JP4548651B2 - Sputtering target, transparent conductive film and transparent conductive glass substrate - Google Patents

Description

  The present invention relates to a method for manufacturing a liquid crystal display device using an amorphous silicon thin film transistor (α-Si TFT) or a polysilicon thin film transistor (p-Si TFT). More specifically, the present invention relates to a liquid crystal display device capable of reducing contact resistance between a pixel electrode pattern and a source / drain wiring, a gate wiring extraction portion, a wiring metal of a source / drain electrode extraction portion and a transparent electrode, and a manufacturing method thereof. .

  The liquid crystal display device has features such as low power consumption and easy full color, so it is regarded as promising among thin displays, and in recent years, development related to enlargement of the display screen has been active. In particular, an active matrix liquid crystal flat panel display in which an α-Si TFT (TFT: Thin Film Transistor) or p-Si TFT is arranged in a matrix as a switching element for each pixel and is driven has a high definition of 800 × 600 pixels or more. Even if it is made, the contrast ratio does not deteriorate, and it has been attracting attention as a flat display for high-performance color display. In such an active matrix liquid crystal flat display, a transparent electrode such as ITO (Indium Tin Oxide) is often used as a pixel electrode, and an Al-based alloy thin film is often used as a source electrode. This is because ITO has a low sheet resistance. This is because the transmittance is high and Al can be easily patterned and has low resistance and high adhesion.

  FIG. 1 shows a cross section in the vicinity of an amorphous-Si TFT at the stage where pixel electrode pattern formation is completed in the manufacturing process of a liquid crystal flat display according to the present invention, but a conventional liquid crystal display also excludes pixel electrode materials. Since the basic structure is the same, this will be used for explanation.

  In FIG. 1, a pattern of a gate electrode 2 is formed on a translucent glass substrate 1, and then a SiN gate insulating film 3 and an amorphous-Si: H (i) film are formed using a plasma CVD (Chemical Vapor Deposition) method. 4. A channel protective film 5 and an amorphous-Si: H (n) film 6 are continuously formed to form a desired shape pattern.

  Further, a metal film mainly composed of Al is deposited by a vacuum evaporation method or a sputtering method, and a pattern of the source electrode 7 and a pattern 8 of the drain electrode 8 are respectively formed by a photolithography technique, thereby completing the α-Si TFT element portion.

  On top of this, an ITO film is deposited by a sputtering method, and a pattern of the pixel electrode 9 electrically connected to the source electrode 7 is formed by a photolithography technique. The reason why the ITO film is deposited after the Al film is that the electrical contact characteristics between the amorphous-Si: H film 4 (and 6), the source electrode 7 and the drain electrode 8 are not deteriorated. Further, Al is inexpensive and has a low specific resistance, and is an indispensable material in terms of preventing deterioration of the display performance of the liquid crystal display due to an increase in resistance of the wiring of the gate electrode 2 and the source electrode 7 and drain electrode 8.

When the pattern of the ITO pixel electrode 9 is processed with an HCl-HNO ₃ —H ₂ O-based etchant after the pattern of the source electrode 7 and the drain electrode 8 mainly composed of Al is formed in the above manufacturing process, the processing is often performed. There may be a situation in which the Al pattern elutes at the end time.

This is because Al originally has a property of being dissolved in an HCl-HNO ₃ —H ₂ O-based etching solution which is an ITO etching solution. HNO ₃ in the etching solution is added to form a thin Al oxide film on the Al surface to prevent the elution of Al, but the etching time of the ITO film is long, or the Al film mixed during Al deposition If there are defective parts such as impurities and foreign matters, it is considered that the above-described oxidation effect of Al does not sufficiently act due to the local battery reaction.

To prevent dissolution of such Al, an ITO film by an amorphous, it is known to increase the ITO / Al etching rate ratio _HCl-HNO 3 -H ₂ O-based etchant Yes. This is described in, for example, Patent Document 1 described later. The etching rate ratio means an etching rate ratio.

However, since the use of ITO film etching solution HCl-HNO 3 _-H 2 _O system even in the amorphous, hard and elution Al is not completely prevented, to achieve a high-definition liquid crystal display Met. Patent Document 2 described later is known as an invention made in view of such a problem. In this patent document 2, patterning of the Al electrode, the transparent electrode, and the pixel electrode 9 on each pattern of the source electrode / drain electrode is facilitated by using an oxalic acid-based etching solution, and high-definition is achieved. For the purpose of providing a method for producing a liquid crystal display, it has been proposed to use a transparent electrode having a composition comprising indium oxide-zinc oxide.

  In such a configuration, it is known that contact resistance occurs between the Al gate line / transparent electrode and the Al source / drain electrode / pixel electrode. Usually, the Al line is formed of a barrier metal such as Ti, Cr, Mo, etc. It is common to cover with. Such barrier metals are described in Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6 described later.

