JPH06234565A - Target and its production - Google Patents
Target and its productionInfo
- Publication number
- JPH06234565A JPH06234565A JP5315084A JP31508493A JPH06234565A JP H06234565 A JPH06234565 A JP H06234565A JP 5315084 A JP5315084 A JP 5315084A JP 31508493 A JP31508493 A JP 31508493A JP H06234565 A JPH06234565 A JP H06234565A
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- transparent conductive
- compound
- target
- sintered body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ターゲットおよびその
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a target and its manufacturing method.
【０００２】[0002]
【従来の技術】近年、表示装置の発展は目覚ましく、液
晶表示装置やＥＬ表示装置等、種々の表示装置がパソコ
ンやワ−プロ等のＯＡ機器へ活発に導入されている。こ
れらの表示装置は、いずれも表示素子を透明導電膜で挟
み込んだサンドイッチ構造を有している。2. Description of the Related Art In recent years, the development of display devices has been remarkable, and various display devices such as liquid crystal display devices and EL display devices have been actively introduced into office automation equipment such as personal computers and word processors. Each of these display devices has a sandwich structure in which a display element is sandwiched between transparent conductive films.
【０００３】透明導電膜としては、現在、ＩＴＯ膜が主
流を占めている。それは、ＩＴＯ膜の高透明性、低抵抗
性の他、エッチング性、基板への付着性等が良好なため
である。このＩＴＯ膜は、一般にスパッタリング法によ
り作製されている。As a transparent conductive film, an ITO film is currently the mainstream. This is because the ITO film has excellent transparency, low resistance, etching properties, and adhesion to the substrate. This ITO film is generally produced by a sputtering method.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ＩＴＯ
膜は耐湿性が比較的低く、湿気により電気抵抗値が増大
するという難点を有している。そして、スパッタリング
法によりＩＴＯ膜を作製する際に用いるＩＴＯターゲッ
トは還元により黒化し易いため、その特性の経時変化が
問題となっている。However, the ITO is
The film has a relatively low humidity resistance, and has a drawback that the electric resistance value increases due to humidity. Since the ITO target used when forming the ITO film by the sputtering method is easily blackened by reduction, the change over time in its characteristics poses a problem.
【０００５】本発明の目的は、ＩＴＯ膜よりも耐湿性に
優れるとともにＩＴＯ膜と同等の導電性および光透過率
を有する透明導電膜を得るための材料等として好適なタ
ーゲットおよびその製造方法を提供することにある。An object of the present invention is to provide a target suitable as a material for obtaining a transparent conductive film which is superior in moisture resistance to an ITO film and has the same conductivity and light transmittance as the ITO film, and a method for producing the target. To do.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成する本発
明のターゲットは、ＩｎとＺｎを主成分とし、一般式Ｉ
ｎ2 Ｏ3 （ＺｎＯ）m （ｍ＝２〜２０）で表される六方
晶層状化合物を含む酸化物の焼結体からなることを特徴
とするものである（以下、このターゲットをターゲット
Ｉという）。また、上記六方晶層状化合物が、正三価以
上の原子価を有する元素の少なくとも１種を全カチオン
元素の合量に対して２０原子％以下でドープしたもので
あることを特徴とするターゲットもまた、上記目的を達
成する（以下、このターゲットをターゲットIIとい
う）。A target of the present invention which achieves the above object is mainly composed of In and Zn and has the general formula I
It is characterized by comprising a sintered body of an oxide containing a hexagonal layered compound represented by n 2 O 3 (ZnO) m (m = 2 to 20) (hereinafter, this target is referred to as target I). ). Further, a target characterized in that the hexagonal layered compound is one in which at least one element having a valence of positive trivalence or more is doped at 20 atom% or less with respect to the total amount of all cationic elements is also provided. , Achieve the above-mentioned purpose (hereinafter, this target is referred to as target II).
【０００７】一方、上記目的を達成する本発明のターゲ
ットの製造方法は、インジウム化合物と亜鉛化合物とを
混合する工程と、前記工程で得られた混合物を仮焼する
工程と、前記工程で得られた仮焼物を成型し焼結して、
ＩｎとＺｎを主成分とし、一般式Ｉｎ2 Ｏ3 （ＺｎＯ）
m （ｍ＝２〜２０）で表される六方晶層状化合物を含む
酸化物の焼結体を得る工程とを含むことを特徴とするも
のである（以下、この方法を方法Ｉという）。さらに、
インジウム化合物と亜鉛化合物に、正三価以上の原子価
を有する元素の化合物の少なくとも１種を加えて混合す
る工程と、前記工程で得られた混合物を仮焼する工程
と、前記工程で得られた仮焼物を成型し焼結して、Ｉｎ
とＺｎを主成分とし、一般式Ｉｎ2 Ｏ3 （ＺｎＯ）
m （ｍ＝２〜２０）で表される六方晶層状化合物に、正
三価以上の原子価を有する元素の少なくとも１種を全カ
チオン元素の合量に対して２０原子％以下でドープした
化合物を含む酸化物の焼結体を得る工程とを含むことを
特徴とするターゲットの製造方法もまた、上記目的を達
成する（以下、この方法を方法IIという）。On the other hand, the method for producing a target of the present invention which achieves the above object, comprises a step of mixing an indium compound and a zinc compound, a step of calcining the mixture obtained in the above step, and a step obtained in the above step. The calcined material is molded and sintered,
The main component is In and Zn, and the general formula is In 2 O 3 (ZnO).
and a step of obtaining a sintered body of an oxide containing a hexagonal layered compound represented by m (m = 2 to 20) (hereinafter, this method is referred to as method I). further,
A step of adding at least one compound of an element having a valence of at least positive trivalence to an indium compound and a zinc compound and mixing, a step of calcining the mixture obtained in the step, and a step obtained in the step The calcined product is molded and sintered to
And Zn as main components, and has the general formula In 2 O 3 (ZnO)
A compound obtained by doping a hexagonal layered compound represented by m (m = 2 to 20) with at least one element having a valence of at least positive trivalence at 20 atom% or less based on the total amount of all cationic elements. A method for producing a target, which comprises a step of obtaining a sintered body of an oxide containing the same, also achieves the above object (hereinafter, this method is referred to as method II).
【０００８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００９】まず、本発明のターゲットＩは、上述した
ようにＩｎとＺｎを主成分とし、一般式Ｉｎ2 Ｏ3 （Ｚ
ｎＯ）m （ｍ＝２〜２０）で表される六方晶層状化合物
を含む酸化物の焼結体からなるものである。First, the target I of the present invention contains In and Zn as the main components as described above, and has the general formula In 2 O 3 (Z
nO) m (m = 2 to 20), which is a sintered body of an oxide containing a hexagonal layered compound.
【００１０】ここに、「六方晶層状化合物を含む酸化物
の焼結体」とは、Ｘ線回折測定で、六方晶層状化合物に
帰属されるＸ線回折パターンを示す物質からなる酸化物
の焼結体または六方晶層状化合物に帰属されるＸ線回折
パターンを示す物質とともに、他の構造に帰属されるＸ
線回折パターンを示す物質、非晶質物質を含む酸化物の
焼結体を意味する。As used herein, the term "sintered body of oxide containing a hexagonal layered compound" means an oxide composed of a substance showing an X-ray diffraction pattern assigned to the hexagonal layered compound by X-ray diffraction measurement. X, which is assigned to another structure, together with a substance showing an X-ray diffraction pattern, which is assigned to a compound or a hexagonal layered compound
It means a sintered body of an oxide including a substance showing a line diffraction pattern and an amorphous substance.
【００１１】より具体的には、この焼結体は、六方晶層
状化合物を５重量％以上、より好ましくは１０重量％以
上含み、その好ましい例としして以下のものが挙げられ
る。 (a)．Ｉｎ2 Ｏ3 （ＺｎＯ）m （ｍ＝２〜２０）の六方
晶層状化合物、 (b)．Ｉｎ2 Ｏ3 （ＺｎＯ）m （ｍ＝２〜２０）の六方
晶層状化合物とＩｎ2 Ｏ3 との混合物、 (c)．Ｉｎ2 Ｏ3 （ＺｎＯ）m （ｍ＝２〜２０）の六方
晶層状化合物とＺｎＯとの混合物、 ここで (b)，(c) 中のＩｎ2 Ｏ3 ，ＺｎＯは、特定の結
晶構造を有していても非晶質であってもよい。More specifically, this sintered body contains the hexagonal layered compound in an amount of 5% by weight or more, more preferably 10% by weight or more, and preferable examples thereof include the following. (a). A hexagonal layered compound of In 2 O 3 (ZnO) m (m = 2 to 20), (b). A mixture of a hexagonal layered compound of In 2 O 3 (ZnO) m (m = 2 to 20) and In 2 O 3 , (c). A mixture of a hexagonal layered compound of In 2 O 3 (ZnO) m (m = 2 to 20) and ZnO, wherein In 2 O 3 and ZnO in (b) and (c) have a specific crystal structure. It may have or be amorphous.
【００１２】本発明のターゲットＩにおいて、ＩｎとＺ
ｎの原子比（Ｉｎ／（Ｉｎ＋Ｚｎ）は０．２〜０．８５
であるのが好ましく、より好ましくは、０．４５〜０．
８５、特に好ましくは０．５５〜０．８５である。その
理由は、０．２未満ではターゲットから得られる透明導
電膜の導電性が低くなり、０．８５を超えると透明導電
膜の耐湿熱性が低下するからである。In the target I of the present invention, In and Z
The atomic ratio of n (In / (In + Zn) is 0.2 to 0.85.
Is preferable, and more preferably 0.45 to 0.
85, particularly preferably 0.55 to 0.85. The reason is that if it is less than 0.2, the conductivity of the transparent conductive film obtained from the target will be low, and if it exceeds 0.85, the wet heat resistance of the transparent conductive film will be reduced.
【００１３】上記のＩｎとＺｎの原子比は焼結前のイン
ジウム化合物と亜鉛化合物の混合比を調整することによ
り得られ、焼結前の混合比により、化学的量論比率に見
合うインジウム酸化物と亜鉛酸化物からなる六方晶層状
化合物が生成し、残りのインジウム酸化物と亜鉛酸化物
が結晶性物質又は非晶質物質等として存在するものと推
定される。The above atomic ratio of In and Zn is obtained by adjusting the mixing ratio of the indium compound and the zinc compound before sintering, and the indium oxide that is in proportion to the stoichiometric ratio is obtained by the mixing ratio before sintering. It is presumed that a hexagonal layered compound composed of zinc oxide and zinc oxide is produced, and the remaining indium oxide and zinc oxide are present as a crystalline substance or an amorphous substance.
【００１４】また本発明のターゲットＩを構成する焼結
体の相対密度は７０％以上であることが好ましく、より
好ましい相対密度は８５％以上であり、更に好ましくは
９０％以上である。焼結体の密度が７０％未満である場
合、成膜速度が遅くなり、又ターゲットおよびそれから
得られる膜が黒化しやすくなる。密度の高い焼結体を得
るためには、ＣＩＰ（冷間静水圧）等で成型後、ＨＩＰ
（熱間静水圧）等により焼結することが好ましい。The relative density of the sintered body constituting the target I of the present invention is preferably 70% or more, more preferably 85% or more, further preferably 90% or more. When the density of the sintered body is less than 70%, the film formation rate becomes slow, and the target and the film obtained therefrom are easily blackened. In order to obtain a sintered body with a high density, after molding with CIP (cold isostatic pressure) etc., HIP
It is preferable to sinter by (hot isostatic pressure) or the like.
