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CN100564579C - Indium oxide-zinc oxide-magnesium oxide sputtering target and transparent conductive film - Google Patents

Indium oxide-zinc oxide-magnesium oxide sputtering target and transparent conductive film Download PDF

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CN100564579C
CN100564579C CNB2005800097523A CN200580009752A CN100564579C CN 100564579 C CN100564579 C CN 100564579C CN B2005800097523 A CNB2005800097523 A CN B2005800097523A CN 200580009752 A CN200580009752 A CN 200580009752A CN 100564579 C CN100564579 C CN 100564579C
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井上一吉
松原雅人
笘井重和
岛根幸朗
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Idemitsu Kosan Co Ltd
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Abstract

本发明提供一种在溅射时不会产生节结的靶。另外，还提供蚀刻性优良并且特别是在400～450nm区域的透明性方面优良的非晶态透明导电膜。是含有氧化铟、氧化锌、氧化镁的溅射靶，该溅射靶在溅射时不会产生节结。另外，是含有氧化铟、氧化锌、氧化镁的非晶态透明导电膜，该非晶态透明导电膜在蚀刻性方面优良，并且400～450nm区域的光线透过率高。The present invention provides a target that does not produce nodules during sputtering. In addition, an amorphous transparent conductive film having excellent etching properties and excellent transparency in a 400 to 450 nm region is also provided. It is a sputtering target containing indium oxide, zinc oxide, and magnesium oxide. This sputtering target will not produce nodules during sputtering. In addition, it is an amorphous transparent conductive film containing indium oxide, zinc oxide, and magnesium oxide. This amorphous transparent conductive film is excellent in etching properties and has high light transmittance in the 400 to 450 nm region.

Description

氧化铟-氧化锌-氧化镁类溅射靶及透明导电膜 Indium oxide-zinc oxide-magnesium oxide sputtering target and transparent conductive film

技术领域 technical field

本发明涉及液晶驱动用的电极基板、EL用的电极基板，特别涉及构成这些电极基板中所用的透明电极的透明导电膜。另外，本发明涉及为了制造该透明导电膜而使用的溅射靶。The present invention relates to an electrode substrate for liquid crystal driving and an electrode substrate for EL, and particularly to a transparent conductive film constituting a transparent electrode used in these electrode substrates. Moreover, this invention relates to the sputtering target used for manufacturing this transparent conductive film.

背景技术 Background technique

一直以来，作为透明导电膜用溅射靶，正在研究掺杂了Sn的材料。特别是，ITO(铟·锡氧化物：Indium Tin Oxide)被广泛地使用。Conventionally, Sn-doped materials have been studied as sputtering targets for transparent conductive films. In particular, ITO (Indium Tin Oxide: Indium Tin Oxide) is widely used.

但是，对于ITO的情况，为了降低其比电阻，需要使之结晶化。由此，需要在高温下成膜，或者在成膜后进行规定的加热处理。However, in the case of ITO, in order to lower its specific resistance, it needs to be crystallized. Therefore, it is necessary to form a film at a high temperature, or to perform a predetermined heat treatment after film formation.

另外，在结晶化了的ITO膜的蚀刻加工时，属于强酸的王水(硝酸·盐酸的混合液)被作为蚀刻液使用，然而有时因使用强酸而造成的不佳状况的产生会成为问题。即，在将TFT(Thin Film Transistor：薄膜晶体管)等作为构成要素使用的液晶显示装置中，有作为栅线、源·漏线(或电极)使用金属细线的情况。该情况下，在ITO膜的蚀刻加工时，有时会产生因王水而使这些配线材料断线或发生细线化的问题。In addition, aqua regia (a mixture of nitric acid and hydrochloric acid), which is a strong acid, is used as an etchant during etching of a crystallized ITO film. However, the use of a strong acid may cause problems. That is, in liquid crystal display devices using TFT (Thin Film Transistor: Thin Film Transistor) etc. as constituent elements, metal thin wires may be used as gate lines and source/drain lines (or electrodes). In this case, during the etching process of the ITO film, there may be a problem that these wiring materials are disconnected or thinned by aqua regia.

所以，提出过如下的方案，即，在成膜时，通过使溅射气体中存在氢或水，而形成非晶态ITO膜，将所形成的非晶态ITO膜用弱酸蚀刻。但是，由于ITO自身为结晶性，因此在用弱酸进行蚀刻的情况下，有时产生蚀刻残渣的情况会成为问题。另外，在成膜时，当在溅射气体中分散有氢或水时，则在ITO溅射靶上会产生被称作节结的突起，有可能成为异常放电的原因。Therefore, it has been proposed to form an amorphous ITO film by allowing hydrogen or water to exist in a sputtering gas during film formation, and to etch the formed amorphous ITO film with a weak acid. However, since ITO itself is crystalline, when it etches with a weak acid, it may become a problem that an etching residue may generate|occur|produce. In addition, when hydrogen or water is dispersed in the sputtering gas during film formation, protrusions called nodules are generated on the ITO sputtering target, which may cause abnormal discharge.

另一方面，作为关于被作为一般添加于透明导电膜中的Sn以外的添加金属，添加Zn的溅射靶或导电材料、透明导电膜的专利的一个例子，公布有如下的专利文献。On the other hand, the following patent documents are published as examples of patents on sputtering targets, conductive materials, and transparent conductive films to which Zn is added as an additive metal other than Sn generally added to transparent conductive films.

例如，在下述专利文献1中，公布有含有以In和Zn作为主成分、以通式In2O3(ZnO)m(m＝2～20)表示的六方晶层状化合物的溅射靶。根据该溅射靶，可以获得与ITO膜相比在耐湿性方面更为优良，并且具有与ITO膜同等的导电性及透光率的透明导电膜。For example, Patent Document 1 below discloses a sputtering target containing a hexagonal layered compound represented by the general formula In 2 O 3 (ZnO) m (m=2 to 20) having In and Zn as main components. According to this sputtering target, it is excellent in moisture resistance compared with an ITO film, and the transparent conductive film which has electrical conductivity and light transmittance equivalent to an ITO film can be obtained.

另外，下述专利文献2中，公布有一种液晶显示器用滤色片，其具备作为非晶态氧化物的锌元素、铟元素的原子比的Zn/(Zn+In)的值为0.2～小于0.9的液晶驱动用透明电极，在所述液晶驱动用透明电极中，难以产生裂纹或剥离。In addition, the following Patent Document 2 discloses a color filter for a liquid crystal display having an atomic ratio of Zn/(Zn+In) of an amorphous oxide of zinc element and indium element having a value of 0.2 to less than 0.2. The transparent electrode for driving a liquid crystal having a value of 0.9 is less likely to cause cracks or peeling in the transparent electrode for driving a liquid crystal.

另外，下述专利文献3中，公布有一种导电性透明基材，是含有In及Zn，In/(In+Zn)的值为0.8～0.9的导电性透明基材，在蚀刻特性、比电阻的热稳定性方面优良。In addition, the following Patent Document 3 discloses a conductive transparent substrate containing In and Zn, a conductive transparent substrate having a value of In/(In+Zn) of 0.8 to 0.9, and is characterized in terms of etching characteristics, specific resistance, etc. Excellent thermal stability.

另外，在这些被公布的专利文献1～3中，还有出示可以获得不产生节结的靶、可以获得蚀刻性优良并且具有与ITO同等的比电阻的透明导电膜的内容的专利文献。In addition, among these published Patent Documents 1 to 3, there are also patent documents showing that a target free from nodules can be obtained and a transparent conductive film having excellent etchability and a specific resistance equivalent to ITO can be obtained.

专利文献1：特开平06-234565号公报Patent Document 1: Japanese Unexamined Patent Application Publication No. 06-234565

专利文献2：特开平07-120612号公报Patent Document 2: Japanese Unexamined Patent Application Publication No. 07-120612

专利文献1：特开平07-235219号公报Patent Document 1: Japanese Unexamined Patent Application Publication No. 07-235219

专利文献1：特开平08-264022号公报Patent Document 1: Japanese Unexamined Patent Application Publication No. 08-264022

但是，在非晶态的透明导电膜中，由于不能明确地产生能带隙，即，能带隙并不很大，因此会有产生在短波长侧，特别是400～450nm区域中的光线透过率降低的问题的情况。However, in an amorphous transparent conductive film, since the energy band gap cannot be clearly generated, that is, the energy band gap is not very large, there will be light transmission on the short wavelength side, especially in the 400 to 450 nm region. The case of the problem of over-rate reduction.

针对于此，所述专利文献4中，制造了通过调整拟三元类氧化物的组成，可以控制折射率，并且透明性高的透明导电膜。但是有如下的问题，即，为了形成该透明导电膜而使用的溅射靶的导电率低，难以进行溅射，或者由于所形成的透明导电膜为结晶性，因此蚀刻性不太高。In view of this, in the above-mentioned Patent Document 4, a transparent conductive film having high transparency and which can control the refractive index by adjusting the composition of the pseudo-ternary oxide is manufactured. However, there are problems in that the sputtering target used for forming the transparent conductive film has low conductivity and sputtering is difficult, or the formed transparent conductive film is crystalline and therefore has a problem that the etchability is not so high.