JP 63-184726 A JP-A-11-264996 JP-A-10-65174 JP-A-11-184195 JP 11-258625 A Japanese Patent Laid-Open No. 11-253976

  This invention is made | formed in view of the said subject, It is simplifying the manufacturing method of a TFT (thin film transistor) board | substrate by using the transparent conductive material containing a specific metal for a pixel electrode and a transparent electrode. . In other words, it is an object of the present invention to provide a manufacturing method that does not require a step for depositing barrier metal or the like.

  Similarly, an object of the present invention is to provide a sputtering target for forming such a pixel electrode and a transparent electrode by sputtering.

  Another object of the present invention is to use a transparent conductive material containing a specific metal for a pixel electrode and a transparent electrode so that an Al gate / transparent electrode and an Al source / drain / pixel electrode can be formed (without a barrier metal). ) The purpose is to reduce the contact resistance even when directly contacting. It is an object of the present invention to provide a liquid crystal display device capable of halftone display using a substrate using this transparent conductive material as a pixel electrode by realizing such a small contact resistance. is there.

A. Sputtering target (1) In order to solve the above-mentioned problems, the present invention provides a main component of indium oxide and one or more selected from the first metal group M1 consisting of W, Mo, Nb, Ni, Pt, and Pd. A sputtering target containing two or more kinds of metals or oxides of the metals and one or more kinds of metal oxides selected from the second metal group M2 made of a lanthanoid metal.

  Thus, in the present invention, one or more metal oxides selected from the second metal group M2 made of a lanthanoid metal, and W, Mo, Nb, Ni, Pt, It is a characteristic point that one or more metals or metal oxides selected from Pd are added simultaneously.

  With such a configuration, when a transparent conductive film is formed by sputtering using the sputtering target of the present invention, the contact resistance between the transparent conductive film and another Al member can be kept at a small value. .

Specifically, when a transparent electrode or a pixel electrode is formed by sputtering using the sputtering target of the present invention,
-Between the Al gate line / transparent electrode-Between the Al source / drain electrode / pixel electrode-The contact resistance value generated between the Al source / drain wiring / transparent electrode is changed to the contact resistance value that has been generated conventionally It is possible to make it smaller.

  In this patent, “main component” refers to a main component in the material, and refers to a component having a composition ratio of approximately 50% or more.

(2) Moreover, in order to solve the said subject, this invention is 1 type, or 2 or more types of metals or metals chosen from said 1st metal group M1 which consists of W, Mo, Nb, Ni, Pt, and Pd. The value of [M1] / ([M1] + [In]), which is the composition of the oxide with respect to indium oxide, is 0.005 to 0.2, and is selected from the second metal group M2 made of a lanthanoid metal The value of [M2] / ([M2] + [In]), which is a composition with respect to indium oxide, of one or more metal oxides is 0.005 to 0.2. The sputtering target according to claim 1. Here, [M1] represents the number of atoms of one or more metals selected from the first metal group, and [M2] is one type selected from the second metal group. Alternatively, it represents the number of atoms of two or more metals, and [In] represents the number of atoms of indium.

The composition thus lanthanoid-based metal oxide, in the present invention, the composition of the lanthanoid-based metal oxide, relative to indium oxide,
"Formula 1"
[M2] / ([M2] + [In]) = 0.005 to 0.2
It is. This value is preferably 0, 01 to 0.15. More preferably, it is 0.01-0.1.

  In this patent, the lanthanoid metal group is referred to as the second metal group and is collectively referred to as “M2”. This M2 is also used as a symbol representing any lanthanoid metal.

  Further, in this patent, the symbol [] is used as a symbol representing the number of atoms per unit weight / volume of the atoms. For example, [cerium] and [Ce] represent the number of cerium atoms. [Indium] and [In] represent the number of indium atoms.

  Furthermore, a description method [M2] in which M2 which is a generic name of the above metal group is inserted in [] is also used. [M2] represents the number of metal atoms appropriately selected from the second metal group.

  If the value of this formula is less than 0.005, the effect of addition hardly appears, and when a transparent electrode or a pixel electrode is manufactured with such a sputtering target, between Al and the transparent electrode, Al and the pixel electrode During this time, a large value of contact resistance may occur.

  On the other hand, if the value of the above formula exceeds 0.2, when a transparent electrode or a pixel electrode is manufactured with such a sputtering target, the specific resistance of the transparent electrode / pixel electrode itself may become a large value. . Similarly, when the value of the above formula exceeds 0.2, the transparent electrode or the pixel electrode itself may be difficult to etch, and as a result, it may be difficult to manufacture a substrate for a liquid crystal display device. There is.

Composition of W, Mo, Nb, Ni, Pt, Pd metal or metal oxide In the present invention, the composition (ratio) of W, Mo, Nb, Ni, Pt, Pd metal or metal oxide is relative to indium oxide. And
"Formula 2"
[M1] / ([M1] + [In]) = 0.005 to 0.2
It is. More preferred values for this formula are from 0.01 to 0.15, even more preferably from 0.01 to 0.1. Moreover, these W, Mo, Nb, Ni, Pt, and Pd may be added in a metal state or a metal oxide state.