【００１５】本発明のターゲットＩは、上述したように
上記インジウム・亜鉛酸化物の焼結体からなり、この焼
結体からなるターゲットＩは導電性および耐湿性に優
れ、液晶表示素子用透明導電膜、ＥＬ表示素子用透明導
電膜、太陽電池用透明導電膜等、種々の用途の透明導電
膜をスパッタリング法により得るためのターゲットとし
て好適である。このターゲットを用いた場合には、ＩＴ
Ｏ膜よりも耐湿性に優れるとともにＩＴＯ膜と同等の導
電性および光透過率を有する透明導電膜を得ることがで
きる。As described above, the target I of the present invention is made of the above-mentioned sintered body of indium-zinc oxide. The target I made of this sintered body is excellent in conductivity and moisture resistance, and is transparent conductive for liquid crystal display devices. It is suitable as a target for obtaining a transparent conductive film for various uses such as a film, a transparent conductive film for an EL display element, a transparent conductive film for a solar cell, etc. by a sputtering method. When using this target, IT
It is possible to obtain a transparent conductive film which is superior in moisture resistance to the O film and has the same conductivity and light transmittance as the ITO film.
【００１６】ターゲットＩは種々の方法により製造する
ことが可能であるが、後述する本発明の方法Ｉにより製
造することが好ましい。Although the target I can be manufactured by various methods, it is preferably manufactured by the method I of the present invention described later.
【００１７】次に、本発明のターゲットIIについて説明
する。Next, the target II of the present invention will be described.
【００１８】このターゲットIIは、前記六方晶層状化合
物が、正三価以上の原子価を有する元素（例えばＳｎ，
Ａｌ，Ｓｂ，Ｇａ、Ｇｅ）の少なくとも１種（以下、ド
ープ元素ということがある）を全カチオン元素の合量に
対して２０原子％以下でドープしたものである。ここ
で、インジウム・亜鉛酸化物の組成、密度等について
は、ターゲットＩと同様であるので、その説明は省略す
る。また、本発明のターゲットIIにおいて、ドープ元素
（Ｓｎ，Ａｌ，Ｓｂ，Ｇａ，Ｇｅ等）の割合を２０原子
％以下に限定する理由は、２０原子％を超えてドープさ
せるとこのターゲットから得られる透明導電膜において
イオンの散乱が起こり、導電性が低下し過ぎるからであ
る。このターゲットIIは、正三価以上の原子価を有する
元素をドープしているため、前述したターゲットＩから
得られた透明導電膜よりも導電性に優れた透明導電膜を
与える。In this target II, the hexagonal layered compound is an element (for example, Sn,
At least one (Al, Sb, Ga, Ge) (hereinafter sometimes referred to as a doping element) is doped at 20 atomic% or less with respect to the total amount of all cation elements. Here, the composition, density, and the like of indium / zinc oxide are the same as those of the target I, so description thereof will be omitted. Further, in the target II of the present invention, the reason for limiting the ratio of the doping elements (Sn, Al, Sb, Ga, Ge, etc.) to 20 atomic% or less is that the target is obtained when the doping exceeds 20 atomic%. This is because ions are scattered in the transparent conductive film and the conductivity is lowered too much. Since this target II is doped with an element having a valence of positive trivalence or more, it gives a transparent conductive film having higher conductivity than the transparent conductive film obtained from the target I described above.
【００１９】本発明のターゲットIIは、ターゲットＩと
同様に、液晶表示素子用透明導電膜、ＥＬ表示素子用透
明導電膜、太陽電池用透明導電膜等、種々の用途の透明
導電膜をスパッタリング法により得るためのターゲット
として好適である。このターゲットを用いた場合にも、
ＩＴＯ膜よりも耐湿性に優れるとともにＩＴＯ膜と同等
の導電性および光透過率を有する透明導電膜を得ること
ができる。The target II of the present invention is, like the target I, a transparent conductive film for various purposes such as a transparent conductive film for liquid crystal display devices, a transparent conductive film for EL display devices, a transparent conductive film for solar cells, etc. It is suitable as a target for obtaining When using this target,
It is possible to obtain a transparent conductive film which is superior in moisture resistance to the ITO film and has the same conductivity and light transmittance as the ITO film.
【００２０】ターゲットIIも種々の方法により製造する
ことが可能であるが、後述する本発明の方法IIにより製
造することが好ましい。The target II can also be produced by various methods, but it is preferably produced by the method II of the present invention described later.
【００２１】次に、本発明の方法Ｉおよび方法IIについ
て説明する。Next, the method I and the method II of the present invention will be described.
【００２２】まず本発明の方法Ｉは、前述したようにイ
ンジウム化合物と亜鉛化合物とを混合する工程と、前記
工程で得られた混合物を仮焼する工程と、前記工程で得
られた仮焼物を成型し焼結して、ＩｎとＺｎを主成分と
し、一般式Ｉｎ2 Ｏ3 （ＺｎＯ）m （ｍ＝２〜２０）で
表される六方晶層状化合物を含む酸化物の焼結体を得る
工程とを含むことを特徴とする。First, in the method I of the present invention, as described above, the step of mixing the indium compound and the zinc compound, the step of calcining the mixture obtained in the above step, and the step of calcining the calcined material obtained in the above step Formed and sintered to obtain a sintered body of an oxide containing In and Zn as main components and containing a hexagonal layered compound represented by the general formula In 2 O 3 (ZnO) m (m = 2 to 20). And a process.
【００２３】方法Ｉで用いるインジウム化合物および亜
鉛化合物は酸化物または焼成後に酸化物になるもの（酸
化物前駆体）であればよい。インジウム酸化物前駆体、
亜鉛酸化物前駆体としては、インジウム、亜鉛のそれぞ
れの硫化物、硫酸塩、硝酸塩、ハロゲン化物（塩化物、
臭化物等）、炭酸塩、有機酸塩（酢酸塩、プロピオン酸
塩、ナフテン酸塩等）、アルコキシド（メトキシド、エ
トキシド等）、有機金属錯体（アセチルアセトナート
等）等が挙げられる。The indium compound and zinc compound used in Method I may be oxides or those that become oxides after firing (oxide precursors). Indium oxide precursor,
As the zinc oxide precursor, indium and zinc sulfides, sulfates, nitrates, halides (chlorides,
Bromide, etc.), carbonate, organic acid salt (acetate, propionate, naphthenate, etc.), alkoxide (methoxide, ethoxide, etc.), organic metal complex (acetylacetonate, etc.) and the like.
【００２４】低温で完全に熱分解し、不純物が残存しな
いようにするためには、この中でも、硝酸塩、有機酸
塩、アルコキシド、有機金属錯体を用いるのが好まし
い。Of these, nitrates, organic acid salts, alkoxides, and organic metal complexes are preferably used in order to completely decompose them at low temperature and prevent impurities from remaining.
【００２５】本発明の方法Ｉにおいては、上記のインジ
ウム化合物と亜鉛化合物と混合して混合物を得る工程を
先ず行なうが、この工程は、下記(i) 溶液法（共沈法）
または(ii)物理混合法により実施するのが好ましい。In the method I of the present invention, the step of mixing the above-mentioned indium compound and zinc compound to obtain a mixture is first carried out. This step is the following (i) solution method (coprecipitation method).
Alternatively, (ii) the physical mixing method is preferable.
【００２６】(i) 溶液法（共沈法） この方法は、インジウム化合物と亜鉛化合物を溶解した
溶液、もしくは少なくともインジウム化合物を溶解した
溶液と少なくとも亜鉛化合物を溶解した溶液、および沈
澱形成剤を溶解した溶液をそれぞれ調製する。そして別
に用意した容器（必要により溶媒を入れておいてもよ
い）に必要により撹拌しながら前述の溶液を同時にある
いは順次添加混合してインジウム化合物と亜鉛化合物の
共沈物を形成させるものである。(I) Solution method (coprecipitation method) In this method, a solution in which an indium compound and a zinc compound are dissolved, or a solution in which at least an indium compound is dissolved and at least a zinc compound are dissolved, and a precipitation forming agent is dissolved. Each of the prepared solutions is prepared. Then, the above solution is simultaneously or sequentially added to and mixed with a separately prepared container (may contain a solvent if necessary) to form a coprecipitate of an indium compound and a zinc compound.
【００２７】またインジウム化合物と亜鉛化合物を溶解
した溶液に沈澱形成剤を溶解した溶液を添加してもよい
し、またその逆であってもよい。The solution in which the precipitation forming agent is dissolved may be added to the solution in which the indium compound and the zinc compound are dissolved, or vice versa.
【００２８】インジウム化合物と亜鉛化合物を溶解した
溶液と沈澱形成剤を溶解した溶液をそれぞれ調製し、別
に溶媒を入れた容器に撹拌しながら両者の溶液を同時に
添加混合して沈澱を形成する場合を例として以下詳細に
説明する。In the case where a solution in which an indium compound and a zinc compound are dissolved and a solution in which a precipitation forming agent is dissolved are prepared, and both solutions are simultaneously added and mixed while stirring in a container containing a solvent to form a precipitate. This will be described in detail below as an example.
【００２９】まず、上記インジウム化合物と亜鉛化合物
を適当な溶媒に溶解させた溶液（以下溶液Ａという）を
準備する。溶媒は、用いるインジウム化合物または亜鉛
化合物の溶解性に応じて適宜選択すればよく、例えば、
水、アルコール、非プロトン性極性溶媒（ＤＭＳＯ、Ｎ
ＭＰ、スルホラン、ＴＨＦ等）を用いることができ、生
成する沈澱の溶解度が低いことから、特に炭素数１〜５
のアルコール（メタノール、エタノール、イソプロパノ
ール、メトキシエタノール、エチレングリコール等）が
好ましい。溶液Ａ中の各金属の濃度は０．０１〜１０ｍ
ｏｌ／リットルが好ましい。その理由は０．０１ｍｏｌ
／リットル未満では生産性が劣り、１０ｍｏｌ／リット
ルを超えると不均一な沈澱が生成するからである。First, a solution (hereinafter referred to as solution A) in which the above indium compound and zinc compound are dissolved in a suitable solvent is prepared. The solvent may be appropriately selected depending on the solubility of the indium compound or zinc compound used, and for example,
Water, alcohol, aprotic polar solvent (DMSO, N
MP, sulfolane, THF, etc.) can be used, and the solubility of the resulting precipitate is low.
Alcohols (methanol, ethanol, isopropanol, methoxyethanol, ethylene glycol, etc.) are preferable. The concentration of each metal in the solution A is 0.01 to 10 m
ol / liter is preferred. The reason is 0.01 mol
This is because if it is less than 1 liter / liter, the productivity is poor, and if it exceeds 10 mol / liter, a non-uniform precipitate is formed.
【００３０】さらに、原料の溶解を促進するため、各種
溶媒により適宜、酸（硝酸、塩酸等）やアセチルアセト
ン類、多価アルコール（エチレングリコール等）、エタ
ノールアミン類（モノエタノールアミン、ジエタノール
アミン等）を溶液中の金属量の０．０１〜１０倍程度添
加してもよい。Further, in order to accelerate the dissolution of the raw materials, an acid (nitric acid, hydrochloric acid, etc.), acetylacetone, polyhydric alcohol (ethylene glycol, etc.), ethanolamines (monoethanolamine, diethanolamine, etc.) are appropriately added with various solvents. You may add about 0.01-10 times the metal amount in a solution.