发明内容 Contents of the invention

本发明是为了解决所述问题而完成的，其目的在于，提供在溅射时不会产生节结的靶。另外，本发明的其他的目的在于，提供蚀刻性优良并且特别是在400～450nm区域的透明性方面优良的(在400～450nm区域中具有高的光线透过率的)非晶态透明导电膜。The present invention has been made to solve the above problems, and an object of the present invention is to provide a target that does not generate nodules during sputtering. In addition, another object of the present invention is to provide an amorphous transparent conductive film that is excellent in etchability and particularly excellent in transparency in the 400-450 nm region (having high light transmittance in the 400-450 nm region). .

溅射靶的发明Invention of the sputtering target

(1)所以，为了解决所述问题，本发明提供一种溅射靶，其特征是，含有氧化铟、氧化锌和氧化镁。(1) Therefore, in order to solve the above problems, the present invention provides a sputtering target characterized by containing indium oxide, zinc oxide, and magnesium oxide.

通过向由氧化铟、氧化锌构成的溅射靶中又添加氧化镁，就可以更为有效地抑制在溅射时发生的节结(nodule)的产生，可以获得异常放电很少的靶。By adding magnesium oxide to a sputtering target made of indium oxide or zinc oxide, the generation of nodules during sputtering can be more effectively suppressed, and a target with little abnormal discharge can be obtained.

(2)另外，本发明提供一种溅射靶，其特征是，在含有氧化铟、氧化锌和氧化镁的溅射靶中，在观察了利用X射线衍射得到的晶体峰的情况下，所述晶体峰含有来源于由氧化铟及氧化锌构成的以通式In2O3(ZnO)m表示的六方晶层状化合物、和由氧化铟及氧化镁构成的In2MgO4的峰。这里，m为3～20的整数。(2) In addition, the present invention provides a sputtering target characterized in that, in a sputtering target containing indium oxide, zinc oxide, and magnesium oxide, when a crystal peak obtained by X-ray diffraction is observed, the The crystal peaks include peaks derived from a hexagonal layered compound represented by the general formula In 2 O 3 (ZnO) m composed of indium oxide and zinc oxide, and In 2 MgO 4 composed of indium oxide and magnesium oxide. Here, m is an integer of 3-20.

利用X射线衍射测定了溅射靶表面的结果为，在观察了所得的晶体峰的情况下，在该晶体峰中，必须含有来源于规定的六方晶层状化合物、In2MgO4的峰。这里，所谓规定的六方晶层状化合物是由氧化铟及氧化锌构成的以通式In2O3(ZnO)m(这里m为3～20的整数)表示的六方晶层状化合物。另外，所述In2MgO4由氧化铟及氧化镁构成。As a result of measuring the surface of the sputtering target by X-ray diffraction, when the obtained crystal peaks were observed, the peaks derived from the specified hexagonal layered compound, In 2 MgO 4 , must be included in the crystal peaks. Here, the predetermined hexagonal layered compound is a hexagonal layered compound represented by the general formula In 2 O 3 (ZnO) m (where m is an integer of 3 to 20) composed of indium oxide and zinc oxide. In addition, the In 2 MgO 4 is composed of indium oxide and magnesium oxide.

作为由氧化铟、氧化锌构成的六方晶层状化合物的具体例，可以举出In2Zn3O6、In2Zn4O7、In2Zn5O8等，其通式被以In2O3(ZnO)m(这里m为3～20的整数)。另外，利用EPMA(Electron Probe Microanalysis：X射线微量分析仪)的测绘得到的这些复合氧化物的晶体粒子的大小最好在10μm以下，优选5μm以下，更优选3μm以下。Specific examples of hexagonal layered compounds composed of indium oxide and zinc oxide include In 2 Zn 3 O 6 , In 2 Zn 4 O 7 , In 2 Zn 5 O 8 , etc., whose general formula is represented by In 2 O 3 (ZnO) m (where m is an integer of 3 to 20). In addition, the size of crystal particles of these complex oxides measured by EPMA (Electron Probe Microanalysis: X-ray microanalyzer) is preferably 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.

在溅射靶不含有由氧化铟、氧化锌构成的所述六方晶层状化合物及In2MgO4等的情况下，则溅射靶的体电阻(bulk resistance)有时会超过10mΩcm。像这样，当体电阻超过10mΩcm时，则会有在溅射中产生异常放电或溅射靶破裂的情况。When the sputtering target does not contain the above-mentioned hexagonal layered compound composed of indium oxide or zinc oxide, In 2 MgO 4 , etc., the bulk resistance of the sputtering target may exceed 10 mΩcm. In this way, when the bulk resistance exceeds 10 mΩcm, abnormal discharge may occur during sputtering or the sputtering target may be broken.

(3)另外，本发明是如下的所述(1)中所记载的溅射靶，其特征是，含有由氧化铟及氧化锌构成的六方晶层状化合物、由氧化铟及氧化镁构成的In2MgO4。(3) In addition, the present invention is the sputtering target described in the following (1), characterized in that it contains a hexagonal layered compound composed of indium oxide and zinc oxide, and a sputtering target composed of indium oxide and magnesium oxide. In 2 MgO 4 .

(4)另外，本发明是如下的所述(1)～(3)中任意一项所记载的溅射靶，其特征是，[In]/([In]+[Zn]+[Mg])＝0.74～0.94，[Zn]/([In]+[Zn]+[Mg])＝0.05～0.25，[Mg]/([In]+[Zn]+[Mg])＝0.01～0.20。这里，[In]表示单位体积中的铟原子的数目，[Zn]表示单位体积中的锌原子的数目，[Mg]表示单位体积中的镁原子的数目。(4) In addition, the present invention is the sputtering target described in any one of the following (1) to (3), characterized in that [In]/([In]+[Zn]+[Mg] )=0.74～0.94, [Zn]/([In]+[Zn]+[Mg])=0.05～0.25, [Mg]/([In]+[Zn]+[Mg])=0.01～0.20. Here, [In] represents the number of indium atoms per unit volume, [Zn] represents the number of zinc atoms per unit volume, and [Mg] represents the number of magnesium atoms per unit volume.

铟的组成Composition of indium

本发明的溅射靶中，[In]/([In]+[Zn]+[Mg])＝0.74～0.94。在[In]/([In]+[Zn]+[Mg])的值小于0.74的情况下，溅射靶的体电阻有时会变得过大，或者所形成的透明导电膜的比电阻变大。另一方面，在[In]/([In]+[Zn]+[Mg])的值超过0.94的情况下，所形成的透明导电膜的比电阻有时会变大，或者透明导电膜结晶化，在蚀刻时产生残渣。In the sputtering target of the present invention, [In]/([In]+[Zn]+[Mg])=0.74 to 0.94. When the value of [In]/([In]+[Zn]+[Mg]) is less than 0.74, the bulk resistance of the sputtering target may become too large, or the specific resistance of the formed transparent conductive film may decrease. big. On the other hand, when the value of [In]/([In]+[Zn]+[Mg]) exceeds 0.94, the specific resistance of the formed transparent conductive film may become large, or the transparent conductive film may be crystallized. , resulting in residue during etching.

锌的组成composition of zinc

另外，本发明的溅射靶中，[Zn]/([In]+[Zn]+[Mg])＝0.05～0.25。在[Zn]/([In]+[Zn]+[Mg])的值小于0.05的情况下，所形成的透明导电膜的比电阻有时会变得过大，或者发生结晶化。另一方面，在[Zn]/([In]+[Zn]+[Mg])的值超过0.25的情况下，所形成的透明导电膜的比电阻有时会变得过大。Moreover, in the sputtering target of this invention, [Zn]/([In]+[Zn]+[Mg])=0.05-0.25. When the value of [Zn]/([In]+[Zn]+[Mg]) is less than 0.05, the specific resistance of the formed transparent conductive film may become too large, or crystallization may occur. On the other hand, when the value of [Zn]/([In]+[Zn]+[Mg]) exceeds 0.25, the specific resistance of the formed transparent conductive film may become too large.

镁的组成Composition of magnesium

另外，本发明的溅射靶中，[Mg]/([In]+[Zn]+[Mg])＝0.01～0.20。在[Mg]/([In]+[Zn]+[Mg])的值小于0.01的情况下，所形成的透明导电膜的比电阻有时会变得过大，或者发生结晶化，另外，透明导电膜的透过率有时不会提高。另一方面，在[Mg]/([In]+[Zn]+[Mg])的值超过0.25的情况下，所形成的透明导电膜的比电阻有时会变得过大。Moreover, in the sputtering target of this invention, [Mg]/([In]+[Zn]+[Mg])=0.01-0.20. When the value of [Mg]/([In]+[Zn]+[Mg]) is less than 0.01, the specific resistance of the formed transparent conductive film may become too large, or crystallization may occur, and the transparent The transmittance of the conductive film may not be improved. On the other hand, when the value of [Mg]/([In]+[Zn]+[Mg]) exceeds 0.25, the specific resistance of the formed transparent conductive film may become too large.

(5)另外，本发明是如下的所述(1)～(4)中任意一项所记载的溅射靶，其特征是，还含有正4价的金属氧化物。(5) In addition, the present invention is the sputtering target described in any one of the following (1) to (4), characterized by further containing a positive tetravalent metal oxide.

所谓正4价是指，金属氧化物中的金属原子的原子价为+4。通过含有正4价的金属氧化物，溅射靶的体电阻即降低，可以防止异常放电。The term "positive tetravalent" means that the atomic valence of the metal atom in the metal oxide is +4. By containing the positive tetravalent metal oxide, the bulk resistance of the sputtering target is reduced, and abnormal discharge can be prevented.