  Similar to the second metal group M2 described above, a metal group composed of W, Mo, Nb, Ni, Pt, and Pd is referred to as a first metal group M1. Similarly to [M2] above, [M1] represents the number of atoms (per unit volume / unit weight) of one or more metals selected from the first metal group.

  In addition, if the value of the said Formula 2 is less than 0.005, the addition effect will not appear easily. That is, the contact resistance may increase between Al and the transparent electrode or between Al and the pixel electrode. On the other hand, if the value of Equation 2 is more than 0.2, the specific resistance of the transparent electrode and the pixel electrode may increase, and it may be difficult to etch the transparent electrode and the pixel electrode.

(3) Further, in the present invention, an oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is made of any one or more metals selected from La, Ce, Ho, and Er. The sputtering target according to claim 1, wherein the sputtering target is an oxide.

  Thus, among the lanthanoid metal oxides, particularly when one or more metal oxides of Ce, Ho, and Er are added, the above-described functions and effects become more remarkable. In addition, since it is 1 or more types, 2 types of metals may be selected from the said metal, and all 3 types of metal oxides may be added.

(4) In the present invention, one or more metals selected from the first metal group M1 mainly composed of indium oxide and made of W, Mo, Nb, Ni, Pt, and Pd, or the metal thereof. From an oxide, an oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal, and a third metal group M3 made of Zn, Sn, Zr, Ga, Ge A sputtering target comprising one or more selected metal oxides.

  Thus, in the present invention, the first metal composed of W, Mo, Nb, Ni, Pt, and Pd and one or more metal oxides selected from the second metal group composed of the lanthanoid metal are used. The structure which adds simultaneously the 1 type (s) or 2 or more types of metal chosen from the group, or the oxide of the metal is employ | adopted.

  Conventionally, a large contact resistance has occurred between the Al gate line / transparent electrode, between the Al source / drain electrode / pixel electrode, and between the Al source / drain wiring / transparent electrode.

  On the other hand, according to the present invention described above, the large contact resistance value that has been conventionally generated can be reduced by the above-described configuration. In other words, the contact resistance can be reduced to such an extent that it can be virtually ignored.

  Furthermore, by adding one or more metal oxides selected from the third metal group consisting of ZnSn, Zr, Ga, and Ge, the resistance value of the sputtering target itself is improved, and nodule generation occurs. Can be suppressed. Here, the improvement of the resistance value is to reduce the resistance value. Further, the transparent conductive film prepared by sputtering using this sputtering target has a beneficial effect as shown below.

・ The specific resistance of the created transparent conductive film can be improved. ・ The etching characteristics of the created transparent conductive film can be improved. ・ The transparency of the created transparent conductive film can be improved. Here, the improvement of the specific resistance is the specific resistance value. Means reduction. Moreover, the improvement of etching characteristics means that it is more easily dissolved by an etchant used for etching. Further, the improvement of transparency means that the transparency is improved, and that the light transmittance value approaches 100%.

(5) Moreover, this invention is a composition with respect to indium oxide of the 1 type, or 2 or more types of metal or metal oxide chosen from said 1st metal group M1 which consists of W, Mo, Nb, Ni, Pt, and Pd. The value of [M1] / ([M1] + [In]) is 0.005 to 0.2, and one or more selected from the second metal group M2 made of the lanthanoid metal The value of [M2] / ([M2] + [In]), which is the composition of the metal oxide with respect to indium oxide, is 0.005 to 0.2, from Zn, Sn, Zr, Ga, and Ge. The value of [M3] / ([M3] + [In]), which is a composition with respect to indium oxide, of an oxide of one or more metals selected from the third metal group is 0.005 to 0 The sputtering target according to claim 4, wherein the sputtering target is. Here, [M1] represents the number of atoms of one or more metals selected from the first metal group, and [M2] is one type selected from the second metal group. Or, the number of atoms of two or more metals is represented, [M3] represents the number of atoms of one or more metals selected from the third metal group, and [In] represents indium. Represents the number of metal atoms.

Thus lanthanoid metal oxide, in the present invention, with respect to the composition of the lanthanoid-based metal oxide is indium oxide, In [In] / ([In] + [M2]) = 0.005~0.2 is there. Here, [M2] is sometimes referred to as [lanthanoid metal], but in any case represents the number of atoms of the lanthanoid metal oxide.

  The range of the value of the ratio of the number of atoms described in the present invention “0.005 to 0.2” is preferably 0.01 to 0.15, and more preferably 0.01 to 0.00. 1.

  If the value of the above formula representing the composition of the lanthanoid metal oxide with respect to indium oxide is less than 0.005, the addition effect may not appear. That is, there may be a contact resistance that cannot be ignored between Al, the transparent electrode, and the pixel electrode.