【００３１】上記溶液Ａとともに、沈澱形成剤を溶解さ
せた溶液（以下、溶液Ｂという）を準備する。溶液Ｂに
溶解させる沈澱形成剤としては、アルカリ（水酸化ナト
リウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウ
ム、重炭酸ナトリウム、重炭酸カリウム、水酸化アンモ
ニウム、炭酸アンモニウム、重炭酸アンモニウム等）、
有機酸（ギ酸、蓚酸、クエン酸等）等を用いることがで
きる。沈澱は、沈澱形成剤により水酸化物、無機酸塩、
有機酸塩となる。A solution (hereinafter referred to as a solution B) in which a precipitation forming agent is dissolved is prepared together with the above solution A. As the precipitation forming agent to be dissolved in the solution B, alkali (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, etc.),
Organic acids (formic acid, oxalic acid, citric acid, etc.) can be used. Precipitation can be carried out by using a precipitation-forming agent, such as hydroxide, inorganic acid salt,
It becomes an organic acid salt.
【００３２】また、沈澱形成剤を溶解するための溶媒お
よび沈澱を形成させる容器に入れる溶媒としては、イン
ジウム化合物、亜鉛化合物を溶解するために用いる前述
の溶媒を用いることができる。As the solvent for dissolving the precipitation forming agent and the solvent placed in the container for forming the precipitate, the above-mentioned solvents used for dissolving the indium compound and the zinc compound can be used.
【００３３】また、各種溶液に用いる溶媒は、操作上同
じものを用いた方がよいが、異なる溶媒を用いてもよ
い。The solvents used for the various solutions should be the same in operation, but different solvents may be used.
【００３４】方法Ｉにおいては上述のいずれかの手段で
沈澱を形成させるが、沈澱形成時の温度は、溶媒の融点
以上沸点以下であればよい。また、沈澱形成後に１〜５
０時間沈澱を熟成させてもよい。In Method I, the precipitate is formed by any of the above means, and the temperature at the time of forming the precipitate may be from the melting point of the solvent to the boiling point thereof. In addition, 1 to 5 after the precipitate is formed
The precipitate may be aged for 0 hours.
【００３５】このようにして得られた沈澱物を次に固液
分離、乾燥する。沈澱物の固液分離は、遠心分離、濾過
等の常法により行われる。固液分離後、沈澱物から陰イ
オンやアルカリ金属イオン等を除去する目的で、溶液
Ａ、Ｂに用いた溶媒またはその他の溶媒で沈澱物を十分
に洗浄することが望ましい。固液分離後の乾燥は、４０
〜２００℃で０．１〜１００時間行うのが好ましい。４
０℃未満では、乾燥に時間がかかり過ぎ、２００℃以上
では粒子の凝集が起きやすくなる。The precipitate thus obtained is then solid-liquid separated and dried. Solid-liquid separation of the precipitate is performed by a conventional method such as centrifugation or filtration. After solid-liquid separation, it is desirable to thoroughly wash the precipitate with the solvent used for the solutions A and B or another solvent for the purpose of removing anions, alkali metal ions and the like from the precipitate. Drying after solid-liquid separation is 40
It is preferable to carry out the treatment at ˜200 ° C. for 0.1 to 100 hours. Four
If the temperature is lower than 0 ° C., it takes too long to dry, and if the temperature is 200 ° C. or higher, aggregation of particles easily occurs.
【００３６】(ii) 物理混合法 この方法は、上記のインジウム化合物が酸化インジウム
またはその前駆体（水溶性、難溶性を問わない）であ
り、上記の亜鉛化合物が酸化亜鉛またはその前駆体（水
溶性、難溶性を問わない）である場合のいずれにも行な
うことができる方法であり、インジウム化合物と亜鉛化
合物をボールミル、ジェットミル、パールミルなどの混
合器に入れ、両化合物を均一に混ぜ合わせるものであ
る。混合時間は１〜２００時間とするのが好ましい。１
時間未満では均一化が不十分となりやすく、２００時間
を超えると生産性が低下するからである。特に好ましい
混合時間は１０〜１２０時間である。(Ii) Physical mixing method In this method, the indium compound is indium oxide or its precursor (whether water soluble or sparingly soluble), and the zinc compound is zinc oxide or its precursor (water soluble). It can be applied to any of the compounds, regardless of its solubility or poor solubility), in which the indium compound and the zinc compound are put into a mixer such as a ball mill, jet mill, or pearl mill, and both compounds are uniformly mixed. Is. The mixing time is preferably 1 to 200 hours. 1
This is because if it is less than the time, the homogenization tends to be insufficient, and if it exceeds 200 hours, the productivity is lowered. A particularly preferable mixing time is 10 to 120 hours.
【００３７】本発明の方法Ｉでは、上述のインジウム化
合物と亜鉛化合物の混合物を得る工程の後、この混合物
を仮焼する工程を行う。In the method I of the present invention, after the step of obtaining the above-mentioned mixture of the indium compound and the zinc compound, the step of calcining this mixture is performed.
【００３８】インジウム化合物と亜鉛化合物との混合物
の仮焼工程は、温度と時間との兼ね合いで種々異なって
くるが、５００〜１２００℃で１〜１００時間行うこと
が好ましい。５００℃未満または１時間未満ではインジ
ウム化合物と亜鉛化合物の熱分解が不十分であり、１２
００℃を超えた場合または１００時間を超えた場合には
粒子が焼結して粒子の粗大化が起こる。特に好ましい焼
成温度および焼成時間は、８００〜１２００℃で２〜５
０時間である。The calcination step of the mixture of the indium compound and the zinc compound varies depending on the balance between temperature and time, but it is preferably performed at 500 to 1200 ° C. for 1 to 100 hours. If the temperature is less than 500 ° C or less than 1 hour, the thermal decomposition of the indium compound and the zinc compound is insufficient.
If the temperature exceeds 00 ° C or exceeds 100 hours, the particles are sintered and the particles become coarse. Particularly preferable firing temperature and firing time are 2 to 5 at 800 to 1200 ° C.
It's 0 hours.
【００３９】本発明の方法Ｉでは、上述のようにして仮
焼した後、得られた仮焼物の粉砕を行なった方が好まし
く、また必要に応じて、粉砕前後に還元処理を行っても
よい。In the method I of the present invention, it is preferable that the calcined product obtained is calcined as described above, and then the calcinated product is crushed. If necessary, a reduction treatment may be performed before and after crushing. .
【００４０】仮焼物の粉砕は、ボールミル、ロールミ
ル、パールミル、ジェットミル等を用いて、粒子径が
０．０１〜１．０μｍになるように行うことが好まし
い。粒子径が０．０１μｍ未満では粉末が凝集しやす
く、ハンドリングが悪くなる上、緻密な焼結体が得にく
い。一方１．０μｍを超えると緻密な焼結体が得にく
い。なお仮焼と粉砕を繰り返し行なった方が組成の均一
な焼結体が得られる。The calcination product is preferably pulverized by using a ball mill, a roll mill, a pearl mill, a jet mill or the like so that the particle diameter becomes 0.01 to 1.0 μm. If the particle size is less than 0.01 μm, the powder tends to agglomerate, resulting in poor handling, and it is difficult to obtain a dense sintered body. On the other hand, if it exceeds 1.0 μm, it is difficult to obtain a dense sintered body. Note that a sintered body having a uniform composition can be obtained by repeating calcination and pulverization.
【００４１】また還元処理を行う場合の還元方法として
は還元性ガスによる還元、真空焼成又は不活性ガスによ
る還元等を適用することができる。還元性ガスによる還
元を行う場合、還元性ガスとしては水素、メタン、ＣＯ
等や、これらのガスと酸素との混合ガス等を用いること
ができる。又、不活性ガス中での焼成による還元の場
合、不活性ガスとしては、窒素、アルゴン等や、これら
ガスと酸素との混合ガス等を用いることができる。還元
温度は１００〜８００℃が好ましい。１００℃未満では
十分な還元を行うことが困難である。一方、８００℃を
超えると酸化亜鉛の蒸発が生じて組成が変化する。特に
好ましい還元温度は２００〜８００℃である。還元時間
は、還元温度にもよるが、０．０１〜１０時間が好まし
い。０．０１時間未満では十分な還元を行うことが困難
である。一方、１０時間を超えると経済性に乏しくな
る。特に好ましい還元時間は０．０５〜５時間である。As a reducing method for carrying out the reducing treatment, reduction with a reducing gas, vacuum firing, reduction with an inert gas, or the like can be applied. When reducing with a reducing gas, the reducing gas is hydrogen, methane, CO
Etc., or a mixed gas of these gases and oxygen can be used. Further, in the case of reduction by firing in an inert gas, nitrogen, argon, etc., a mixed gas of these gases and oxygen, etc. can be used as the inert gas. The reduction temperature is preferably 100 to 800 ° C. If it is less than 100 ° C, it is difficult to perform sufficient reduction. On the other hand, when the temperature exceeds 800 ° C., zinc oxide is evaporated and the composition changes. A particularly preferable reduction temperature is 200 to 800 ° C. The reduction time depends on the reduction temperature, but is preferably 0.01 to 10 hours. If it is less than 0.01 hours, it is difficult to perform sufficient reduction. On the other hand, if it exceeds 10 hours, the economy becomes poor. Particularly preferable reduction time is 0.05 to 5 hours.
【００４２】本発明の方法Ｉにおいては、前工程で得ら
れた仮焼物を成型し焼結する工程を次に行なう。In the method I of the present invention, the step of molding and sintering the calcined product obtained in the previous step is performed next.
【００４３】仮焼粉末の成型は、金型成型、鋳込み成
型、射出成型等により行なわれるが、焼結密度の高い焼
結体を得るためには、ＣＩＰ（冷間静水圧）等で成型
し、後記する焼結処理に付するのが好ましい。成型体の
形状は、ターゲットとして好適な各種形状とすることが
できる。また成型するにあたっては、ＰＶＡ（ポリビニ
ルアルコール）、ＭＣ（メチルセルロース）、ポリワッ
クス、オレイン酸等の成型助剤を用いてもよい。The calcined powder is molded by die molding, casting molding, injection molding or the like. In order to obtain a sintered body having a high sintering density, it is molded by CIP (cold isostatic pressure) or the like. It is preferable to apply the sintering treatment described later. The shape of the molded body can be various shapes suitable as a target. When molding, a molding aid such as PVA (polyvinyl alcohol), MC (methyl cellulose), polywax, or oleic acid may be used.
【００４４】成型後の焼結は、常圧焼成、ＨＩＰ（熱間
静水圧）焼成等により行なわれる。焼結温度は、インジ
ウム化合物と亜鉛化合物が熱分解し、酸化物となる温度
以上であればよく、通常８００〜１７００℃が好まし
い。１７００℃を超えると酸化亜鉛および酸化インジウ
ムが昇華し組成のずれを生じるので好ましくない。特に
好ましい焼結温度は１２００〜１７００℃である。焼結
時間は焼結温度にもよるが、１〜５０時間、特に２〜１
０時間が好ましい。Sintering after molding is performed by normal pressure firing, HIP (hot isostatic pressure) firing, or the like. The sintering temperature may be at least a temperature at which an indium compound and a zinc compound are thermally decomposed to form an oxide, and usually 800 to 1700 ° C is preferable. If it exceeds 1700 ° C., zinc oxide and indium oxide are sublimated to cause compositional shift, which is not preferable. A particularly preferable sintering temperature is 1200 to 1700 ° C. Although the sintering time depends on the sintering temperature, it is 1 to 50 hours, especially 2-1.