(6)另外，本发明是如下的所述(5)中所记载的溅射靶，其特征是，正4价的所述金属氧化物为SnO2、ZrO2、GeO2、CeO2。(6) In addition, the present invention is the sputtering target described in the following (5), wherein the metal oxide having a positive tetravalent valence is SnO 2 , ZrO 2 , GeO 2 , or CeO 2 .

在正4价的金属氧化物当中，可以优选使用SnO2、ZrO2、GeO2、CeO2。Among positive tetravalent metal oxides, SnO 2 , ZrO 2 , GeO 2 , and CeO 2 can be preferably used.

(7)另外，本发明是如下的所述(6)中所记载的溅射靶，其特征是，含有选自由SnO2、ZrO2、GeO2、CeO2及Ga2O3构成的组M中的1种或2种以上的金属氧化物。( 7 ) In addition , the present invention is the sputtering target described in the following (6) , characterized by containing One or more than two metal oxides.

(8)另外，本发明是如下的所述(7)中所记载的溅射靶，其特征是，选自所述组M中的1种或2种以上的所述金属氧化物的添加量为[M]/[全部金属]＝0.0001～0.15。这里，[M]表示单位体积中的从所述组M中选择的1种或2种以上的金属氧化物中的金属，即，单位体积中的Sn、Zr、Ge、Ce、Ga的任意1种或2种以上的原子的数目，[全部金属]表示单位体积中的全部金属，即，单位体积中的In、Zn、Mg和从所述组M中选择的1种或2种以上的金属氧化物中的金属的原子的总数。(8) In addition, the present invention is the sputtering target described in the following (7), wherein the addition amount of the metal oxide of one or more kinds selected from the group M is [M]/[all metals]=0.0001 to 0.15. Here, [M] represents the metal in one or more metal oxides selected from the group M per unit volume, that is, any one of Sn, Zr, Ge, Ce, and Ga per unit volume. The number of atoms of one or more kinds, [all metals] means all metals in a unit volume, that is, In, Zn, Mg in a unit volume and one or two or more metals selected from the group M The total number of atoms of the metal in the oxide.

在溅射靶中，[M]/[全部金属]的值为0.0001～0.15，优选0.0003～0.12，更优选0.0005～0.1。在[M]/[全部金属]的值小于0.0001的情况下，有时不会产生添加效果，另一方面，在[M]/[全部金属]的值超过0.15的情况下，有时所形成的透明导电膜的蚀刻性基本上不会提高。In the sputtering target, the value of [M]/[all metals] is 0.0001 to 0.15, preferably 0.0003 to 0.12, more preferably 0.0005 to 0.1. When the value of [M]/[All Metals] is less than 0.0001, the additive effect may not be produced. On the other hand, when the value of [M]/[All Metals] exceeds 0.15, the formed transparent The etchability of the conductive film does not substantially improve.

非晶态透明导电膜的发明Invention of amorphous transparent conductive film

(9)另外，本发明是一种非晶态透明导电膜，其特征是，含有氧化铟、氧化锌和氧化镁。(9) In addition, the present invention is an amorphous transparent conductive film characterized by containing indium oxide, zinc oxide and magnesium oxide.

因透明导电膜含有氧化铟、氧化锌以及氧化镁，从而可以获得完全非晶态的透明导电膜。通过像这样将透明导电膜设为非晶态，在蚀刻时，基本上就不会产生蚀刻残渣。另外，因透明导电膜含有氧化镁，从而可以有效地防止透明导电膜的400～450nm区域中的光线透过率的降低。Since the transparent conductive film contains indium oxide, zinc oxide and magnesium oxide, a completely amorphous transparent conductive film can be obtained. By making the transparent conductive film amorphous in this way, almost no etching residue is generated during etching. In addition, since the transparent conductive film contains magnesium oxide, it is possible to effectively prevent the decrease of the light transmittance in the 400-450 nm region of the transparent conductive film.

(10)另外，本发明是如下的所述(9)中所记载的非晶态透明导电膜，其特征是，[In]/([In]+[Zn]+[Mg])＝0.74～0.94，[Zn]/([In]+[Zn]+[Mg])＝0.05～0.25，[Mg]/([In]+[Zn]+[Mg])＝0.01～0.20。这里，[In]表示单位体积中的铟原子的数目，[Zn]表示单位体积中的锌原子的数目，[Mg]表示单位体积中的镁原子的数目。(10) In addition, the present invention is an amorphous transparent conductive film described in the following (9), characterized in that [In]/([In]+[Zn]+[Mg])=0.74～ 0.94, [Zn]/([In]+[Zn]+[Mg])=0.05-0.25, [Mg]/([In]+[Zn]+[Mg])=0.01-0.20. Here, [In] represents the number of indium atoms per unit volume, [Zn] represents the number of zinc atoms per unit volume, and [Mg] represents the number of magnesium atoms per unit volume.

铟的组成Composition of indium

本发明的透明导电膜中，[In]/([In]+[Zn]+[Mg])的值为0.74～0.94，优选0.7～0.92，更优选0.75～0.9。在[In]/([In]+[Zn]+[Mg])的值小于0.74的情况下，透明导电膜的比电阻有时就会变得过大，在[In]/([In]+[Zn]+[Mg])的值超过0.94的情况下，有时透明导电膜容易结晶化，或者比电阻变大。In the transparent conductive film of the present invention, the value of [In]/([In]+[Zn]+[Mg]) is 0.74 to 0.94, preferably 0.7 to 0.92, more preferably 0.75 to 0.9. When the value of [In]/([In]+[Zn]+[Mg]) is less than 0.74, the specific resistance of the transparent conductive film sometimes becomes too large, at [In]/([In]+ When the value of [Zn]+[Mg]) exceeds 0.94, the transparent conductive film tends to be crystallized or the specific resistance may increase.

锌的组成composition of zinc

本发明的透明导电膜中，[Zn]/([In]+[Zn]+[Mg])的值为0.05～0.25，优选0.07～0.25，更优选0.08～0.22。在[Zn]/([In]+[Zn]+[Mg])的值小于0.05的情况下，有时透明导电膜容易结晶化，或者比电阻变大。另一方面，在[Zn]/([In]+[Zn]+[Mg])的值超过0.25的情况下，会有透明导电膜的比电阻变得过大的情况。In the transparent conductive film of the present invention, the value of [Zn]/([In]+[Zn]+[Mg]) is 0.05 to 0.25, preferably 0.07 to 0.25, more preferably 0.08 to 0.22. When the value of [Zn]/([In]+[Zn]+[Mg]) is less than 0.05, the transparent conductive film is likely to crystallize or the specific resistance may become large. On the other hand, when the value of [Zn]/([In]+[Zn]+[Mg]) exceeds 0.25, the specific resistance of the transparent conductive film may become too large.

镁的组成Composition of magnesium

本发明的透明导电膜中，[Mg]/([In]+[Zn]+[Mg])的值为0.01～0.2，优选0.01～0.15，更优选0.02～0.1。在[Mg]/([In]+[Zn]+[Mg])的值小于0.01的情况下，有透明导电膜的透过率不会提高，或者容易结晶化，比电阻变大的情况。在[Mg]/([In]+[Zn]+[Mg])的值超过0.20的情况下，所形成的透明导电膜的比电阻有时就会变得过大。In the transparent conductive film of the present invention, the value of [Mg]/([In]+[Zn]+[Mg]) is 0.01 to 0.2, preferably 0.01 to 0.15, more preferably 0.02 to 0.1. When the value of [Mg]/([In]+[Zn]+[Mg]) is less than 0.01, the transmittance of the transparent conductive film may not be improved, or crystallization may be easy to increase the specific resistance. When the value of [Mg]/([In]+[Zn]+[Mg]) exceeds 0.20, the specific resistance of the formed transparent conductive film may become too large.

在透明导电膜中的In、Zn、Mg的含量不处于所述范围内的情况下，透明导电膜就会无法获得理想的透明性、比电阻、蚀刻性等。When the contents of In, Zn, and Mg in the transparent conductive film are not within the above-mentioned ranges, the transparent conductive film cannot obtain desired transparency, specific resistance, etching property, and the like.

(11)另外，本发明是如下的所述(9)或(10)中所记载的非晶态透明导电膜，其特征是，还含有正4价的金属氧化物。(11) In addition, the present invention is the amorphous transparent conductive film described in the following (9) or (10), characterized in that it further contains a positive tetravalent metal oxide.

通过使透明导电膜中含有正4价的金属氧化物，溅射靶的体电阻即被降低，能够以稳定的放电状态形成透明导电膜。由此就可以获得更为稳定的透明导电膜。By including positive tetravalent metal oxide in the transparent conductive film, the volume resistance of the sputtering target is reduced, and the transparent conductive film can be formed in a stable discharge state. Thus, a more stable transparent conductive film can be obtained.

(12)另外，本发明是如下的所述(11)中所记载的非晶态透明导电膜，其特征是，正4价的所述金属氧化物为SnO2、ZrO2、GeO2、CeO2。(12) In addition, the present invention is the amorphous transparent conductive film described in the following (11), characterized in that the positive tetravalent metal oxide is SnO 2 , ZrO 2 , GeO 2 , CeO 2 .