  On the other hand, if the value is more than 0 or 2, there may be a case where the specific resistance of the transparent electrode or the pixel electrode becomes large, or the etching of the transparent electrode / pixel electrode becomes difficult in the manufacturing process. .

W, Mo, Nb, Ni, Pt, Pd metal or metal oxide In the present invention, the composition of W, Mo, Nb, Ni, Pt, Pd metal or metal oxide is [In ] / ([In] + [M1]) = 0.005 to 0.2. The value of this formula is more preferably 0.01 to 0.15, and even more preferably 0.01 to 0.1. [M1] represents the number of one or more metals selected from the first metal group W, Mo, Nb, Ni, Pt, and Pd.

  W, Mo, Nb, Ni, Pt, and Pd in the first metal group M1 may be added in a metal state or in a metal oxide state.

  If the value of the above formula is less than 0.005, the effect of adding W, Mo, Nb, Ni, Pt, and Pd may not appear. Specifically, regarding transparent electrodes and pixel electrodes created by sputtering using the sputtering target of the present invention, non-negligible contact resistance occurs between Al and its transparent electrodes and between Al and its pixel electrodes. There is a case.

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent electrode / pixel electrode may increase. Further, in the manufacturing process, it may be difficult to etch the transparent electrode and the pixel electrode.

Zn, Sn, Zr, Ga, Ge oxide In the present invention, as described above, one or more selected from the oxides of Zn, Sn, Zr, Ga, Ge in the third metal group M3 The composition of the metal oxide is [M3] / ([In] + [M3]) = 0.005 to 0.2 with respect to indium oxide. Here, [M3] represents the number per unit volume / unit mass of one or more metals selected from the third metal group, and the above formula represents the number of metals in the third metal group relative to indium. Represents the atomic composition ratio. Note that the value of this equation is also substantially the composition ratio of the metal oxide in the third metal group M3 with respect to indium oxide.

  If the value of this formula is less than 0.005, the effect of addition is unlikely to appear. Specifically, with respect to the transparent electrode / pixel electrode formed by sputtering using the sputtering target of the present invention, contact resistance with a non-negligible magnitude occurs between Al and the transparent electrode and between Al and the pixel electrode. There is a case.

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent electrode and the pixel electrode may increase, or it may be difficult to etch these transparent electrodes in the manufacturing process.

(6) Further, in the present invention, the metal oxide selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. (4) or (5) is a sputtering target.

  Among lanthanoid metal oxides, oxides made of Ce, Ho, Er are particularly suitable. Therefore, oxides made of Ce, Ho, Er are used in the present invention.

(7) In addition, the present invention includes indium oxide as a main component, one or more metals selected from the first metal group M1 composed of W, Mo, Nb, Ni, Pt, and Pd, or a metal thereof. A transparent conductive film comprising an oxide and an oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal.

  Thus, in the present invention, the following two types of substances are added to indium oxide.

One or more metal oxides selected from lanthanoid metal oxides One or more metals or metal oxides selected from W, Mo, Nb, Ni, Pt, and Pd Then, these are simultaneously added to the transparent conductive film. Therefore, when a transparent electrode or a pixel electrode is configured using the transparent conductive film of the present invention,
• Between Al gate line / transparent electrode • Between Al source / drain electrode / pixel electrode • Contact resistance generated between Al source / drain wiring / transparent electrode, etc. can be reduced to a negligible value.

  On the other hand, when a transparent electrode / pixel electrode is configured using a conventional transparent conductive film, the Al gate line / transparent electrode, the Al source / drain electrode / pixel electrode, and the Al source / pixel electrode Between the drain wiring / transparent electrode, contact resistance with a magnitude that cannot be ignored has occurred.

(8) Moreover, this invention is a composition with respect to indium oxide of the 1 type, or 2 or more types of metal or metal oxide selected from the said 1st metal group M1 which consists of W, Mo, Nb, Ni, Pt, and Pd. The value of [M1] / ([M1] + [In]) is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is The transparent conductive film according to (7), which is 0.005 to 0.2. [M1] represents the number of one or more metal atoms selected from the first metal group, and [M2] represents one or two kinds selected from the second metal group. The number of atoms of the above metal is represented, and [In] represents the number of atoms of indium.

Thus lanthanoid metal oxide, in the present invention, with respect to the composition of the lanthanoid-based metal oxide is indium oxide, [M2] / ([In ] + [M2]) = 0.005~0.2 and It is set to be. [M2] represents the number of one or more metal atoms in the second metal group M2 made of a lanthanoid metal. Here, this number is a number per unit mass / unit volume. [In] represents the number of indium atoms per unit volume / unit mass. Therefore, the above formula is the composition ratio of the metal in the second metal group M2 to indium in terms of the number of atoms. This composition ratio is also the composition ratio of the metal oxide in the second metal group M2 to indium oxide.