0 hours is preferred.
【００４５】焼結は還元雰囲気で行なってもよく、還元
雰囲気としては、Ｈ2 、メタン、ＣＯなどの還元性ガ
ス、Ａｒ、Ｎ2 などの不活性ガスの雰囲気が挙げられ
る。なお、この場合酸化亜鉛、酸化インジウムが蒸発し
やすいので、ＨＩＰ焼結等により加圧焼結することが望
ましい。Sintering may be carried out in a reducing atmosphere, and examples of the reducing atmosphere include reducing gases such as H 2 , methane and CO, and inert gases such as Ar and N 2 . In this case, since zinc oxide and indium oxide are easily evaporated, it is desirable to perform pressure sintering such as HIP sintering.
【００４６】このようにして焼結を行なうことにより、
ＩｎとＺｎを主成分とし、一般式Ｉｎ2 Ｏ3 （ＺｎＯ）
m （ｍ＝２〜２０）で表される六方晶層状化合物を含む
酸化物の焼結体からなる、目的とするターゲットＩを得
ることができる。By carrying out the sintering in this way,
The main component is In and Zn, and the general formula is In 2 O 3 (ZnO).
The target I can be obtained, which is composed of a sintered body of an oxide containing a hexagonal layered compound represented by m (m = 2 to 20).
【００４７】次に、本発明の方法IIについて説明する。Next, the method II of the present invention will be described.
【００４８】方法IIはターゲットIIを得るための方法と
して好適である。この方法IIは前述したように、インジ
ウム化合物と亜鉛化合物に、正三価以上の原子価を有す
る元素の化合物（例えば錫化合物，アルミニウム化合
物，アンチモン化合物，ガリウム化合物およびゲルマニ
ウム化合物）の少なくとも１種を加えて混合させて混合
物を得る点でのみ上記方法Ｉと異なり、他は上記方法Ｉ
と同様に行うものである。 方法IIにおいて用いられる
錫化合物としては酸化錫または焼成後に酸化錫になる酸
化錫前駆体、例えば酢酸錫、しゅう酸錫、２−エチルヘ
キシル錫、ジメトキシ錫、ジエトキシ錫、ジプロポキシ
錫、ジブトキシ錫、テトラメトキシ錫、テトラエトキシ
錫、テトラプロポキシ錫、テトラブトキシ錫などの錫ア
ルコキシド、塩化錫、フッ化錫、硝酸錫、硫酸錫等が挙
げられる。Method II is suitable as a method for obtaining Target II. In this method II, as described above, at least one compound of an element having a valence of positive trivalence or more (for example, a tin compound, an aluminum compound, an antimony compound, a gallium compound and a germanium compound) is added to an indium compound and a zinc compound. Except that the above method I is different from the above method I only in that the mixture is mixed to obtain a mixture.
The same is done as. The tin compound used in Method II is tin oxide or a tin oxide precursor which becomes tin oxide after firing, such as tin acetate, tin oxalate, 2-ethylhexyl tin, dimethoxy tin, diethoxy tin, dipropoxy tin, dibutoxy tin, tetramethoxy. Examples thereof include tin alkoxides such as tin, tetraethoxytin, tetrapropoxytin and tetrabutoxytin, tin chloride, tin fluoride, tin nitrate, tin sulfate and the like.
【００４９】また、アルミニウム化合物としては酸化ア
ルミニウムまたはその前駆体、例えば塩化アルミニウ
ム、トリメトキシアルミニウム、トリエトキシアルミニ
ウム、トリプロポキシアルミニウム、トリブトキシアル
ミニウムなどのアルミニウムアルコキシド、硫酸アルミ
ニウム、硝酸アルミニウム、しゅう酸アルミニウム等が
挙げられる。As the aluminum compound, aluminum oxide or its precursor, for example, aluminum alkoxide such as aluminum chloride, trimethoxy aluminum, triethoxy aluminum, tripropoxy aluminum, tributoxy aluminum, aluminum sulfate, aluminum nitrate, aluminum oxalate, etc. Is mentioned.
【００５０】アンチモン化合物としては酸化アンチモン
またはその前駆体、例えば塩化アンチモン、フッ化アン
チモン、トリメトキシアンチモン、トリエトキシアンチ
モン、トリプロポキシアンチモン、トリブトキシアンチ
モンなどのアンチモンアルコキシド、硫酸アンチモン、
水酸化アンチモン等があげられる。As the antimony compound, antimony oxide or a precursor thereof, for example, antimony alkoxide such as antimony chloride, antimony fluoride, trimethoxyantimony, triethoxyantimony, tripropoxyantimony, tributoxyantimony, antimony sulfate, and the like,
Examples thereof include antimony hydroxide.
【００５１】ガリウム化合物としては酸化ガリウムまた
はその前駆体、例えば塩化ガリウム、トリメトキシガリ
ウム、トリエトキシガリウム、トリプロポキシガリウ
ム、トリブトキシガリウムなどのガリウムアルコキシ
ド、硝酸ガリウム等が挙げられる。 そして、ゲルマニ
ウム化合物としては酸化ゲルマニウムまたはその前駆
体、例えば塩化ゲルマニウム、テトラメトキシゲルマニ
ウム、テトラエトキシゲルマニウム、テトラプロポキシ
ゲルマニウム、テトラブトキシゲルマニウムなどのゲル
マニウムアルコキシド等が挙げられる。Examples of the gallium compound include gallium oxide or a precursor thereof, for example, gallium alkoxides such as gallium chloride, trimethoxygallium, triethoxygallium, tripropoxygallium and tributoxygallium, gallium nitrate and the like. Examples of the germanium compound include germanium oxide or its precursor, for example, germanium alkoxide such as germanium chloride, tetramethoxygermanium, tetraethoxygermanium, tetrapropoxygermanium, and tetrabutoxygermanium.
【００５２】ドーピング原料である正三価以上の原子価
を有する元素の化合物、すなわち錫、アルミニウム、ア
ンチモン、ガリウム、ゲルマニウムの化合物の添加量
は、最終的に得られるターゲットにおけるドープ元素
（Ｓｎ，Ａｌ，Ｓｂ，Ｇａ，Ｇｅなど）の割合が全カチ
オン元素の合量に対して２０原子％以下となるように、
製造過程での各成分の蒸散を考慮して適宜設定すること
が好ましい。ドープ元素の割合が最終的に２０原子％を
超えると、イオンの散乱によりターゲット、ひいては透
明導電膜の導電性が低下する。The doping amount of the compound of an element having a valence of positive trivalence or more, that is, the compound of tin, aluminum, antimony, gallium, or germanium, which is a doping raw material, depends on the doping element (Sn, Al, Sb, Ga, Ge, etc.) is 20 atomic% or less based on the total amount of all cationic elements,
It is preferable to appropriately set in consideration of transpiration of each component in the manufacturing process. When the proportion of the doping element finally exceeds 20 atomic%, the conductivity of the target, and by extension, the transparent conductive film, decreases due to the scattering of ions.
【００５３】本発明の方法IIにより、六方晶層状化合物
が、正三価以上の原子価の元素を所定量ドープしたもの
である、目的とするターゲットIIを得ることができる。By the method II of the present invention, it is possible to obtain the target II which is a hexagonal layered compound doped with a predetermined amount of an element having a valence of at least positive trivalence.
【００５４】[0054]
【実施例】以下、本発明の実施例について説明するが、
実施例で得られた物質の測定方法について説明してお
く。EXAMPLES Examples of the present invention will be described below.
The measuring method of the substances obtained in the examples will be described.
【００５５】体積固体抵抗の測定 体積固体抵抗（一般に「粉体抵抗」と表現されることも
ある）は試料１ｇを内径１０ｍｍの円筒に入れ、１００
ｋｇ／ｃｍ2 の加圧を行い、テスターで抵抗を測定し、
下記の式により求めた。Measurement of Volume Solid Resistance The volume solid resistance (generally referred to as “powder resistance”) is 100% when 1 g of a sample is put into a cylinder having an inner diameter of 10 mm.
Apply a pressure of kg / cm 2 , measure the resistance with a tester,
It was calculated by the following formula.
【００５６】＝［全抵抗（Ω）×シリンダ−の内面積
（cm2 ）］／試料の厚さ（cm）= [Total resistance (Ω) × internal area of cylinder (cm 2 )] / thickness of sample (cm)
【００５７】実施例１ （１）ターゲットＩの製造 まず、硝酸インジウム７０．９７ｇと硝酸亜鉛８９．２
５ｇとを１リットルのイオン交換水に溶解させて、イン
ジウム塩と亜鉛塩とが溶解した水溶液を調製した。ま
た、アンモニア水（濃度２８％）７８ｇを７５０ミリリ
ットルのイオン交換水に溶解させて、アルカリ性水溶液
を調製した。Example 1 (1) Production of Target I First, 70.97 g of indium nitrate and 89.2 of zinc nitrate were prepared.
5 g was dissolved in 1 liter of ion-exchanged water to prepare an aqueous solution in which an indium salt and a zinc salt were dissolved. Further, 78 g of ammonia water (concentration 28%) was dissolved in 750 ml of ion-exchanged water to prepare an alkaline aqueous solution.
【００５８】次いで、イオン交換水１００ｃｃが入った
容積５リットルの容器に、上で得られた水溶液とアルカ
リ性水溶液とを室温下で激しく攪拌しながら同時に滴下
して、両液を反応させた。このとき、反応系のｐＨが
９．０に保たれるように滴下速度を調節した。そして、
滴下終了後も更に１時間攪拌した。このようにして上記
水溶液とアルカリ性水溶液とを反応させることにより沈
澱物が生じ、スラリーが得られた。なお、この反応系に
おける金属（ＩｎおよびＺｎ）の濃度は０．３ mol／リ
ットルであった。Then, the aqueous solution obtained above and the alkaline aqueous solution were simultaneously added dropwise at room temperature to a container having a volume of 5 liters containing 100 cc of ion-exchanged water with vigorous stirring to react the two solutions. At this time, the dropping rate was adjusted so that the pH of the reaction system was maintained at 9.0. And
After the dropping was completed, the mixture was further stirred for 1 hour. By reacting the above aqueous solution with the alkaline aqueous solution in this way, a precipitate was produced and a slurry was obtained. The concentration of metals (In and Zn) in this reaction system was 0.3 mol / liter.
【００５９】次に、得られたスラリーを十分に水洗した
後、沈澱物を濾取した。そして、濾取した沈澱物を１２
０℃で一晩乾燥した後、９００℃で５時間焼成した。Next, the resulting slurry was thoroughly washed with water, and the precipitate was collected by filtration. Then, the precipitate collected by filtration is used for 12
After drying overnight at 0 ° C., it was baked at 900 ° C. for 5 hours.
【００６０】この後、得られた焼成物を直径２ｍｍのア
ルミナボールとともに容積８０ｃｃのポリイミド製ポッ
トに入れ、エタノールを加えて、遊星ボールミルで２時
間粉砕した。Then, the obtained fired product was put together with alumina balls having a diameter of 2 mm in a pot made of polyimide having a volume of 80 cc, ethanol was added, and the mixture was pulverized by a planetary ball mill for 2 hours.