在正4价的金属氧化物当中，可以优选使用SnO2、ZrO2、GeO2、CeO2。Among positive tetravalent metal oxides, SnO 2 , ZrO 2 , GeO 2 , and CeO 2 can be preferably used.

(13)另外，本发明是如下的所述(9)或(10)中所记载的非晶态透明导电膜，其特征是，含有选自由SnO2、ZrO2及GeO2、CeO2及Ga2O3构成的组M中的1种或2种以上的金属氧化物。(13) In addition, the present invention is the amorphous transparent conductive film described in the following (9) or (10), characterized in that it contains One or two or more metal oxides in Group M consisting of 2 O 3 .

(14)另外，本发明是如下的所述(13)中所记载的非晶态透明导电膜，其特征是，选自所述组M中的1种或2种以上的所述金属氧化物的添加量为[M]/[全部金属]＝0.0001～0.15。这里，[M]表示单位体积中的从所述组M中选择的1种或2种以上的金属氧化物中的金属，即，单位体积中的Sn、Zr、Ge、Ce、Ga的任意1种或2种以上的原子的数目，[全部金属]表示单位体积中的全部金属，即，单位体积中的In、Zn、Mg和从所述组M中选择的1种或2种以上的金属氧化物中的金属的原子的总数。(14) In addition, the present invention is the amorphous transparent conductive film described in the following (13), characterized in that one or more metal oxides selected from the group M are The added amount of the metal is [M]/[all metals]=0.0001～0.15. Here, [M] represents the metal in one or more metal oxides selected from the group M per unit volume, that is, any one of Sn, Zr, Ge, Ce, and Ga per unit volume. The number of atoms of one or more kinds, [all metals] means all metals in a unit volume, that is, In, Zn, Mg in a unit volume and one or two or more metals selected from the group M The total number of atoms of the metal in the oxide.

在透明导电膜中，[M]/[全部金属]的值为[M]/[全部金属]＝0.0001～0.15，优选0.0003～0.12，更优选0.0005～0.1。在[M]/[全部金属]的值小于0.0001的情况下，不会产生添加效果，在[M]/[全部金属]的值超过0.15的情况下，透明导电膜的蚀刻性基本上不会提高。In the transparent conductive film, the value of [M]/[total metal]=[M]/[total metal]=0.0001 to 0.15, preferably 0.0003 to 0.12, more preferably 0.0005 to 0.1. When the value of [M]/[all metals] is less than 0.0001, the additive effect does not occur, and when the value of [M]/[all metals] exceeds 0.15, the etchability of the transparent conductive film is basically not improve.

如上所示，本发明的溅射靶在溅射时基本上不会产生节结。As described above, the sputtering target of the present invention hardly generates nodules during sputtering.

另外，本发明的非晶态透明导电膜基本上不会因利用弱酸(有机酸等)的蚀刻而产生残渣等，并且在400～450nm区域的透明性(光线透过性)方面优良。In addition, the amorphous transparent conductive film of the present invention hardly generates residues or the like by etching with a weak acid (organic acid, etc.), and is excellent in transparency (light transmittance) in the 400 to 450 nm region.

附图说明 Description of drawings

图1是表示本实施例1～9及比较例1、2的溅射用靶及透明导电膜的物性参数的图。FIG. 1 is a graph showing physical property parameters of sputtering targets and transparent conductive films of Examples 1 to 9 and Comparative Examples 1 and 2. FIG.

图2是表示本实施例1的靶1的X射线表图的图。FIG. 2 is a diagram showing an X-ray diagram of the target 1 in Example 1. FIG.

具体实施方式 Detailed ways

下面将对本发明的优选的实施方式进行说明。Preferred embodiments of the present invention will be described below.

实施例1Example 1

靶1Target 1

将平均粒径为1μm以下的In2O3粉末、平均粒径为1μm以下的ZnO粉末及平均粒径为1μm以下的MgO粉末以规定的比例称量、混合后，加入树脂制锅中，再添加水，进行了使用硬质ZrO2球的湿式球磨机混合。此时，将混合时间设为20小时。利用该混合，将所得的混合料浆取出，进行了过滤、干燥及造粒。将所得的造粒物放入成形模具，在冷等静压压力机中施加3ton/cm2的压力而成形，得到了成形体。In 2 O 3 powder with an average particle size of 1 μm or less, ZnO powder with an average particle size of 1 μm or less, and MgO powder with an average particle size of 1 μm or less were weighed and mixed in a predetermined ratio, and then put into a resin pot, and then Water was added, and wet ball mill mixing using hard ZrO 2 balls was performed. At this time, the mixing time was set to 20 hours. By this mixing, the obtained mixed slurry was taken out, filtered, dried and granulated. The obtained granulated material was put into a forming die, and formed by applying a pressure of 3 ton/cm 2 in a cold isostatic pressing machine to obtain a formed body.

然后，将所得的成形体如下所示地烧结。首先，在烧结炉内，放置成形体，以相对于该烧结炉内的每0.1m3容积为5升/分钟的比例流入了氧。在该气氛中，将所述成形体在1470℃下烧结了5小时。此时，将烧结炉内的温度以1℃/分钟升温至1000℃，1000℃～1470℃之间以3℃/分钟进行了升温。Then, the obtained molded body was sintered as shown below. First, a compact was placed in a sintering furnace, and oxygen was flowed in at a rate of 5 liters/minute per 0.1 m 3 volume in the sintering furnace. In this atmosphere, the molded body was sintered at 1470° C. for 5 hours. At this time, the temperature in the sintering furnace was raised to 1000° C. at 1° C./min., and the temperature was raised at 3° C./min. between 1000° C. and 1470° C.

其后，停止氧流入，将所述烧结炉内的温度从1470℃以10℃/分钟降温到1300℃。此外，以相对于该烧结炉内的每0.1m3容积为10升/分钟的比例流入了Ar，在该气氛中，将所述成形体在1300℃下保持了3小时后，自然冷却，得到了烧结体。Thereafter, the inflow of oxygen was stopped, and the temperature in the sintering furnace was lowered from 1470° C. to 1300° C. at 10° C./min. In addition, Ar was flowed at a rate of 10 liters/minute per 0.1 m 3 volume in the sintering furnace, and in this atmosphere, the molded body was kept at 1300° C. for 3 hours, and then cooled naturally to obtain sintered body.

所得的烧结体的相对密度是如下所示地求得的。首先，利用使用了水的阿基米德法进行测定，根据理论密度算出了相对密度，其值为97％。该相对密度被表示于图1中。而且，此时的理论密度是根据没有氧缺陷的In2O3晶体(红绿柱石型构造)、Zn、Mg的氧化物的重量百分率算出的。The relative density of the obtained sintered body was obtained as follows. First, the relative density was calculated from the theoretical density by the Archimedes method using water, and the value was 97%. This relative density is represented in FIG. 1 . In addition, the theoretical density at this time was calculated from the weight percentage of the In2O3 crystal (beryl type structure) without an oxygen defect, and the oxide of Zn and Mg.

另外，利用ICP(感应耦合等离子体：Inductively Coupled Plasma)发光分析法定量分析了烧结体中的Zn和Mg的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，作为所确认的烧结体中的具体的原子组成比率的[In]/([In]+[Zn]+[Mg])的值、[Zn]/([In]+[Zn]+[Mg])的值、[Mg]/([In]+[Zn]+[Mg])的值被表示于图1中。In addition, the content of Zn and Mg in the sintered body was quantitatively analyzed by ICP (Inductively Coupled Plasma) emission analysis method, and it was confirmed that the feed composition when mixing the raw material powder was also maintained in the sintered body. At this time, the value of [In]/([In]+[Zn]+[Mg]), [Zn]/([In]+[Zn]+ The values of [Mg]) and [Mg]/([In]+[Zn]+[Mg]) are shown in FIG. 1 .

而且，图1中的[In]表示烧结体中的单位体积中的铟原子的数目，[Zn]表示烧结体中的单位体积中的锌原子的数目，[Mg]表示烧结体中的单位体积中的镁原子的数目。Moreover, [In] in FIG. 1 represents the number of indium atoms per unit volume in the sintered body, [Zn] represents the number of zinc atoms per unit volume in the sintered body, and [Mg] represents the number of zinc atoms per unit volume in the sintered body. The number of magnesium atoms in .

然后，将所述烧结体的溅射面用杯状砂轮研磨，加工为直径100mm，厚度5mm，使用In类合金贴合背板，制造了溅射用靶1。对于该溅射用靶1的体电阻，首先使用ロレスタ(三菱油化制)，利用4探针法，计测靶1的比电阻，基于所计测的比电阻的值，利用计算求得。所算出的体电阻的值被表示于图1中。Then, the sputtering surface of the sintered body was ground with a cup wheel, processed to a diameter of 100 mm, and a thickness of 5 mm, and a back plate was bonded using an In-based alloy to manufacture a sputtering target 1 . The bulk resistance of the target 1 for sputtering was first measured by the four-probe method using Loresta (manufactured by Mitsubishi Oil Chemicals), and the specific resistance of the target 1 was calculated based on the measured specific resistance value. The calculated values of bulk resistance are shown in FIG. 1 .