  This value is preferably 0.01 to 0.15, and more preferably 0.01 to 0.1.

  If the value of the above formula representing the composition of the lanthanoid metal oxide with respect to indium oxide is less than 0.005, the addition effect may not appear. That is, with respect to the transparent electrode or pixel electrode using this transparent conductive film, a non-negligible contact resistance may occur between Al of other wiring and this transparent electrode / pixel electrode.

  On the other hand, when the above value is more than 0 or 2, the specific resistance of the transparent electrode / pixel electrode made of the transparent conductive film of the present invention becomes large, or the etching of the transparent electrode / pixel electrode becomes difficult in the manufacturing process. , Etc. may occur.

Thus, in the present invention, the composition of the lanthanoid metal oxide is [M2] / ([In] + [M2]) = 0.005 to 0.2 with respect to indium oxide. The ratio is preferably 0.01 to 0.15. Furthermore, it is still more preferably 0.01 to 0.1.
W, Mo, Nb, Ni, Pt, Pd metal or metal oxide In the present invention, the composition of the metal or metal oxide in the first metal group consisting of W, Mo, Nb, Ni, Pt, Pd is For indium oxide, a configuration of [M1] / ([In] + [M1]) = 0.005 to 0.2 is employed. The value of this formula is more preferably 0.01 to 0.15, and even more preferably 0.01 to 0.1. The W, Mo, Nb, Ni, Pt, and Pd may be added in a metal state or may be added in a metal oxide state.

  M1 is a generic name for the first metal group consisting of W, Mo, Nb, Ni, Pt, and Pd, and [M1] is a unit mass and unit volume of one or more metals in the first metal group. Represents the number. As described above, [In] represents the number of indium atoms per unit mass / unit volume.

  If the value of the above formula is less than 0.005, the effect of adding W, Mo, Nb, Ni, Pt, and Pd may not appear. Specifically, with respect to the transparent electrode / pixel electrode using the transparent conductive film of the present invention, a non-negligible contact resistance may occur between Al and the transparent electrode and between Al and the pixel electrode. .

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent electrode / pixel electrode made of the transparent conductive film of the present invention may increase. Furthermore, the transparent electrode / pixel electrode may be difficult to etch in the manufacturing process.

(9) Further, in the present invention, the metal oxide selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. The transparent conductive film according to (7) or (8), wherein

  Thus, among the lanthanoid metal oxides, it is preferable to employ an oxide made of Ce, Ho, Er.

(10) Further, the present invention provides indium oxide as a main component, one or more metals selected from the first metal group M1 consisting of W, Mo, Nb, Ni, Pt, and Pd, or a metal thereof. From an oxide, an oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal, and a third metal group M3 made of Zn, Sn, Zr, Ga, Ge A transparent conductive film comprising one or more selected metal oxides.

  Thus, in the present invention, an oxide of one or more metals selected from the lanthanoid metal group (second metal group) and W, Mo, Nb, Ni, Pt, Pd (first metal) The structure which adds simultaneously the 1 type (s) or 2 or more types of metal or metal oxide chosen from the group) is employ | adopted.

When a conventional transparent conductive film is used as a transparent electrode or a pixel electrode,
• Between Al gate line / transparent electrode • Between Al source / drain electrode / pixel electrode • Large contact resistance occurred between Al source / drain wiring / transparent electrode.

  On the other hand, if a transparent electrode or a pixel electrode is configured using the transparent conductive film according to the present invention, the above-described configuration can reduce the value of a large contact resistance that has been conventionally generated. In other words, the contact resistance can be reduced to a level that can be ignored.

  Furthermore, the addition of one or more metal oxides selected from ZnSn, Zr, Ga, Ge (third metal group M3) has a beneficial effect as shown below.

・ The specific resistance of the created transparent conductive film can be improved. ・ The etching characteristics of the created transparent conductive film can be improved. ・ The transparency of the created transparent conductive film can be improved. Here, the improvement of the specific resistance is the specific resistance value. Means reduction. Moreover, the improvement of etching characteristics means that it is more easily dissolved by an etchant used for etching. Moreover, the improvement of transparency means that the value of light transmittance approaches 100%.

(11) Moreover, this invention is a composition with respect to indium oxide of the 1 type, or 2 or more types of metal or metal oxide chosen from said 1st metal group M1 which consists of W, Mo, Nb, Ni, Pt, and Pd. The value of [M1] / ([M1] + [In]) is 0.005 to 0.2, and one or more selected from the second metal group M2 made of the lanthanoid metal The value of [M2] / ([M2] + [In]), which is the composition of the metal oxide with respect to indium oxide, is 0.005 to 0.2, from Zn, Sn, Zr, Ga, and Ge. The value of [M3] / ([M3] + [In]), which is a composition with respect to indium oxide, of an oxide of one or more metals selected from the third metal group is 0.005 to 0 The transparent conductive film according to claim 10, which is .2. Here, [M1] represents the number of atoms of one or more metals selected from the first metal group, and [M2] is one type selected from the second metal group. Or, the number of atoms of two or more metals is represented, [M3] represents the number of atoms of one or more metals selected from the third metal group, and [In] represents indium. Represents the number of atoms.