【００６１】このようにして得られた粉末についてＸ線
回折測定を行ったところ、Ｉｎ2 Ｏ3 （ＺｎＯ）3 の六
方晶層状化合物の生成が確認され、その組成は実質的に
均一であった。また、ＳＥＭ（走査型電子顕微鏡）観察
の結果、得られた粉末は平均粒子径が０．１２μｍで、
実質的に均一粒径であることが確認された。When X-ray diffraction measurement was performed on the powder thus obtained, formation of a hexagonal layered compound of In 2 O 3 (ZnO) 3 was confirmed, and its composition was substantially uniform. . As a result of SEM (scanning electron microscope) observation, the obtained powder had an average particle diameter of 0.12 μm,
It was confirmed that the particle size was substantially uniform.
【００６２】また、得られた粉末の体積固体抵抗は９５
０Ωｃｍであった。そして、この体積固体抵抗は、４０
℃、９０％ＲＨの条件での耐湿性試験１０００時間後で
も１０００Ωｃｍと低く、得られた粉末は耐湿性に優れ
ていることが確認された。The volume solid resistance of the obtained powder is 95.
It was 0 Ωcm. And this volume solid resistance is 40
Even after 1000 hours of humidity resistance test under conditions of ° C and 90% RH, it was as low as 1000 Ωcm, and it was confirmed that the obtained powder had excellent humidity resistance.
【００６３】次に、上記（１）で得られた粉末を１０ｍ
ｍφの金型に装入し、金型プレス成型機により１００ｋ
ｇ／ｃｍ2 の圧力で予備成型を行った。次に、冷間静水
圧プレス成型機により４ｔ／ｃｍ2 の圧力で圧密化した
後、１３００℃で５時間焼結して、焼結体を得た。Next, the powder obtained in the above (1)
Insert into mφ die and press 100k by die press molding machine.
Preforming was performed at a pressure of g / cm 2 . Next, it was consolidated at a pressure of 4 t / cm 2 by a cold isostatic press molding machine and then sintered at 1300 ° C. for 5 hours to obtain a sintered body.
【００６４】このようにして得られた焼結体はＩｎ2 Ｏ
3 （ＺｎＯ）3 の六方晶層状化合物からなるターゲット
Ｉであることが確認され、その組成および粒径は実質的
に均一であった。また、この焼結体の密度は９５％であ
った。The sintered body thus obtained was In 2 O
It was confirmed that the target I was a hexagonal layered compound of 3 (ZnO) 3 , and its composition and particle size were substantially uniform. The density of this sintered body was 95%.
【００６５】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いて、以下の要領で透明導電膜を製造した。(2) Production of transparent conductive film Using the sintered body obtained in (1) above as a sputtering target, a transparent conductive film was produced in the following procedure.
【００６６】まず、基板（厚さ１２５μｍのガラス板）
をマグネトロン高速スパッタ装置に装着し、真空槽内を
１×１０-6ｔｏｒｒ以下まで減圧した。この後、アルゴ
ンガスと酸素ガスとの混合ガスを真空圧２×１０-3ｔｏ
ｒｒまで導入し、ターゲット印加電圧４３０Ｖ、基板温
度２８０℃の条件でスパッタリングを行い、膜厚２００
ｎｍの透明導電膜を成膜した。First, a substrate (a glass plate having a thickness of 125 μm)
Was attached to a magnetron high-speed sputtering apparatus, and the pressure inside the vacuum chamber was reduced to 1 × 10 −6 torr or less. After that, a mixed gas of argon gas and oxygen gas is applied at a vacuum pressure of 2 × 10 −3 to.
rr is introduced, sputtering is performed under the conditions of a target applied voltage of 430 V and a substrate temperature of 280 ° C., and a film thickness of 200
nm transparent conductive film was formed.
【００６７】このようにして得られた透明導電膜の表面
抵抗は１５０Ω／□であり、可視光透過率は８２％であ
った。また、４０℃、９０％ＲＨの条件での耐湿性試験
１０００時間後でも表面抵抗は１５９Ω／□と低く、得
られた透明導電膜は耐湿性に優れていることが確認され
た。The surface resistance of the transparent conductive film thus obtained was 150 Ω / □, and the visible light transmittance was 82%. Further, the surface resistance was as low as 159 Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【００６８】実施例２ （１）ターゲットＩの製造 まず、硝酸インジウム５０．６９ｇと硝酸亜鉛１０６．
２４ｇとを１リットルのイオン交換水に溶解させて、イ
ンジウム塩と亜鉛塩とが溶解した水溶液を調製し、この
水溶液と実施例１（１）と同様にして調製したアルカリ
性水溶液とを実施例１（１）と同様にして反応させて、
スラリーを得た。なお、この反応系における金属（Ｉｎ
およびＺｎ）濃度は０．３ mol／リットルであった。Example 2 (1) Production of Target I First, 50.69 g of indium nitrate and 106.
24 g was dissolved in 1 liter of ion-exchanged water to prepare an aqueous solution in which an indium salt and a zinc salt were dissolved, and this aqueous solution and an alkaline aqueous solution prepared in the same manner as in Example 1 (1) were used. React as in (1),
A slurry was obtained. In addition, the metal (In
And Zn) concentration was 0.3 mol / l.
【００６９】次に、得られたスラリーを十分に水洗した
後、沈澱物を濾取した。そして、濾取した沈澱物を１２
０℃で一晩乾燥した後、９００℃で５時間焼成した。Next, the obtained slurry was thoroughly washed with water, and the precipitate was collected by filtration. Then, the precipitate collected by filtration is used for 12
After drying overnight at 0 ° C., it was baked at 900 ° C. for 5 hours.
【００７０】この後、得られた焼成物を実施例１（１）
と同様にして粉砕して、粉末を得た。 このようにして
得られた粉末についてＸ線回折測定を行ったところ、Ｉ
ｎ2Ｏ3 （ＺｎＯ）5 の六方晶層状化合物の生成が確認
され、その組成は実質的に均一であった。また、ＳＥＭ
観察の結果、得られた粉末は平均粒子径が０．２０μｍ
で、実質的に均一粒径であることが確認された。Thereafter, the obtained fired product was used in Example 1 (1).
It was crushed in the same manner as above to obtain a powder. When X-ray diffraction measurement was performed on the powder thus obtained, I
Formation of a hexagonal layered compound of n 2 O 3 (ZnO) 5 was confirmed, and its composition was substantially uniform. Also, SEM
As a result of observation, the obtained powder has an average particle size of 0.20 μm.
It was confirmed that the particle size was substantially uniform.
【００７１】また、得られた粉末の体積固体抵抗は７０
０Ωｃｍであった。そして、この体積固体抵抗は、４０
℃、９０％ＲＨの条件での耐湿性試験１０００時間後で
も７３０Ωｃｍと低く、得られた粉末は耐湿性に優れて
いることが確認された。The volume solid resistance of the obtained powder is 70.
It was 0 Ωcm. And this volume solid resistance is 40
Even after 1000 hours of humidity resistance test under conditions of ° C and 90% RH, it was as low as 730 Ωcm, and it was confirmed that the obtained powder had excellent humidity resistance.
【００７２】次に、上記（１）で得られた粉末を実施例
１（１）と同様にして予備成型および圧密化した後、１
３５０℃で５時間焼結して、焼結体を得た。Next, the powder obtained in (1) above was preformed and compacted in the same manner as in Example 1 (1), and then 1
It sintered at 350 degreeC for 5 hours, and obtained the sintered compact.
【００７３】このようにして得られた焼結体はＩｎ2 Ｏ
3 （ＺｎＯ）5 の六方晶層状化合物からなるターゲット
Ｉであることが確認され、その組成および粒径は実質的
に均一であった。また、この焼結体の密度は９６％であ
った。The sintered body thus obtained was made of In 2 O 3.
It was confirmed that the target I was a hexagonal layered compound of 3 (ZnO) 5 , and its composition and particle size were substantially uniform. The density of this sintered body was 96%.
【００７４】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例１（２）と同様にして、膜
厚２００ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a film thickness of 200 nm was formed in the same manner as in Example 1 (2) except that the sintered body obtained in (1) above was used as a sputtering target. Filmed
【００７５】このようにして得られた透明導電膜の表面
抵抗は１１０Ω／□であり、可視光透過率は８４．１％
であった。また、４０℃、９０％ＲＨの条件での耐湿性
試験１０００時間後でも表面抵抗は１１８Ω／□と低
く、得られた透明導電膜は耐湿性に優れていることが確
認された。The transparent conductive film thus obtained had a surface resistance of 110 Ω / □ and a visible light transmittance of 84.1%.
Met. Further, the surface resistance was as low as 118Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【００７６】実施例３ （１）ターゲットIIの製造 実施例２（１）と同様にして、インジウムと亜鉛の金属
塩を溶解した水溶液を調製した後、これに更に塩化第二
錫７．２ｇ（５原子％）を添加した。次にこの水溶液
と、実施例１（１）と同様にして調製したアルカリ性水
溶液とを実施例１（１）と同様にして反応させて、スラ
リーを得た。Example 3 (1) Production of Target II In the same manner as in Example 2 (1), an aqueous solution in which a metal salt of indium and zinc was dissolved was prepared, and then 7.2 g of stannic chloride was added thereto ( 5 atomic%) was added. Next, this aqueous solution and an alkaline aqueous solution prepared in the same manner as in Example 1 (1) were reacted in the same manner as in Example 1 (1) to obtain a slurry.
【００７７】次に、得られたスラリーを十分に水洗した
後、沈澱物を濾取した。そして、濾取した沈澱物を１２
０℃で一晩乾燥した後、９００℃で５時間焼成した。Next, the resulting slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is used for 12
After drying overnight at 0 ° C., it was baked at 900 ° C. for 5 hours.
【００７８】この後、得られた焼成物を実施例１（１）
と同様にして粉砕して、粉末を得た。このようにして得
られた粉末のＸ線回折測定の結果、Ｉｎ2 Ｏ3 （Ｚｎ
Ｏ）5の六方晶層状化合物が生成していることが確認さ
れた。粉末の体積固体抵抗は、３３０Ωｃｍであった。
そして、この体積固体抵抗は、４０℃、９０％ＲＨの条
件での耐湿性試験１０００時間後でも３５０Ωｃｍと低
く、得られた粉末は耐湿性に優れていることが確認され
た。Thereafter, the obtained fired product was used in Example 1 (1).
It was crushed in the same manner as above to obtain a powder. As a result of X-ray diffraction measurement of the powder thus obtained, In 2 O 3 (Zn
It was confirmed that a hexagonal layered compound of O) 5 was produced. The volume solid resistance of the powder was 330 Ωcm.
The volume solid resistance was as low as 350 Ωcm even after 1000 hours of the humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained powder had excellent humidity resistance.
【００７９】次に、上記（１）で得られた粉末を実施例
１（１）と同様にして予備成型及び圧密化した後、１３
５０℃で５時間焼結して、焼結体を得た。Next, the powder obtained in (1) above was preformed and consolidated in the same manner as in Example 1 (1), and then 13
It sintered at 50 degreeC for 5 hours, and obtained the sintered compact.
【００８０】このようにして得られた焼結体はＩｎ2 Ｏ
3 （ＺｎＯ）5 の六方晶層状化合物からなるターゲット
IIであることが確認され、その組成及び粒径は実質的に
均一であった。また、この焼結体の密度は９５％であっ
た。The sintered body thus obtained was made of In 2 O 3.
Target composed of hexagonal layered compound of 3 (ZnO) 5
It was confirmed to be II, and its composition and particle size were substantially uniform. The density of this sintered body was 95%.