锌或镁在靶1内被包含的形态最好不是作为氧化锌(ZnO)、氧化镁(MgO)分散，而是作为氧化铟-氧化锌的复合氧化物(例如In2Zn5O8、In2Zn7O10、In2Zn3O6、In2Zn4O7等)分散。图2中，给出了表示靶1的X射线的图。图2中，纵轴表示衍射了的X射线的强度，横轴表示衍射了的X射线的角度。而且，由氧化铟及氧化锌构成的所述六方晶层状化合物例如优选In2Zn3O6、In2Zn4O7、In2Zn5O8等，以通式In2O3(ZnO)m(这里m为3～20的整数)表示。The form in which zinc or magnesium is contained in the target 1 is preferably not dispersed as zinc oxide (ZnO) or magnesium oxide (MgO), but as a composite oxide of indium oxide-zinc oxide (for example, In 2 Zn 5 O 8 , In 2 Zn 7 O 10 , In 2 Zn 3 O 6 , In 2 Zn 4 O 7 etc.) dispersion. In FIG. 2 , a diagram showing X-rays of the target 1 is shown. In FIG. 2 , the vertical axis represents the intensity of the diffracted X-rays, and the horizontal axis represents the angle of the diffracted X-rays. Moreover, the hexagonal layered compound composed of indium oxide and zinc oxide is preferably, for example, In 2 Zn 3 O 6 , In 2 Zn 4 O 7 , In 2 Zn 5 O 8 , etc., with the general formula In 2 O 3 (ZnO ) m (where m is an integer of 3 to 20) represents.

在锌原子或镁原子在氧化铟的铟位点置换固溶，以原子水平分散于氧化铟烧结体中的情况下，靶1的体电阻变得过大，在溅射时，放电不稳定，有可能引发异常放电。In the case where zinc atoms or magnesium atoms are substituted into solid solution at the indium site of indium oxide and dispersed at the atomic level in the indium oxide sintered body, the volume resistance of the target 1 becomes too large, and the discharge becomes unstable during sputtering. Abnormal discharge may occur.

靶1中的氧化铟、氧化锌及氧化镁例如优选以由氧化铟及氧化锌构成的六方晶层状化合物的形态、由氧化铟及氧化镁构成的In2MgO4的形态分散。通过以此种形态分散，靶1的体电阻就不会变得过大，在溅射时，放电稳定。Indium oxide, zinc oxide, and magnesium oxide in the target 1 are preferably dispersed in the form of a hexagonal layered compound composed of indium oxide and zinc oxide, or in the form of In 2 MgO 4 composed of indium oxide and magnesium oxide, for example. By dispersing in this form, the bulk resistance of the target 1 does not become too large, and the discharge is stabilized during sputtering.

利用X射线衍射确认，本实施例1的靶1中的氧化铟、氧化锌及氧化镁以所述六方晶层状化合物、In2MgO4这样的形态分散。而且，溅射用靶1中的氧化铟、氧化锌及氧化镁所分散的如上所述的形态是基于利用X射线衍射得到的晶体峰而确认的。It was confirmed by X-ray diffraction that indium oxide, zinc oxide, and magnesium oxide in the target 1 of Example 1 were dispersed in the form of the hexagonal layered compound and In 2 MgO 4 . In addition, the above-described form in which indium oxide, zinc oxide, and magnesium oxide are dispersed in the sputtering target 1 was confirmed based on crystal peaks obtained by X-ray diffraction.

而且，由氧化铟及氧化锌构成的所述六方晶层状化合物例如优选In2Zn3O6、In2Zn4O7、In2Zn5O8等，以通式In2O3(ZnO)m(这里m为3～20的整数)表示。Moreover, the hexagonal layered compound composed of indium oxide and zinc oxide is preferably, for example, In 2 Zn 3 O 6 , In 2 Zn 4 O 7 , In 2 Zn 5 O 8 , etc., with the general formula In 2 O 3 (ZnO ) m (where m is an integer of 3 to 20) represents.

通过以此种形态分散，靶1的体电阻就会小于10mΩcm，能够实现稳定的溅射。另外，在使用该靶1进行了溅射后，并未产生节结(图1)。By dispersing in such a form, the bulk resistance of the target 1 becomes less than 10 mΩcm, and stable sputtering can be realized. In addition, after sputtering using this target 1 , no nodules were generated ( FIG. 1 ).

透明导电膜1atransparent conductive film 1a

在将所得的靶1安装于DC溅射装置中后，在200℃下，在载玻片上，形成了130nm膜厚的透明导电膜1a。测定了所形成的透明导电膜1a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜1a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜1a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 1 in a DC sputtering apparatus, a transparent conductive film 1a having a film thickness of 130 nm was formed on a slide glass at 200°C. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 1 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 1a, no peak was observed, and it was found that it was an amorphous state. In addition, the transparent conductive film 1 a was etched using a weak acid, and no residue was generated ( FIG. 1 ).

像这样，本实施例1中，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜1a。Thus, in the present Example 1, the transparent conductive film 1a which improved the light transmittance of 400-450 nm although it was an amorphous state was obtained.

实施例2Example 2

靶2Target 2

除了平均粒径为1μm以下的In2O3粉末、平均粒径为1μm以下的ZnO粉末、平均粒径为1μm以下的MgO粉末的混合比例不同这一点以外，通过用与所述实施例1相同的方法，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。Except that the mixing ratios of In 2 O 3 powder with an average particle diameter of 1 μm or less, ZnO powder with an average particle diameter of 1 μm or less, and MgO powder with an average particle diameter of 1 μm or less were different, by using the same method as in Example 1, According to the method, the powders are mixed, shaped and sintered to obtain a sintered body. The relative density of the obtained sintered body was obtained by the same method as in Example 1 above. The obtained relative density is shown in FIG. 1 .

另外，与所述实施例1相同，利用ICP发光分析法定量分析了所得的烧结体中的Zn和Mg的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, as in Example 1, the contents of Zn and Mg in the obtained sintered compact were quantitatively analyzed by ICP emission spectrometry, and it was confirmed that the feed composition when mixing the raw material powders was also maintained in the sintered compact. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶2。另外，用与所述实施例1相同的方法，求得了该靶2的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶2进行了溅射，并未产生节结(图1)。Then, in the same manner as in Example 1, a backing plate was bonded to the sputtering surface of the sintered body to manufacture a sputtering target 2 . In addition, the volume resistance of the target 2 was obtained by the same method as in the above-mentioned Example 1. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 2 , and no nodules were generated ( FIG. 1 ).

另外，利用X射线衍射确认，本实施例2的溅射用靶2中的氧化铟、氧化锌及氧化镁以与所述实施例1相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 2 of Example 2 were hexagonal layered compounds in the same form as in Example 1, and In 2 MgO 4 . form exists.

透明导电膜2atransparent conductive film 2a

在将所得的靶2安装于DC溅射装置中后，与所述实施例1相同，在200℃下，在载玻片上，形成了130nm膜厚的透明导电膜2a。测定了所形成的透明导电膜2a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜2a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜2a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 2 in a DC sputtering apparatus, a transparent conductive film 2 a having a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Example 1 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 2 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 2a, no peak was observed, and it was found that it was an amorphous state. In addition, the transparent conductive film 2 a was etched using a weak acid, and no residue was generated ( FIG. 1 ).

像这样，本实施例2中，也与所述实施例1相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜2a。In this way, also in this Example 2, similarly to the above-mentioned Example 1, a transparent conductive film 2 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例3Example 3

靶3Target 3

除了平均粒径为1μm以下的In2O3粉末、平均粒径为1μm以下的ZnO粉末、平均粒径为1μm以下的MgO粉末的混合比例不同这一点以外，通过用与所述实施例1及2相同的方法，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1及2相同的方法求得了所得的烧结体的相对密度。此时，所求得的相对密度被表示于图1中。Except that the mixing ratio of In 2 O 3 powder with an average particle diameter of 1 μm or less, ZnO powder with an average particle diameter of 1 μm or less, and MgO powder with an average particle diameter of 1 μm or less is different, by using the same method as in Example 1 and 2. In the same way, the powders were mixed, shaped and sintered to obtain a sintered body. The relative density of the obtained sintered body was obtained by the same method as in Examples 1 and 2 above. The relative density obtained at this time is shown in FIG. 1 .

另外，与所述实施例1及2相同，利用ICP发光分析法定量分析了所得的烧结体中的Zn和Mg的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, as in Examples 1 and 2, the contents of Zn and Mg in the obtained sintered body were quantitatively analyzed by ICP emission analysis, and it was confirmed that the feed composition when mixing the raw material powders was also determined in the sintered body. maintain. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1及2相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶3。另外，用与所述实施例1及2相同的方法，求得了该靶3的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶3进行了溅射，并末产生节结(图1)。Then, in the same manner as in Examples 1 and 2, a backing plate was bonded to the sputtering surface of the sintered body to manufacture a sputtering target 3 . In addition, the bulk resistance of the target 3 was obtained by the same method as in Examples 1 and 2 above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 3, and no nodules were generated (FIG. 1).

另外，利用X射线衍射确认，本实施例3的溅射用靶3中的氧化铟、氧化锌及氧化镁以与所述实施例1及2相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 3 of Example 3 were hexagonal layered compounds in the same form as those in Examples 1 and 2, In 2 MgO 4 Such a form exists.