Thus lanthanoid metal oxide, in the present invention, the composition of the oxide of the lanthanoid-based metal group (second metal group) relative to indium oxide, [M2] / ([In ] + [M2]) = It is set to 0.005 to 0.2. M2 is a generic name for the second metal group made of a lanthanoid metal, and [M2] represents the number of one or more metals selected from the second metal group. Here, [M2] is a number per unit mass / unit weight. As described above, [In] is the number of indium atoms per unit mass / unit weight. Therefore, the above formula represents the ratio of the number of atoms to the indium of the metal contained in the second metal group. The value of this formula is also the composition ratio of the metal oxide contained in the second metal group to indium oxide.

  This value is preferably 0.01 to 0.15, and more preferably 0.01 to 0.1.

  If the value of the above formula representing the composition of the lanthanoid metal oxide with respect to indium oxide is less than 0.005, the addition effect may not appear. That is, there may be a contact resistance that cannot be ignored between Al and a transparent electrode or pixel electrode made of the transparent conductive film of the present invention.

  On the other hand, when the above value is more than 0 or 2, the specific resistance of the transparent electrode / pixel electrode made of the transparent conductive film of the present invention becomes large, or the etching of the transparent electrode / pixel electrode becomes difficult in the manufacturing process. , Etc. may occur.

W, Mo, Nb, Ni, Pt, Pd metal or metal oxide In the present invention, the metal contained in the first metal group M1 composed of W, Mo, Nb, Ni, Pt, Pd or oxidation of the metal The composition of the product employs a configuration of [M1] / ([In] + [M1]) = 0.005 to 0.2 with respect to indium oxide. As already described, [M1] represents the number of metal atoms in the first metal group. This number is a number per unit mass / unit volume.

  The value of this formula is more preferably 0.01 to 0.15, and even more preferably 0.01 to 0.1. The W, Mo, Nb, Ni, Pt, and Pd may be added in a metal state or may be added in a metal oxide state.

  If the value of the above formula is less than 0.005, the effect of adding W, Mo, Nb, Ni, Pt, and Pd may not appear. Specifically, regarding the transparent electrode / pixel electrode made of the transparent conductive film of the present invention, a contact resistance that cannot be ignored may occur between Al and the transparent electrode and between Al and the pixel electrode.

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent electrode / pixel electrode made of the transparent conductive film of the present invention may increase. Furthermore, the transparent electrode / pixel electrode may be difficult to etch in the manufacturing process.

Zn, Sn, Zr, Ga, Ge oxide In the present invention, as described above, one or more metals selected from the third metal group M3 made of Zn, Sn, Zr, Ga, Ge are used. The composition of the oxide is [M3] / ([In] + [M3]) = 0.005 to 0.2 with respect to indium oxide. [M3] represents the number of atoms of one or more metals selected from the third metal group M3. Therefore, this formula is the composition ratio (the number of atoms) of one or more metals in the third metal group M3 to indium. This value also represents the composition ratio of the oxide of one or more metals selected from the third metal group to indium oxide.

  When the value (composition ratio) of this formula is less than 0.005, the effect of addition hardly appears. Specifically, with respect to the transparent electrode / pixel electrode made of the transparent conductive film of the present invention, a contact resistance with a non-negligible magnitude may occur between Al and the transparent electrode and between Al and the pixel electrode. .

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent electrode / pixel electrode using the transparent conductive film of the present invention may increase, or the transparent electrode / pixel electrode may be etched in the manufacturing process. May be difficult.

(12) Further, according to the present invention, the metal oxide selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. The transparent conductive film according to (11) or (12), wherein

  Thus, among the lanthanoid metal oxides, it is preferable to employ an oxide made of Ce, Ho, Er.

(13) Further, the present invention is selected from a glass substrate and a first metal group M1 provided on the glass substrate, the main component being indium oxide, and W, Mo, Nb, Ni, Pt, and Pd. A transparent conductive film comprising one or two or more metals or oxides of the metals and one or more oxides of one or more metals selected from the second metal group M2 made of a lanthanoid metal; A transparent conductive glass substrate comprising a metal thin film mainly composed of Al or Ag provided on the glass substrate.

  As described above, in the present invention, the oxide of one or more metals selected from the second metal group M2 made of the lanthanoid metal, and W, Mo, Nb, Ni, Pt, and Pd are used. A configuration in which one or more metals or metal oxides selected from the first metal group M1 are added simultaneously (referred to as a simultaneous addition configuration) is employed.