【００８１】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は、実施例１（２）と同様にして、
膜厚２００ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film The procedure of Example 1 (2) was repeated except that the sintered body obtained in (1) above was used as a sputtering target.
A transparent conductive film having a film thickness of 200 nm was formed.
【００８２】このようにして得られた透明導電膜の表面
抵抗は７０Ω／□であり、可視光透過率は８５．０％で
あった。また、４０℃、９０％ＲＨの条件での耐湿性試
験１０００時間後でも表面抵抗は７５Ω／□と低く、得
られた透明導電膜は耐湿性に優れていることが確認され
た。The transparent conductive film thus obtained had a surface resistance of 70 Ω / □ and a visible light transmittance of 85.0%. Moreover, the surface resistance was low at 75Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【００８３】実施例４ （１）ターゲットＩの製造 酸化インジウム２７８ｇと酸化亜鉛３２６ｇを直径２ｍ
ｍのアルミナボールとともに容積８００ｃｃのポリイミ
ド製のポットに入れ、エタノールを加えて遊星ボールミ
ルで１００時間粉砕混合した。その後１０００℃で５時
間仮焼し、更に遊星ボールミルで２４時間粉砕混合し
た。Example 4 (1) Manufacture of Target I 278 g of indium oxide and 326 g of zinc oxide were used and the diameter was 2 m.
m alumina balls were placed in a polyimide pot having a volume of 800 cc, ethanol was added, and the mixture was pulverized and mixed for 100 hours in a planetary ball mill. Thereafter, the mixture was calcined at 1000 ° C. for 5 hours, and further pulverized and mixed by a planetary ball mill for 24 hours.
【００８４】この粉末を直径４インチの金型に装入し、
１００ｋｇ／ｃｍ2 の圧力で金型プレス成型機にて予備
成型を行なった。その後、冷間静水圧プレス成型機にて
４ｔ／ｃｍ2 の圧力で圧密化し、熱間静水圧プレスにて
１０００ｋｇｆ／ｃｍ2 、１３００℃で３時間焼成し焼
結体を得た。得られた焼結体はＸ線回折測定結果、Ｉｎ
2 Ｏ3 （ＺｎＯ）4 の六方晶層状化合物であることが確
認された。This powder was placed in a mold having a diameter of 4 inches,
Pre-molding was performed with a die press molding machine at a pressure of 100 kg / cm 2 . Then, it was consolidated by a cold isostatic press molding machine at a pressure of 4 t / cm 2 , and fired at 1000 kgf / cm 2 and 1300 ° C. for 3 hours by a hot isostatic press to obtain a sintered body. The obtained sintered body was measured by X-ray diffraction and In
It was confirmed to be a hexagonal layered compound of 2 O 3 (ZnO) 4 .
【００８５】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、セイコー電子工業
社製のＳＰＳ−１５００ＶＲを用いたＩＣＰ分析（誘導
結合プラズマ発光分光分析）の結果０．３３であった。
また、焼結体の相対密度は８８％であった。I in the thus obtained sintered body
The atomic ratio In / (In + Zn) of n was 0.33 as a result of ICP analysis (inductively coupled plasma emission spectroscopic analysis) using SPS-1500VR manufactured by Seiko Instruments Inc.
The relative density of the sintered body was 88%.
【００８６】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いて、以下の要領で透明導電膜を製造した。(2) Production of transparent conductive film Using the sintered body obtained in (1) above as a sputtering target, a transparent conductive film was produced in the following procedure.
【００８７】まず、基板（厚さ１．１ｍｍのガラス板）
をＲＦマグネトロンスパッタ装置に装着し、真空槽内を
５×１０-4Ｐａ以下まで減圧した。この後、アルゴンガ
スを真空圧３×１０-1Ｐａまで導入し、出力１００Ｗ、
基板温度２００℃の条件でスパッタリングを行い、膜厚
２００ｎｍの透明導電膜を成膜した。First, the substrate (1.1 mm thick glass plate)
Was attached to an RF magnetron sputtering device, and the inside of the vacuum chamber was depressurized to 5 × 10 −4 Pa or less. Then, argon gas was introduced up to a vacuum pressure of 3 × 10 −1 Pa, and an output of 100 W,
Sputtering was performed at a substrate temperature of 200 ° C. to form a transparent conductive film having a film thickness of 200 nm.
【００８８】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．４０であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.40.
【００８９】このようにして得られた透明導電膜の表面
抵抗は１２０Ω／□であり、可視光透過率は８３．８％
であった。また、４０℃、９０％ＲＨの条件での耐湿性
試験１０００時間後でも表面抵抗は１２８Ω／□と低
く、得られた透明導電膜は、耐湿性に優れていることが
確認された。The transparent conductive film thus obtained had a surface resistance of 120 Ω / □ and a visible light transmittance of 83.8%.
Met. Further, the surface resistance was as low as 128Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【００９０】実施例５ （１）ターゲットＩの製造 酸化インジウム１７５ｇと酸化亜鉛１００ｇを直径２ｍ
ｍのアルミナボールとともに容積８００ｃｃのポリイミ
ド製のポットに入れ、エタノールを加えて遊星ボールミ
ルで１００時間粉砕混合した。その後１０００℃で５時
間仮焼し、更に遊星ボールミルで２４時間粉砕混合し
た。Example 5 (1) Production of Target I 175 g of indium oxide and 100 g of zinc oxide were used and the diameter was 2 m.
m alumina balls were placed in a polyimide pot having a volume of 800 cc, ethanol was added, and the mixture was pulverized and mixed for 100 hours in a planetary ball mill. Thereafter, the mixture was calcined at 1000 ° C. for 5 hours, and further pulverized and mixed by a planetary ball mill for 24 hours.
【００９１】この粉末を直径４インチの金型に装入し、
１００ｋｇ／ｃｍ2 の圧力で金型プレス成型機にて予備
成型を行なった。その後、冷間静水圧プレス成型機にて
４ｔ／ｃｍ2 の圧力で圧密化し、熱間静水圧プレスにて
１５００ｋｇｆ／ｃｍ2 、１４５０℃で３時間焼成し焼
結体を得た。得られた焼結体はＸ線回折測定結果、Ｉｎ
2 Ｏ3 （ＺｎＯ）5 の六方晶層状化合物とＩｎ2 Ｏ3 と
の混合物であることが確認された。This powder was placed in a mold having a diameter of 4 inches,
Pre-molding was performed with a die press molding machine at a pressure of 100 kg / cm 2 . Then, it was consolidated with a pressure of 4 t / cm 2 by a cold isostatic press molding machine, and fired by a hot isostatic press at 1500 kgf / cm 2 and 1450 ° C. for 3 hours to obtain a sintered body. The obtained sintered body was measured by X-ray diffraction and In
It was confirmed to be a mixture of a hexagonal layered compound of 2 O 3 (ZnO) 5 and In 2 O 3 .
【００９２】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析（誘導
結合プラズマ発光分光分析）の結果０．５０であった。
また、焼結体の相対密度は９３％であった。I in the thus obtained sintered body
The atomic ratio In / (In + Zn) of n was 0.50 as a result of ICP analysis (ICP-AES).
The relative density of the sintered body was 93%.
【００９３】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例４（２）と同様にして、膜
厚２００ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a film thickness of 200 nm was formed in the same manner as in Example 4 (2) except that the sintered body obtained in (1) above was used as a sputtering target. Filmed
【００９４】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．５６であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.56.
【００９５】このようにして得られた透明導電膜の表面
抵抗は２５．４Ω／□であり、可視光透過率は８４．６
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は２６．８Ω／□と
低く、得られた透明導電膜は、耐湿性に優れていること
が確認された。The transparent conductive film thus obtained had a surface resistance of 25.4 Ω / □ and a visible light transmittance of 84.6.
%Met. Further, the surface resistance was as low as 26.8 Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【００９６】実施例６ （１）ターゲットＩの製造 酸化インジウム３００ｇと酸化亜鉛８０ｇを用いた他
は、実施例５（１）と同様に粉砕混合、仮焼、成型、焼
結を行った。得られた焼結体はＸ線回折測定結果、Ｉｎ
2 Ｏ3 （ＺｎＯ）3 の六方晶層状化合物とＩｎ2 Ｏ3 と
の混合物であることが確認された。Example 6 (1) Manufacture of Target I The same procedures as in Example 5 (1) except that 300 g of indium oxide and 80 g of zinc oxide were used were pulverized and mixed, calcined, molded and sintered. The obtained sintered body was measured by X-ray diffraction and In
It was confirmed to be a mixture of a hexagonal layered compound of 2 O 3 (ZnO) 3 and In 2 O 3 .
【００９７】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．６７であった。また、焼結体の相対密度は９２
％であった。I in the thus obtained sintered body
The atomic ratio In / (In + Zn) of n was 0.67 as a result of ICP analysis. The relative density of the sintered body is 92
%Met.
【００９８】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いて、以下の要領で透明導電膜を製造した。(2) Production of transparent conductive film Using the sintered body obtained in (1) above as a sputtering target, a transparent conductive film was produced in the following procedure.
【００９９】まず、透明高分子フィルム（厚さ１２５μ
ｍ、２軸延伸ポリエステルフィルム）をＲＦマグネトロ
ンスパッタ装置に装着し、真空槽内を５×１０-4Ｐａ以
下まで減圧した。この後、アルゴンガス（純度９９．９
９％）と酸素ガス（純度９９．９９％）との混合ガスを
真空圧３×１０-1Ｐａまで導入し、出力１００Ｗ、基板
温度２０℃の条件でスパッタリングを行い、膜厚２００
ｎｍの透明導電膜を透明高分子フィルム上に成膜した。First, a transparent polymer film (thickness 125 μm
m biaxially stretched polyester film) was attached to an RF magnetron sputtering apparatus, and the pressure in the vacuum chamber was reduced to 5 × 10 −4 Pa or less. After this, argon gas (purity 99.9
A mixed gas of 9%) and oxygen gas (purity 99.99%) was introduced up to a vacuum pressure of 3 × 10 −1 Pa, sputtering was performed under the conditions of an output of 100 W and a substrate temperature of 20 ° C., and a film thickness of 200
nm transparent conductive film was formed on the transparent polymer film.
【０１００】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．７０であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.70.
【０１０１】このようにして得られた透明導電膜の表面
抵抗は２１．０Ω／□であり、可視光透過率は８３．５
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は２２．５Ω／□と
低く、得られた透明導電膜は、耐湿性に優れていること
が確認された。The transparent conductive film thus obtained had a surface resistance of 21.0 Ω / □ and a visible light transmittance of 83.5.
%Met. Further, the surface resistance was as low as 22.5 Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１０２】実施例７ （１）ターゲットＩの製造 酸化インジウム２７８ｇと酸化亜鉛５２ｇを用いた他
は、実施例５（１）と同様に粉砕混合、仮焼、成型、焼
結を行った。得られた焼結体はＸ線回折測定結果、Ｉｎ
2 Ｏ3 （ＺｎＯ）3 の六方晶層状化合物とＩｎ2 Ｏ3 と
の混合物であることが確認された。Example 7 (1) Manufacture of Target I In the same manner as in Example 5 (1) except that 278 g of indium oxide and 52 g of zinc oxide were used, pulverization and mixing, calcination, molding and sintering were performed. The obtained sintered body was measured by X-ray diffraction and In
It was confirmed to be a mixture of a hexagonal layered compound of 2 O 3 (ZnO) 3 and In 2 O 3 .