透明导电膜3aTransparent Conductive Film 3a

在将所得的靶3安装于DC溅射装置中后，与所述实施例1及2相同，在200℃下，在载玻片上，形成了130nm膜厚的透明导电膜3a。测定了所形成的透明导电膜3a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜3a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜3a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 3 in a DC sputtering apparatus, a transparent conductive film 3 a with a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 and 2 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 3 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 3a, no peak was observed, and it was found that it was an amorphous state. In addition, the transparent conductive film 3 a was etched using a weak acid, and no residue was generated ( FIG. 1 ).

像这样，本实施例3中，也与所述实施例1及2相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜3a。In this manner, also in Example 3, as in Examples 1 and 2, a transparent conductive film 3 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例4Example 4

靶4Target 4

除了平均粒径为1μm以下的In2O3粉末、平均粒径为1μm以下的ZnO粉末、平均粒径为1μm以下的MgO粉末的混合比例不同这一点以外，通过用与所述实施例1～3相同的方法，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1～3相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。Except that the mixing ratio of In 2 O 3 powder with an average particle diameter of 1 μm or less, ZnO powder with an average particle diameter of 1 μm or less, and MgO powder with an average particle diameter of 1 μm or less is different, by using the same method as in Examples 1 to 1 3. In the same way, the powders were mixed, shaped and sintered to obtain a sintered body. The relative density of the obtained sintered body was obtained by the same method as in Examples 1 to 3 above. The obtained relative density is shown in FIG. 1 .

另外，与所述实施例1～3相同，利用ICP发光分析法定量分析了所得的烧结体中的Zn和Mg的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, in the same manner as in Examples 1 to 3, the contents of Zn and Mg in the obtained sintered body were quantitatively analyzed by ICP emission analysis, and it was confirmed that the feed composition when mixing the raw material powder was also determined in the sintered body. maintain. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1～3相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶4。另外，用与所述实施例1～3相同的方法，求得了该靶4的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶4进行了溅射，并未产生节结(图1)。Then, a backing plate was bonded to the sputtering surface of the sintered body in the same manner as in Examples 1 to 3 to manufacture a sputtering target 4 . In addition, the bulk resistance of the target 4 was obtained by the same method as in Examples 1 to 3 above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 4, and no nodules were generated (FIG. 1).

另外，利用X射线衍射确认，本实施例4的溅射用靶4中的氧化铟、氧化锌及氧化镁以与所述实施例1～3相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 4 of Example 4 were hexagonal layered compounds in the same form as those in Examples 1 to 3, In 2 MgO 4 Such a form exists.

透明导电膜4atransparent conductive film 4a

在将所得的靶2安装于DC溅射装置中后，与所述实施例1相同，在200℃下，在载玻片上，形成了130nm膜厚的透明导电膜4a。测定了所形成的透明导电膜4a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜4a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜4a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 2 in a DC sputtering apparatus, a transparent conductive film 4 a having a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Example 1 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 4 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 4a, no peak was observed, and it was found that it was an amorphous state. In addition, no residue was generated after etching the transparent conductive film 4 a using a weak acid ( FIG. 1 ).

像这样，本实施例4中，也与所述实施例1～3相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜4a。In this way, also in this Example 4, similarly to the above-mentioned Examples 1 to 3, a transparent conductive film 4 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例5Example 5

靶5Target 5

除了还将SnO2粉末以规定的比例混合这一点以外，通过用与所述实施例1相同的组成比率，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1～4相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。A sintered body was obtained by mixing, molding, and sintering the powders at the same composition ratio as in Example 1 except that SnO 2 powders were mixed in a predetermined ratio. The relative density of the obtained sintered body was obtained by the same method as in Examples 1 to 4 above. The obtained relative density is shown in FIG. 1 .

另外，用与所述实施例1～4相同的方法，利用ICP发光分析法定量分析了所得的烧结体中的Zn、Mg及Sn的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, the contents of Zn, Mg, and Sn in the obtained sintered body were quantitatively analyzed by ICP emission analysis in the same manner as in Examples 1 to 4, and it was confirmed that the feed composition when mixing the raw material powders was between It is also maintained in the sintered body. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

而且，本专利中，M表示由Sn、Zr及Ge构成的组，特别是在图1中，M表示Sn、Zr及Ge的某种。另外，[M]表示烧结体中的单位体积中的Sn、Zr及Ge的原子的数目。Furthermore, in this patent, M represents a group consisting of Sn, Zr, and Ge, and particularly in FIG. 1 , M represents one of Sn, Zr, and Ge. In addition, [M] represents the number of atoms of Sn, Zr, and Ge per unit volume in the sintered body.

然后，用与所述实施例1～4相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶5。另外，用与所述实施例1～4相同的方法，求得了该靶5的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶5进行了溅射，并未产生节结(图1)。Then, a backing plate was bonded to the sputtering surface of the sintered body by the same method as in Examples 1 to 4 above to manufacture a sputtering target 5 . In addition, the bulk resistance of the target 5 was obtained by the same method as in Examples 1 to 4 above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 5 , and no nodules were generated ( FIG. 1 ).

另外，利用X射线衍射确认，本实施例5的溅射用靶5中的氧化铟、氧化锌及氧化镁以与所述实施例1～4相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 5 of Example 5 were hexagonal layered compounds in the same form as those in Examples 1 to 4, In 2 MgO 4 Such a form exists.

透明导电膜5atransparent conductive film 5a

在将所得的靶5安装于DC溅射装置中后，与所述实施例1～4相同，在200℃下，在载玻片上，形成了130nm膜厚的透明导电膜5a。测定了所形成的透明导电膜5a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜5a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜5a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 5 in a DC sputtering apparatus, a transparent conductive film 5 a having a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 4 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 5 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 5a, no peak was observed, and it was found that it was an amorphous state. In addition, no residue was generated after etching the transparent conductive film 5 a using a weak acid ( FIG. 1 ).

像这样，本实施例5中，也与所述实施例1～4相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜5a。In this manner, also in Example 5, as in Examples 1 to 4, a transparent conductive film 5 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例6Example 6

靶6Target 6

除了平均粒径为1μm以下的In2O3粉末、平均粒径为1μm以下的ZnO粉末、平均粒径为1μm以下的MgO粉末、SnO2粉末的混合比例不同这一点以外，通过用与所述实施例5相同的方法，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1～5相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。In addition to the point that the mixing ratio of In2O3 powder with an average particle size of 1 μm or less , ZnO powder with an average particle size of 1 μm or less, MgO powder with an average particle size of 1 μm or less, and SnO 2 powder is different, by using the above-mentioned In the same manner as in Example 5, the powders were mixed, shaped, and sintered to obtain a sintered body. The relative density of the obtained sintered body was obtained by the same method as in Examples 1 to 5 described above. The obtained relative density is shown in FIG. 1 .

另外，与所述实施例5相同，利用ICP发光分析法定量分析了所得的烧结体中的Zn、Mg及Sn的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, as in Example 5, the contents of Zn, Mg, and Sn in the obtained sintered body were quantitatively analyzed by ICP emission analysis, and it was confirmed that the feed composition when mixing the raw material powders was also determined in the sintered body. maintain. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1～5相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶6。另外，用与所述实施例1～5相同的方法，求得了该靶6的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶6进行了溅射，并未产生节结(图1)。Then, in the same manner as in Examples 1 to 5, a backing plate was bonded to the sputtering surface of the sintered body to manufacture a sputtering target 6 . In addition, the bulk resistance of the target 6 was obtained by the same method as in Examples 1 to 5 described above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 6 , and no nodules were generated ( FIG. 1 ).

另外，利用X射线衍射确认，本实施例6的溅射用靶6中的氧化铟、氧化锌及氧化镁以与所述实施例1～5相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 6 of this Example 6 were hexagonal layered compounds in the same form as those in Examples 1 to 5, and In 2 MgO 4 Such a form exists.

透明导电膜6aTransparent conductive film 6a

在将所得的靶6安装于DC溅射装置中后，与所述实施例1～5相同，在200℃下，在载玻片上，形成了130nm的膜厚的透明导电膜6a。测定了所形成的透明导电膜6a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜6a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜6a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 6 in a DC sputtering apparatus, a transparent conductive film 6 a with a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 5 described above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 6 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 6a, no peak was observed, and it was found that it was an amorphous state. In addition, no residue was generated after etching the transparent conductive film 6 a using a weak acid ( FIG. 1 ).

像这样，本实施例6中，也与所述实施例1～5相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜6a。In this way, also in this Example 6, similarly to the above-mentioned Examples 1 to 5, a transparent conductive film 6 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例7Example 7

靶7Target 7

除了平均粒径为1μm以下的In2O3粉末、平均粒径为1μm以下的ZnO粉末、平均粒径为1μm以下的MgO粉末、SnO2粉末的混合比例不同这一点以外，通过用与所述实施例5及6相同的方法，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1～6相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。In addition to the point that the mixing ratio of In2O3 powder with an average particle size of 1 μm or less , ZnO powder with an average particle size of 1 μm or less, MgO powder with an average particle size of 1 μm or less, and SnO 2 powder is different, by using the above-mentioned In the same manner as in Examples 5 and 6, the powders were mixed, shaped, and sintered to obtain a sintered body. The relative density of the obtained sintered body was obtained by the same method as in Examples 1 to 6 described above. The obtained relative density is shown in FIG. 1 .