  Moreover, the transparent conductive glass of this invention can be utilized as a board | substrate provided with the transparent electrode and the pixel electrode by utilizing a transparent conductive film as a transparent electrode or a pixel electrode. When the metal thin film of the present invention adopts Al, it can constitute an Al gate line and an Al source / drain electrode. Therefore, the transparent conductive glass substrate of the present invention can be used as a substrate with wiring.

Now, in such a case, according to the conventional transparent conductive glass,
・ Between Al gate line and transparent electrode,
・ Between Al source / drain electrode / pixel electrode ・ A large contact resistance was generated between the Al source / drain wiring / transparent electrode. On the other hand, according to the transparent conductive glass of this invention, a big contact resistance is not produced.

  In addition, when using Ag for a metal thin film, an Ag gate line and an Ag source / drain electrode can be constituted. Also in this case, the same effect as that of Al is obtained.

  As described above, according to the present invention, the large contact resistance value that has been conventionally generated can be reduced by the above-described configuration (simultaneous addition configuration). In other words, the contact resistance can be reduced to such an extent that it can be virtually ignored.

  Furthermore, by adopting a structure laminated with Al or Ag, a transparent conductive glass with lower resistance can be obtained. Such transparent conductive glass is sometimes referred to as laminated transparent conductive glass.

Use of Al or Al alloy In (13) and (16) described later, Al or Al alloy is preferably used for the gate line, source / drain electrode or wiring. In this case, it is called an Al gate line or an Al source / drain electrode, but an alloy containing Al as a main component is often used. Al or Al alloy used in these materials contains Al as a main component, but may contain heavy metals IIIa to VIIIa or lanthanoid metals in the periodic table. For example, it is desirable to include Nd, Ni, Co, Zr and the like. The content depends on the required performance of the Al gate line and Al source / drain electrodes, but is generally preferably in the range of 0.1 to 5% by weight. A more preferable content is 0.5 to 2.0% by weight.

  When the content is less than 0.1% by weight, the effect of addition may not appear, and when the content is 0.1% by weight, protrusions such as hillocks may be generated on the Al thin film.

  On the other hand, if the content exceeds 0.5% by weight, the resistance value of Al itself (Al alloy itself) may increase.

  In the present invention, Ag or an Ag alloy is also preferably used for the gate line, source / drain electrode, or wiring. Moreover, although the reflective electrode which reflects light may be provided, Ag and Ag alloy may be used suitably also for this reflective electrode.

  When Ag is used, it is called an Ag gate line, an Ag source / drain electrode, or the like. Ag or an Ag alloy used for these may contain Ag as a main component and include heavy metals from IIIa to VIIIa in the periodic table or lanthanoid metals. For example, it is desirable to include Nd, Ni, Co, Zr and the like. The content depends on the performance of the required Al gate line, Al source / drain electrode, wiring or reflective electrode, but is generally preferably in the range of 0.1 to 5% by weight. A more preferable content is 0.5 to 2.0% by weight.

  If the content is less than 0.1% by weight, the effect of addition may not appear. Further, if the content is 0.1% by weight, protrusions such as hillocks may occur on the Ag thin film, or the adhesion of the Ag thin film may be poor. This is because it may decrease.

  On the other hand, if the content exceeds 0.5% by weight, the resistance value of Ag itself (Ag alloy itself) may increase.

(14) Further, the present invention provides a composition of indium oxide of one or more metals or metal oxides selected from the first metal group M1 composed of W, Mo, Nb, Ni, Pt, and Pd. The value of [M1] / ([M1] + [In]) is 0.005 to 0.2, and one or more selected from the second metal group M2 made of the lanthanoid metal The value of [M2] / ([M2] + [In]), which is the composition of the metal oxide with respect to indium oxide, is 0.005 to 0.2. It is a conductive glass substrate. Here, [M1] represents the number of atoms of one or more metals selected from the first metal group, and [M2] is one type selected from the second metal group. Or it represents the number of atoms of two or more metals.

Thus lanthanoid metal oxide, in the present invention, the composition of the lanthanoid-based metal oxide with respect to indium oxide, is the In / (In + lanthanide metal) = 0.005 to 0.2.

  This value is preferably 0.01 to 0.15, and more preferably 0.01 to 0.1.

  If the value of the above formula representing the composition of the lanthanoid metal oxide with respect to indium oxide is less than 0.005, the addition effect may not appear. That is, there may be a case where non-negligible contact resistance occurs between a metal thin film mainly composed of Al or Ag and a transparent conductive film (for example, constituting a transparent electrode or a pixel electrode).

  On the other hand, when the value is more than 0 or 2, when the specific resistance of the transparent conductive film of the present invention (for example, constituting a transparent electrode / pixel electrode) is increased, or in the manufacturing process, the transparent conductive film is etched. When it becomes difficult, there exists a possibility that etc. may arise.