【０１０３】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．７５であった。また、焼結体の相対密度は９６
％であった。I in the sintered body thus obtained
The atomic ratio In / (In + Zn) of n was 0.75 as a result of ICP analysis. The relative density of the sintered body is 96
%Met.
【０１０４】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例６（２）と同様にして膜厚
２００ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a film thickness of 200 nm was formed in the same manner as in Example 6 (2) except that the sintered body obtained in (1) above was used as a sputtering target. did.
【０１０５】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．８１であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.81.
【０１０６】このようにして得られた透明導電膜の表面
抵抗は１９．３Ω／□であり、可視光透過率は８３．４
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は２０．８Ω／□と
低く、得られた透明導電膜は、耐湿性に優れていること
が確認された。The transparent conductive film thus obtained has a surface resistance of 19.3 Ω / □ and a visible light transmittance of 83.4.
%Met. Further, the surface resistance was as low as 20.8 Ω / □ even after 1000 hours of the humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１０７】実施例８ （１）ターゲットＩの製造 酸化インジウム２７８ｇと酸化亜鉛３８ｇを用いた他
は、実施例５（１）と同様に粉砕混合、仮焼、成型、焼
結を行った。得られた焼結体はＸ線回折測定結果、Ｉｎ
2 Ｏ3 （ＺｎＯ）3 の六方晶層状化合物とＩｎ2 Ｏ3 と
の混合物であることが確認された。Example 8 (1) Manufacture of Target I [0107] Grinding and mixing, calcination, molding and sintering were performed in the same manner as in Example 5 (1) except that 278 g of indium oxide and 38 g of zinc oxide were used. The obtained sintered body was measured by X-ray diffraction and In
It was confirmed to be a mixture of a hexagonal layered compound of 2 O 3 (ZnO) 3 and In 2 O 3 .
【０１０８】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．８０であった。また、焼結体の相対密度は９５
％であった。I in the sintered body thus obtained
The atomic ratio In / (In + Zn) of n was 0.80 as a result of ICP analysis. The relative density of the sintered body is 95
%Met.
【０１０９】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用い、透明高分子フィルムとしてポリカーボネ
ートを用いた以外は実施例６（２）と同様にして、膜厚
２００ｎｍの透明導電膜を成膜した。(2) Production of Transparent Conductive Film The procedure of Example 6 (2) was repeated except that the sintered body obtained in (1) above was used as the sputtering target and polycarbonate was used as the transparent polymer film. A transparent conductive film having a film thickness of 200 nm was formed.
【０１１０】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．８５であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.85.
【０１１１】このようにして得られた透明導電膜の表面
抵抗は１９．０Ω／□であり、可視光透過率は８２．４
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は２０．１Ω／□と
低く、得られた透明導電膜は耐湿性に優れていることが
確認された。The transparent conductive film thus obtained had a surface resistance of 19.0 Ω / □ and a visible light transmittance of 82.4.
%Met. Moreover, the surface resistance was as low as 20.1 Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１１２】実施例９ （１）ターゲットＩの製造 酸化インジウム２７８ｇと酸化亜鉛３８ｇを用いた他
は、実施例５（１）と同様に粉砕混合、仮焼、成型を行
い、熱間静水圧プレスにて１０００ｋｇｆ／ｃｍ2 、１
２００℃で３時間焼結を行なった。得られた焼結体はＸ
線回折測定結果、Ｉｎ2 Ｏ3 （ＺｎＯ）5 の六方晶層状
化合物とＩｎ2 Ｏ3 との混合物であることが確認され
た。Example 9 (1) Production of Target I Hot milling was carried out by crushing, mixing, calcining and molding in the same manner as in Example 5 (1) except that 278 g of indium oxide and 38 g of zinc oxide were used. At 1000 kgf / cm 2 , 1
Sintering was performed at 200 ° C. for 3 hours. The obtained sintered body is X
As a result of line diffraction measurement, it was confirmed to be a mixture of a hexagonal layered compound of In 2 O 3 (ZnO) 5 and In 2 O 3 .
【０１１３】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．８０であった。また、焼結体の相対密度は８２
％であった。I in the sintered body thus obtained
The atomic ratio In / (In + Zn) of n was 0.80 as a result of ICP analysis. The relative density of the sintered body is 82
%Met.
【０１１４】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例６（２）と同様にして膜厚
１８０ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a film thickness of 180 nm was formed in the same manner as in Example 6 (2) except that the sintered body obtained in (1) above was used as the sputtering target. did.
【０１１５】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．８５であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.85.
【０１１６】このようにして得られた透明導電膜の表面
抵抗は２１．２Ω／□であり、可視光透過率は８２．７
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は２２．０Ω／□と
低く、得られた透明導電膜は、耐湿性に優れていること
が確認された。The transparent conductive film thus obtained had a surface resistance of 21.2 Ω / □ and a visible light transmittance of 82.7.
%Met. Moreover, the surface resistance was as low as 22.0 Ω / □ even after 1000 hours of the humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１１７】実施例１０ （１）ターゲットＩの製造 酸化インジウム２７８ｇと酸化亜鉛２７．５ｇを用いた
他は、実施例５（１）と同様に粉砕混合、仮焼、成型、
焼結を行った。得られた焼結体はＸ線回折測定結果、Ｉ
ｎ2 Ｏ3 （ＺｎＯ）3 の六方晶層状化合物とＩｎ2 Ｏ3
との混合物であることが確認された。Example 10 (1) Manufacture of Target I In the same manner as in Example 5 (1) except that 278 g of indium oxide and 27.5 g of zinc oxide were used, pulverization and mixing, calcination, molding,
Sintering was performed. The obtained sintered body was measured by X-ray diffraction, and I
Hexagonal layered compound of n 2 O 3 (ZnO) 3 and In 2 O 3
It was confirmed to be a mixture with.
【０１１８】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．８５であった。また、焼結体の相対密度は９５
％であった。I in the thus obtained sintered body
The atomic ratio In / (In + Zn) of n was 0.85 as a result of ICP analysis. The relative density of the sintered body is 95
%Met.
【０１１９】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例６（２）と同様にして膜厚
２２０ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a thickness of 220 nm was formed in the same manner as in Example 6 (2) except that the sintered body obtained in (1) above was used as a sputtering target. did.
【０１２０】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．８９であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.89.
【０１２１】このようにして得られた透明導電膜の表面
抵抗は１５．６Ω／□であり、可視光透過率は８２．５
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は１６．０Ω／□と
低く、得られた透明導電膜は、耐湿性に優れていること
が確認された。The transparent conductive film thus obtained had a surface resistance of 15.6 Ω / □ and a visible light transmittance of 82.5.
%Met. In addition, the surface resistance was as low as 16.0 Ω / □ even after 1000 hours of the humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１２２】実施例１１ （１）ターゲットＩの製造 塩化インジウム４水和物４３５ｇ、酢酸亜鉛２水和物５
０．３ｇをメトキシエタノール２．５リットルに溶解し
て溶液Ａを得た。Example 11 (1) Production of Target I Indium chloride tetrahydrate 435 g, zinc acetate dihydrate 5
Solution A was obtained by dissolving 0.3 g in 2.5 liters of methoxyethanol.
【０１２３】一方、しゅう酸２水和物２５０ｇをエタノ
ール２．５リットルに溶解して溶液Ｂを得た。On the other hand, 250 g of oxalic acid dihydrate was dissolved in 2.5 liter of ethanol to obtain a solution B.
【０１２４】室温下、容器にエタノール０．５リットル
を入れて撹拌しておき、そこへ同じ流量に制御した溶液
ＡとＢを同時に滴下した。滴下終了後、温度を４０℃に
上げて沈澱物を４時間熟成した。その後、沈澱物を濾過
し、エタノールで洗浄し、１１０℃で１２時間乾燥し、
更に、７００℃で５時間焼成した。直径２ｍｍのアルミ
ナボールとともに容積８００ｃｃのポリイミド製のポッ
トに入れ、エタノールを加えて遊星ボールミルで１００
時間粉砕混合した。その後１０００℃で５時間仮焼し、
更に遊星ボールミルで２４時間粉砕混合した。At room temperature, 0.5 liter of ethanol was placed in a container and stirred, and solutions A and B controlled to the same flow rate were simultaneously added dropwise thereto. After the dropping was completed, the temperature was raised to 40 ° C. and the precipitate was aged for 4 hours. Then the precipitate was filtered, washed with ethanol and dried at 110 ° C. for 12 hours,
Further, it was baked at 700 ° C. for 5 hours. Alumina balls with a diameter of 2 mm are put in a polyimide pot with a volume of 800 cc, ethanol is added, and a planetary ball mill is used for 100
Milled and mixed for hours. Then calcination at 1000 ℃ for 5 hours,
Further, the mixture was pulverized and mixed with a planetary ball mill for 24 hours.
【０１２５】この粉末を直径４インチの金型に装入し、
１００ｋｇ／ｃｍ2 の圧力で金型プレス成型機にて予備
成型を行った。その後、冷間静水圧プレス成型機にて４
ｔ／ｃｍ2 の圧力で圧密化し、熱間静水圧プレスにて、
１５００ｋｇｆ／ｃｍ2 、１４５０℃で３時間焼成し焼
結体を得た。得られた焼結体のＸ線回折測定の結果、Ｉ
ｎ2 Ｏ3 （ＺｎＯ）4 の六方晶層状化合物とＩｎ2 Ｏ3
との混合物であることが確認された。This powder was placed in a mold having a diameter of 4 inches,
Pre-molding was performed with a die press molding machine at a pressure of 100 kg / cm 2 . Then, cold isostatic press molding machine 4
Consolidate at a pressure of t / cm 2 and press with a hot isostatic press.
It was fired at 1500 kgf / cm 2 and 1450 ° C. for 3 hours to obtain a sintered body. As a result of X-ray diffraction measurement of the obtained sintered body, I
Hexagonal layered compound of n 2 O 3 (ZnO) 4 and In 2 O 3
It was confirmed to be a mixture with.
【０１２６】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．８５であった。また、焼結体の相対密度は９５
％であった。I in the sintered body thus obtained
The atomic ratio In / (In + Zn) of n was 0.85 as a result of ICP analysis. The relative density of the sintered body is 95
%Met.
【０１２７】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例６（２）と同様にして膜厚
２２０ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a thickness of 220 nm was formed in the same manner as in Example 6 (2) except that the sintered body obtained in (1) above was used as the sputtering target. did.
【０１２８】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．８９であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.89.
【０１２９】このようにして得られた透明導電膜の表面
抵抗は１６．０Ω／□であり、可視光透過率は８２．４
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は１６．４Ω／□と
低く、得られた透明導電膜は耐湿性に優れていることが
確認された。The transparent conductive film thus obtained had a surface resistance of 16.0 Ω / □ and a visible light transmittance of 82.4.
%Met. Further, the surface resistance was as low as 16.4 Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１３０】実施例１２ （１）ターゲットIIの製造 ドープ元素としてＳｎを５原子％添加した以外は、実施
例１０（１）と同様に粉砕混合、仮焼、成型、焼結を行
なった。得られた焼結体はＸ線回折測定結果、Ｉｎ2 Ｏ
3 （ＺｎＯ）3 の六方晶層状化合物とＩｎ2 Ｏ3 との混
合物であることが確認された。Example 12 (1) Manufacture of Target II The same pulverization and mixing, calcination, molding and sintering were carried out as in Example 10 (1) except that 5 atom% of Sn was added as a doping element. The obtained sintered body was In 2 O
It was confirmed to be a mixture of a hexagonal layered compound of 3 (ZnO) 3 and In 2 O 3 .