另外，与所述实施例5及6相同，利用ICP发光分析法定量分析了所得的烧结体中的Zn、Mg及Sn的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, as in Examples 5 and 6, the contents of Zn, Mg, and Sn in the obtained sintered body were quantitatively analyzed by ICP emission analysis, and it was confirmed that the feed composition when mixing the raw material powders was the same as in the sintered body. is also maintained. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1～6相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶7。另外，用与所述实施例1～6相同的方法，求得了该靶7的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶7进行了溅射，并未产生节结(图1)。Then, in the same manner as in Examples 1 to 6, a backing plate was bonded to the sputtering surface of the sintered body to manufacture a sputtering target 7 . In addition, the bulk resistance of the target 7 was obtained by the same method as in Examples 1 to 6 described above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 7, and no nodules were generated (FIG. 1).

另外，利用X射线衍射确认，本实施例7的溅射用靶7中的氧化铟、氧化锌及氧化镁以与所述实施例1～6相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 7 of Example 7 were hexagonal layered compounds in the same form as those in Examples 1 to 6, In 2 MgO 4 Such a form exists.

透明导电膜7aTransparent conductive film 7a

在将所得的靶7安装于DC溅射装置中后，与所述实施例1～6相同，在200℃下，在载玻片上，形成了130nm的膜厚的透明导电膜7a。测定了所形成的透明导电膜7a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜7a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜7a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 7 in a DC sputtering apparatus, a transparent conductive film 7 a with a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 6 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 7 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 7a, no peak was observed, and it was found that it was an amorphous state. In addition, no residue was generated after etching the transparent conductive film 7 a using a weak acid ( FIG. 1 ).

像这样，本实施例7中，也与所述实施例1～6相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜7a。In this manner, also in Example 7, as in Examples 1 to 6, a transparent conductive film 7 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例8Example 8

靶8Target 8

除了还将ZrO2粉末以规定的比例混合这一点以外，通过用与所述实施例4相同的组成比率，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1～7相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。A sintered body was obtained by mixing, molding, and sintering the powders at the same composition ratio as in Example 4 except that ZrO 2 powders were also mixed in a predetermined ratio. The relative density of the obtained sintered compact was obtained by the same method as in Examples 1 to 7 above. The obtained relative density is shown in FIG. 1 .

另外，用与所述实施例1～7相同的方法，利用ICP发光分析法定量分析了所得的烧结体中的Zn、Mg及Zr的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, the Zn, Mg, and Zr contents in the obtained sintered body were quantitatively analyzed by ICP emission analysis in the same manner as in Examples 1 to 7, and it was confirmed that the feed composition when mixing the raw material powders was between It is also maintained in the sintered body. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1～7相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶8。另外，用与所述实施例1～7相同的方法，求得了该靶8的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶8进行了溅射，并未产生节结(图1)。Then, in the same manner as in Examples 1 to 7, a backing plate was bonded to the sputtering surface of the sintered body to manufacture a sputtering target 8 . In addition, the volume resistance of the target 8 was obtained by the same method as in Examples 1 to 7 above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 8, and no nodules were generated (FIG. 1).

另外，利用X射线衍射确认，本实施例8的溅射用靶8中的氧化铟、氧化锌及氧化镁以与所述实施例1～7相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 8 of Example 8 were hexagonal layered compounds in the same form as those in Examples 1 to 7, and In 2 MgO 4 Such a form exists.

透明导电膜8aTransparent conductive film 8a

在将所得的靶8安装于DC溅射装置中后，与所述实施例1～7相同，在200℃下，在载玻片上，形成了130nm的膜厚的透明导电膜8a。测定了所形成的透明导电膜8a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜8a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜8a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 8 in a DC sputtering apparatus, a transparent conductive film 8 a with a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 7 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 8 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . Moreover, as a result of X-ray diffraction measurement of this transparent conductive film 8a, no peak was observed, and it was found that it was an amorphous state. In addition, no residue was generated after etching the transparent conductive film 8 a using a weak acid ( FIG. 1 ).

像这样，本实施例8中，也与所述实施例1～7相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜8a。In this manner, also in Example 8, as in Examples 1 to 7, a transparent conductive film 8 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例9Example 9

靶9Target 9

除了取代ZrO2粉末而混合了GeO2粉末这一点以外，通过用与所述实施例8相同的组成比率，将所述粉末混合、成形、烧结，得到了烧结体。利用与所述实施例1～8相同的方法求得了所得的烧结体的相对密度。所求得的相对密度被表示于图1中。A sintered body was obtained by mixing, molding, and sintering the powders at the same composition ratio as in Example 8 except that GeO 2 powder was mixed instead of ZrO 2 powder. The relative density of the obtained sintered body was obtained by the same method as in Examples 1 to 8 described above. The obtained relative density is shown in FIG. 1 .

另外，用与所述实施例1～8相同的方法，利用ICP发光分析法定量分析了所得的烧结体中的Zn、Mg及Ge的含量，可以确认，将原料粉末混合时的进料组成在烧结体中也被维持。此时，所确认的烧结体中的具体的组成比率的值被表示于图1中。In addition, the contents of Zn, Mg, and Ge in the obtained sintered body were quantitatively analyzed by ICP emission analysis in the same manner as in Examples 1 to 8, and it was confirmed that the feed composition when mixing the raw material powders was between It is also maintained in the sintered body. At this time, the values of the specific composition ratios in the sintered body confirmed are shown in FIG. 1 .

然后，用与所述实施例1～8相同的方法，在该烧结体的溅射面上贴合背板，制造了溅射用靶9。另外，用与所述实施例1～8相同的方法，求得了该靶9的体电阻。所求得的体电阻的值被表示于图1中。另外，使用该靶9进行了溅射，并未产生节结(图1)。Then, in the same manner as in Examples 1 to 8, a backing plate was attached to the sputtering surface of the sintered body to manufacture a sputtering target 9 . In addition, the bulk resistance of the target 9 was obtained by the same method as in Examples 1 to 8 above. The obtained values of bulk resistance are shown in FIG. 1 . In addition, sputtering was performed using this target 9, and no nodules were generated (FIG. 1).

另外，利用X射线衍射确认，本实施例9的溅射用靶9中的氧化铟、氧化锌及氧化镁以与所述实施例1～8相同的形态的六方晶层状化合物、In2MgO4这样的形态存在。In addition, it was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target 9 of Example 9 were hexagonal layered compounds in the same form as in Examples 1 to 8, In 2 MgO 4 Such a form exists.

透明导电膜9aTransparent conductive film 9a

在将所得的靶9安装于DC溅射装置中后，与所述实施例1～8相同，在200℃下，在载玻片上，形成了130nm的膜厚的透明导电膜9a。测定了所形成的透明导电膜9a的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜9a，进行X射线衍射的测定，结果未观测到峰，判明为非晶态。另外，对于该透明导电膜9a，使用弱酸进行了蚀刻后，未产生残渣(图1)。After mounting the obtained target 9 in a DC sputtering apparatus, a transparent conductive film 9 a with a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 8 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film 9 a were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . In addition, as a result of performing X-ray diffraction measurement on this transparent conductive film 9a, no peak was observed, and it was found to be an amorphous state. In addition, no residue was generated after etching the transparent conductive film 9 a using a weak acid ( FIG. 1 ).

像这样，本实施例9中，也与所述实施例1～8相同，可以获得虽然是非晶态然而改善了400～450nm的光线透过率的透明导电膜9a。In this manner, also in Example 9, as in Examples 1 to 8, a transparent conductive film 9 a having an improved light transmittance of 400 to 450 nm can be obtained although it is in an amorphous state.

实施例10Example 10

本发明的溅射用靶除了以规定的比例含有氧化铟、氧化锌及氧化镁这3个成分以外，没有特别限制。所以，例如可以通过使用公知的方法，将由所述3个成分构成的粉体混合、成形、烧结来制造。The target for sputtering of the present invention is not particularly limited except that three components of indium oxide, zinc oxide, and magnesium oxide are contained in a predetermined ratio. Therefore, it can be manufactured, for example, by mixing, molding, and sintering powders composed of the three components using known methods.

而且，只要是在不损害本发明的效果的范围内，也优选含有所述3个成分以外的成分。例如，在所述实施例5～9中，溅射用靶除了所述3个成分以外，还以规定的比例含有SnO2、ZrO2或GeO2，作为它们以外的成分，也优选含有Ga2O3或CeO2等。另外，除了所述3个成分以外，也优选同时含有选自SnO2、ZrO2、GeO2、Ga2O3及CeO2等中的2个以上的成分。Furthermore, it is also preferable to contain components other than the above-mentioned three components within the range which does not impair the effect of this invention. For example, in Examples 5 to 9, the sputtering target contains SnO 2 , ZrO 2 , or GeO 2 at a predetermined ratio in addition to the three components described above, and Ga 2 is also preferably contained as components other than these. O 3 or CeO 2 etc. In addition to the above three components, it is also preferable to contain at least two components selected from SnO 2 , ZrO 2 , GeO 2 , Ga 2 O 3 , and CeO 2 at the same time.

