producing same, and oxide semiconductor film |
| JP6453528B1 (en) * | 2017-05-15 | 2019-01-16 | 三井金属鉱業株式会社 | Sputtering target for transparent conductive film |
| WO2023127195A1 (en) * | 2021-12-28 | 2023-07-06 | 三井金属鉱業株式会社 | Oxide sintered body, method for producing same, and sputtering target material |
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