【０１３１】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結
果、０．８５であった。また、Ｓｎの原子比Ｓｎ／（Ｉ
ｎ＋Ｚｎ＋Ｓｎ）は０．０５であった。また、焼結体の
相対密度は９２％であった。I in the thus obtained sintered body
The atomic ratio In / (In + Zn) of n was 0.85 as a result of ICP analysis. Further, the atomic ratio of Sn is Sn / (I
n + Zn + Sn) was 0.05. The relative density of the sintered body was 92%.
【０１３２】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用いた以外は実施例６（２）と同様にして膜厚
２３０ｎｍの透明導電膜を成膜した。(2) Production of transparent conductive film A transparent conductive film having a film thickness of 230 nm was formed in the same manner as in Example 6 (2) except that the sintered body obtained in (1) above was used as a sputtering target. did.
【０１３３】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、非晶質であることが確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．８９であった。The transparent conductive film thus obtained is X
As a result of line diffraction measurement, it was confirmed to be amorphous. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.89.
【０１３４】このようにして得られた透明導電膜の表面
抵抗は１４．３Ω／□であり、可視光透過率は８３．０
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後でも表面抵抗は１４．９Ω／□と
低く、得られた透明導電膜は、耐湿性に優れていること
が確認された。The transparent conductive film thus obtained had a surface resistance of 14.3 Ω / □ and a visible light transmittance of 83.0.
%Met. Further, the surface resistance was as low as 14.9 Ω / □ even after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and it was confirmed that the obtained transparent conductive film had excellent humidity resistance.
【０１３５】比較例１ （１）ターゲットの製造 酸化インジウム２７８ｇと酸化亜鉛１１ｇを用いた他
は、実施例５（１）と同様に粉砕混合、仮焼、焼結を行
なった。得られた焼結体はＸ線回折測定結果、Ｉｎ2 Ｏ
3 であることが確認された。Comparative Example 1 (1) Production of Target In the same manner as in Example 5 (1) except that 278 g of indium oxide and 11 g of zinc oxide were used, pulverization and mixing, calcination and sintering were performed. The obtained sintered body was In 2 O
It was confirmed to be 3 .
【０１３６】このようにして得られた焼結体におけるＩ
ｎの原子比Ｉｎ／（Ｉｎ＋Ｚｎ）は、ＩＣＰ分析の結果
０．９３であった。また、焼結体の相対密度は９０％で
あった。I in the thus obtained sintered body
The atomic ratio In / (In + Zn) of n was 0.93 as a result of ICP analysis. The relative density of the sintered body was 90%.
【０１３７】（２）透明導電膜の製造 上記（１）で得られた焼結体をスパッタリングターゲッ
トとして用い、基板温度を８０℃にした以外は、実施例
６（２）と同様にして、膜厚２００ｎｍの透明導電膜を
成膜した。(2) Production of transparent conductive film A film was formed in the same manner as in Example 6 (2), except that the sintered body obtained in (1) above was used as a sputtering target and the substrate temperature was set to 80 ° C. A transparent conductive film having a thickness of 200 nm was formed.
【０１３８】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、Ｉｎ2 Ｏ3 の結晶が確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）はＩＣＰ分析の結果、０．９７であった。The transparent conductive film thus obtained is X
As a result of the line diffraction measurement, crystals of In 2 O 3 were confirmed. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.97.
【０１３９】このようにして得られた透明導電膜の表面
抵抗は２１０．０Ω／□であり、可視光透過率は８１．
８％であった。また、４０℃、９０％ＲＨの条件での耐
湿性試験１０００時間後には表面抵抗は３８０Ω／□と
なり、得られた透明導電膜は化学的安定性に欠けてい
た。The surface resistance of the transparent conductive film thus obtained was 210.0 Ω / □, and the visible light transmittance was 81.
It was 8%. Further, the surface resistance was 380 Ω / □ after 1000 hours of the humidity resistance test under the conditions of 40 ° C. and 90% RH, and the obtained transparent conductive film lacked chemical stability.
【０１４０】比較例２ 比較例１（１）の焼結体をスパッタリングターゲットと
して用いた他は、実施例４（２）と同様にして、膜厚２
００ｎｍの透明導電膜を成膜した。Comparative Example 2 A film having a film thickness of 2 was formed in the same manner as in Example 4 (2) except that the sintered body of Comparative Example 1 (1) was used as a sputtering target.
A transparent conductive film having a thickness of 00 nm was formed.
【０１４１】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、Ｉｎ2 Ｏ3 の結晶が確認された。ま
た、この透明導電膜におけるＩｎの原子比Ｉｎ／（Ｉｎ
＋Ｚｎ）は、ＩＣＰ分析の結果、０．９７であった。The transparent conductive film thus obtained is X
As a result of the line diffraction measurement, crystals of In 2 O 3 were confirmed. Further, the atomic ratio of In in the transparent conductive film In / (In
As a result of ICP analysis, + Zn) was 0.97.
【０１４２】このようにして得られた透明導電膜の表面
抵抗は１１００．０Ω／□であり、可視光透過率は８
２．５％であった。また、４０℃、９０％ＲＨの条件で
の耐湿性試験１０００時間後には表面抵抗は１３００Ω
／□となり、得られた透明導電膜は化学的安定性に欠け
ていた。The transparent conductive film thus obtained had a surface resistance of 1100.0 Ω / □ and a visible light transmittance of 8
It was 2.5%. Further, the surface resistance is 1300Ω after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH.
/, And the obtained transparent conductive film lacked chemical stability.
【０１４３】比較例３ Ｓｎを１０原子％添加したＩＴＯをターゲットとして用
いた他は、実施例６（２）と同様にして、膜厚２００ｎ
ｍの透明導電膜を成膜した。Comparative Example 3 A film thickness of 200 n was obtained in the same manner as in Example 6 (2) except that ITO containing 10 atomic% of Sn was used as a target.
m transparent conductive film was formed.
【０１４４】このようにして得られた透明導電膜は、Ｘ
線回折測定の結果、Ｉｎ2 Ｏ3 の結晶が確認された。The transparent conductive film thus obtained is X
As a result of the line diffraction measurement, crystals of In 2 O 3 were confirmed.
【０１４５】このようにして得られた透明導電膜の表面
抵抗は２８．０Ω／□であり、可視光透過率は８２．６
％であった。また、４０℃、９０％ＲＨの条件での耐湿
性試験１０００時間後には表面抵抗は５６．２Ω／□と
なり、得られた透明導電膜は化学的安定性に欠けてい
た。The transparent conductive film thus obtained had a surface resistance of 28.0 Ω / □ and a visible light transmittance of 82.6.
%Met. Further, the surface resistance was 56.2 Ω / □ after 1000 hours of humidity resistance test under the conditions of 40 ° C. and 90% RH, and the obtained transparent conductive film lacked chemical stability.
【０１４６】[0146]
【発明の効果】以上説明したように、本発明によれば、
ＩＴＯ膜よりも耐湿性に優れるとともにＩＴＯ膜と同等
の導電性および光透過率を有する透明導電膜を得るため
のターゲットおよびその製造方法が提供された。As described above, according to the present invention,
A target and a method for manufacturing the same have been provided for obtaining a transparent conductive film that is superior in moisture resistance to an ITO film and has conductivity and light transmittance equivalent to those of an ITO film.
Claims (5)
Ｏ3 （ＺｎＯ）m （ｍ＝２〜２０）で表される六方晶層
状化合物を含む酸化物の焼結体からなることを特徴とす
るターゲット。1. A general formula In 2 containing In and Zn as main components.
A target comprising an oxide sintered body containing a hexagonal layered compound represented by O 3 (ZnO) m (m = 2 to 20).
正三価以上の原子価を有する元素の少なくとも１種を、
六方晶層状化合物を形成する全カチオン元素の合量に対
して２０原子％以下でドープしたものであることを特徴
とするターゲット。2. The hexagonal layered compound according to claim 1,
At least one element having a valence of positive trivalence or more,
A target which is doped at 20 atomic% or less based on the total amount of all cationic elements forming a hexagonal layered compound.
ｎ）］が０．２〜０．８５である請求項１または２に記
載のターゲット。3. An atomic ratio of In and Zn [In / (In + Z
n)] is 0.2 to 0.85, The target according to claim 1 or 2.
する工程と、前記工程で得られた混合物を仮焼する工程
と、前記工程で得られた仮焼物を成型し焼結して、Ｉｎ
とＺｎを主成分とし、一般式Ｉｎ2 Ｏ3 （ＺｎＯ）
m （ｍ＝２〜２０）で表される六方晶層状化合物を含む
焼結体を得る工程とを含むことを特徴とするターゲット
の製造方法。4. A step of mixing an indium compound and a zinc compound, a step of calcining the mixture obtained in the step, and a step of molding and sintering the calcined material obtained in the step
And Zn as main components, and has the general formula In 2 O 3 (ZnO)
and a step of obtaining a sintered body containing the hexagonal layered compound represented by m (m = 2 to 20).
価以上の原子価を有する元素の少なくとも１種を加えて
混合する工程と、前記工程で得られた混合物を仮焼する
工程と、前記工程で得られた仮焼物を成型し焼結して、
ＩｎとＺｎを主成分とし、一般式Ｉｎ2 Ｏ3 （ＺｎＯ）
m （ｍ＝２〜２０）で表される六方晶層状化合物に、正
三価以上の原子価を有する元素の少なくとも１種を全カ
チオン元素の合量に対して２０原子％以下でドープした
化合物を含む焼結体を得る工程とを含むことを特徴とす
るターゲットの製造方法。5. A step of adding at least one element having a valence of at least positive trivalence to an indium compound and a zinc compound and mixing, a step of calcining the mixture obtained in the step, and a step of The obtained calcined product is molded and sintered,
The main component is In and Zn, and the general formula is In 2 O 3 (ZnO).
A compound obtained by doping a hexagonal layered compound represented by m (m = 2 to 20) with at least one element having a valence of at least positive trivalence at 20 atom% or less based on the total amount of all cationic elements. And a step of obtaining a sintered body containing the target.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5315084A JP2695605B2 (en) | 1992-12-15 | 1993-12-15 | Target and manufacturing method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33474592 | 1992-12-15 | ||
| JP4-334745 | 1992-12-15 | ||
| JP5315084A JP2695605B2 (en) | 1992-12-15 | 1993-12-15 | Target and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06234565A true JPH06234565A (en) | 1994-08-23 |
| JP2695605B2 JP2695605B2 (en) | 1998-01-14 |
Family
ID=26568174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5315084A Expired - Lifetime JP2695605B2 (en) | 1992-12-15 | 1993-12-15 | Target and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2695605B2 (en) |
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| CN100476017C (en) | 2003-03-04 | 2009-04-08 | 日矿金属株式会社 | Sputtering target and process for producing the same, thin film for optical information recording medium and process for producing the same |
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| JPH0350148A (en) * | 1989-07-19 | 1991-03-04 | Tosoh Corp | Zinc oxide sintered compact, production and its application |
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| JPS62157618A (en) * | 1985-09-18 | 1987-07-13 | セイコーエプソン株式会社 | Manufacture of transparent conductive film |
| JPH0350148A (en) * | 1989-07-19 | 1991-03-04 | Tosoh Corp | Zinc oxide sintered compact, production and its application |
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