而且，在靶中添加了Ga2O3的情况下，最好以InGaMgO4、InGaMg2O5或InGaMgZnO5、InGaMgZn2O6、In2Ga2ZnO7、InGaZnO4、InGaZn2O5、InGaZn3O6、InGaZn4O7、InGaZn5O8、InGaZn6O9、InGaZn7O10等复合氧化物的形态分散。Furthermore, when Ga 2 O 3 is added to the target, it is preferable to use InGaMgO 4 , InGaMg 2 O 5 or InGaMgZnO 5 , InGaMgZn 2 O 6 , In 2 Ga 2 ZnO 7 , InGaZnO 4 , InGaZn 2 O 5 , InGaZn 3 O 6 , InGaZn 4 O 7 , InGaZn 5 O 8 , InGaZn 6 O 9 , InGaZn 7 O 10 and other composite oxides are dispersed in morphology.

在本实施例10的溅射用靶除了氧化铟、氧化锌及氧化镁这3个成分以外，还含有所述SnO2、ZrO2、GeO2、Ga2O3、CeO2等成分的情况下，本实施例10的溅射用靶也起到与所述实施例1～9的溅射用靶相同的作用效果。另外，使用此种溅射用靶形成的透明导电膜也起到与所述实施例1～9的透明导电膜相同的作用效果。In the case where the sputtering target of Example 10 contains the above-mentioned components such as SnO 2 , ZrO 2 , GeO 2 , Ga 2 O 3 , and CeO 2 in addition to the three components of indium oxide, zinc oxide, and magnesium oxide , The target for sputtering of this Example 10 also exhibits the same effect as the targets for sputtering of Examples 1 to 9 described above. Moreover, the transparent conductive film formed using such a target for sputtering also exhibited the same operation effect as the transparent conductive film of the said Examples 1-9.

『比较例1』"Comparative Example 1"

ITO靶ITO target

使用市售的ITO靶，即，由氧化铟及氧化锡构成的溅射用靶，进行了与所述实施例1～9相同的处理·操作。Using a commercially available ITO target, that is, a sputtering target made of indium oxide and tin oxide, the same treatments and operations as in Examples 1 to 9 were performed.

用与所述实施例1～9相同的方法，求得了ITO靶的相对密度、组成比率、体电阻。所求得的相对密度、组成比率、体电阻的值被表示于图1中。而且，图1中的[X]表示靶中的单位体积中的Sn或Zn的原子的数目。另外，使用该ITO靶进行了溅射，产生了节结(图1)。The relative density, composition ratio, and bulk resistance of the ITO target were obtained by the same method as in Examples 1 to 9 above. The obtained values of relative density, composition ratio, and bulk resistance are shown in FIG. 1 . Also, [X] in FIG. 1 represents the number of atoms of Sn or Zn per unit volume in the target. In addition, when sputtering was performed using this ITO target, nodules were generated ( FIG. 1 ).

透明导电膜transparent conductive film

在将该ITO靶安装于DC溅射装置中后，与所述实施例1～9相同，在200℃下，在载玻片上，形成了130nm的膜厚的透明导电膜。测定了所形成的透明导电膜的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜，使用弱酸进行了蚀刻后，产生了残渣(图1)。After installing this ITO target in a DC sputtering apparatus, a transparent conductive film having a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 9 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . In addition, when this transparent conductive film was etched using a weak acid, a residue was generated ( FIG. 1 ).

像这样，当对比较例1的透明导电膜使用弱酸进行蚀刻时，即产生了残渣。In this way, when the transparent conductive film of Comparative Example 1 was etched using a weak acid, residues were generated.

『比较例2』"Comparative Example 2"

IZO靶IZO target

使用市售的IZO(铟-锌氧化物：「IZO」为注册商标)靶，即，由氧化铟及氧化锌构成的溅射用靶，进行了与所述实施例1～9相同的处理·操作。Using a commercially available IZO (indium-zinc oxide: "IZO" is a registered trademark) target, that is, a sputtering target made of indium oxide and zinc oxide, the same treatments as in Examples 1 to 9 were performed. operate.

用与所述实施例1～9相同的方法，求得了IZO靶的相对密度、组成比率、体电阻。所求得的相对密度、组成比率、体电阻的值被表示于图1中。另外，使用该IZO靶进行了溅射，产生了节结(图1)。The relative density, composition ratio, and bulk resistance of the IZO target were obtained in the same manner as in Examples 1 to 9 above. The obtained values of relative density, composition ratio, and bulk resistance are shown in FIG. 1 . In addition, when sputtering was performed using this IZO target, nodules were generated ( FIG. 1 ).

透明导电膜transparent conductive film

在将该IZO靶安装于DC溅射装置中后，与所述实施例1～9相同，在200℃下，在载玻片上，形成了130nm的膜厚的透明导电膜。测定了所形成的透明导电膜的比电阻及光线透过率(400nm、450nm)。所测定的比电阻及光线透过率的值被表示于图1中。另外，对于该透明导电膜，使用弱酸进行了蚀刻后，并未产生残渣(图1)。After installing this IZO target in a DC sputtering apparatus, a transparent conductive film having a film thickness of 130 nm was formed on a slide glass at 200° C. in the same manner as in Examples 1 to 9 above. The specific resistance and light transmittance (400 nm, 450 nm) of the formed transparent conductive film were measured. The measured values of specific resistance and light transmittance are shown in FIG. 1 . In addition, this transparent conductive film was etched using a weak acid, and no residue was generated ( FIG. 1 ).

像这样，在比较例2的透明导电膜中，400nm～450nm的光线透过率并未变得很高。In this way, in the transparent conductive film of Comparative Example 2, the light transmittance at 400 nm to 450 nm did not become very high.

Claims (11)

1. a sputtering target is characterized in that, contain by Indium sesquioxide and zinc oxide constitute with general formula I n 2O 3(ZnO) mThe hexagonal crystal lamellar compound of expression and the In that constitutes by Indium sesquioxide and magnesium oxide 2MgO 4, here, m is 3～20 integer,
And [In]/([In]+[Zn]+[Mg])=0.74～0.94, [Zn]/([In]+[Zn]+[Mg])=0.05～0.25, [Mg]/([In]+[Zn]+[Mg])=0.01～0.20, the number of the phosphide atom in [In] representation unit volume, the number of the zinc atom in [Zn] representation unit volume, the number of the magnesium atom in [Mg] representation unit volume.
2. sputtering target according to claim 1 is characterized in that,
Observing under the situation of utilizing the crystal peak that X-ray diffraction obtains,
Described crystal peak contain derive from by Indium sesquioxide and zinc oxide constitute with general formula I n 2O 3(ZnO) the hexagonal crystal lamellar compound represented of m and the In that constitutes by Indium sesquioxide and magnesium oxide 2MgO 4The peak, here, m is 3～20 integer.
3. sputtering target according to claim 1 and 2 is characterized in that, also contains the metal oxide of positive 4 valencys.
4. sputtering target according to claim 3 is characterized in that, the described metal oxide of positive 4 valencys is SnO 2, ZrO 2, GeO 2, CeO 2
5. sputtering target according to claim 1 and 2 is characterized in that,
Contain and be selected from by SnO 2, ZrO 2, GeO 2, CeO 2And Ga 2O 3The metal oxide more than a kind or 2 kinds among the group M that constitutes.
6. sputtering target according to claim 5 is characterized in that,
The addition that is selected from the described metal oxide more than a kind or 2 kinds among the described group of M is [M]/[all metals]=0.0001～0.15, here, metal in the metal oxide of from described group of M, selecting more than a kind or 2 kinds in [M] representation unit volume, promptly, Sn in the unit volume, Zr, Ge, Ce, the number of any atom more than a kind or 2 kinds of Ga, whole metals in [all metals] representation unit volume, that is the In in the unit volume,, Zn, the sum of the atom of the metal in Mg and the metal oxide more than a kind or 2 kinds from described group of M, selected.
7. a non-crystalline state nesa coating contains Indium sesquioxide, zinc oxide and magnesium oxide, it is characterized in that,
[In]/([In]+[Zn]+[Mg])=0.74～0.94, [Zn]/([In]+[Zn]+[Mg])=0.05～0.25, [Mg]/([In]+[Zn]+[Mg])=0.01～0.20, here, the number of the phosphide atom in [In] representation unit volume, the number of the zinc atom in [Zn] representation unit volume, the number of the magnesium atom in [Mg] representation unit volume.
8. non-crystalline state nesa coating according to claim 7 is characterized in that, also contains the metal oxide of positive 4 valencys.
9. non-crystalline state nesa coating according to claim 8 is characterized in that, the described metal oxide of positive 4 valencys is SnO 2, ZrO 2, GeO 2, CeO 2
10. non-crystalline state nesa coating according to claim 7 is characterized in that, contains to be selected from by SnO 2, ZrO 2, GeO 2, CeO 2And Ga 2O 3The metal oxide more than a kind or 2 kinds among the group M that constitutes.
11. non-crystalline state nesa coating according to claim 10, it is characterized in that, the addition that is selected from the described metal oxide more than a kind or 2 kinds among the described group of M is [M]/[all metals]=0.0001～0.15, here, metal in the metal oxide of from described group of M, selecting more than a kind or 2 kinds in [M] representation unit volume, promptly, Sn in the unit volume, Zr, Ge, Ce, the number of any atom more than a kind or 2 kinds of Ga, whole metals in [all metals] representation unit volume, that is the In in the unit volume,, Zn, the sum of the atom of the metal in Mg and the metal oxide more than a kind or 2 kinds from described group of M, selected.
CNB2005800097523A 2004-04-21 2005-02-23 Indium oxide-zinc oxide-magnesium oxide sputtering target and transparent conductive film Expired - Fee Related CN100564579C (en)

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