W, Mo, Nb, Ni, Pt, Pd metal or metal oxide In the present invention, the composition of W, Mo, Nb, Ni, Pt, Pd metal or metal oxide is In / A configuration of (In + (W, Mo, Nb, Ni, Pt, Pd)) = 0.005 to 0.2 is employed. The value of this formula is more preferably 0.01 to 0.15, and even more preferably 0.01 to 0.1. The W, Mo, Nb, Ni, Pt, and Pd may be added in a metal state or may be added in a metal oxide state.

  If the value of the above formula is less than 0.005, the effect of adding W, Mo, Nb, Ni, Pt, and Pd may not appear. Specifically, a non-negligible contact resistance may occur between the transparent conductive film of the present invention (for example, constituting a transparent electrode / pixel electrode) and a metal thin film containing Al or Ag as a main component. is there.

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent conductive film (for example, transparent electrode / pixel electrode) of the present invention may increase. Furthermore, it may be difficult to etch the transparent conductive film in the manufacturing process.

Laminating Thus, a transparent conductive film composition as described above, and the metal thin film, by laminating, it is possible to provide a transparent conductive glass of lower resistance.

(15) Further, in the present invention, the metal oxide selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. The transparent conductive glass substrate according to (13) or (14), wherein

  As described above, among lanthanoid metal oxides, it is more effective to use an oxide composed of at least one of Ce, Ho, and Er, which can be suitably used.

(16) In addition, the present invention is selected from a glass substrate and a first metal group M1 provided on the glass substrate, the main component being indium oxide, and W, Mo, Nb, Ni, Pt, and Pd. One or more metals or oxides of the metals, oxides of one or more metals selected from the second metal group M2 made of lanthanoid metals, and Zn, Sn, Zr A transparent conductive film composed of an oxide of one or more metals selected from the third metal group M3 composed of Ga, Ge, and Al or Ag as a main component provided on the glass substrate. A transparent conductive glass substrate comprising: a metal thin film.

  As described above, in the present invention, the oxide of one or more metals selected from the second metal group M2 made of the lanthanoid metal, and W, Mo, Nb, Ni, Pt, and Pd are used. A configuration in which one or more metals or metal oxides selected from the first metal group M1 are added simultaneously (referred to as a simultaneous addition configuration) is employed.

  Moreover, the transparent conductive glass of this invention can be utilized as a board | substrate provided with the transparent electrode and the pixel electrode by utilizing a transparent conductive film as a transparent electrode or a pixel electrode. When the metal thin film of the present invention adopts Al, it can constitute an Al gate line and an Al source / drain electrode. Therefore, the transparent conductive glass substrate of the present invention can be used as a substrate with wiring.

Now, in such a case, according to the conventional transparent conductive glass,
・ Between Al gate line and transparent electrode,
・ Between Al source / drain electrode / pixel electrode ・ A large contact resistance was generated between the Al source / drain wiring / transparent electrode. On the other hand, according to the transparent conductive glass of this invention, a big contact resistance is not produced.

  In addition, when using Ag for a metal thin film, an Ag gate line and an Ag source / drain electrode can be constituted. Also in this case, the same effect as that of Al is obtained.

  As described above, according to the present invention, the large contact resistance value that has been conventionally generated can be reduced by the above-described configuration (simultaneous addition configuration). In other words, the contact resistance can be reduced to such an extent that it can be virtually ignored.

  Further, by adding one or more metal oxides selected from ZnSn, Zr, Ga, and Ge, the transparent conductive film on the transparent conductive glass has a beneficial effect as described below.

・ The specific resistance of the created transparent conductive film can be improved. ・ The etching characteristics of the created transparent conductive film can be improved. ・ The transparency of the created transparent conductive film can be improved. Here, the improvement of the specific resistance is the specific resistance value. Means reduction. Moreover, the improvement of etching characteristics means that it is more easily dissolved by an etchant used for etching. Moreover, the improvement of transparency means that the value of light transmittance is improved. Furthermore, by adopting a structure laminated with Al or Ag, a transparent conductive glass with lower resistance can be obtained.

Such transparent conductive glass is sometimes referred to as laminated transparent conductive glass.

  Further, also in (16), as described in (13) above, Al or an Al alloy is preferably used for the gate line, source / drain electrode or wiring. The contents are the same as in the case of (13) above.

(17) Further, the present invention provides a composition of indium oxide of one or more metals or metal oxides selected from the first metal group M1 made of W, Mo, Nb, Ni, Pt, and Pd. The value of [M1] / ([M1] + [In]) is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is 0.005 to 0.2,
[M3] / ([M3] + [In] is a composition of indium oxide of an oxide of one or more metals selected from the third metal group consisting of Zn, Sn, Zr, Ga, and Ge. ]) Is 0.005 to 0.2. The transparent conductive glass substrate according to (16). Here, [M1] represents the number of atoms of one or more metals selected from the first metal group, and [M2] is one type selected from the second metal group. Or, the number of atoms of two or more metals is represented, [M3] represents the number of atoms of one or more metals selected from the third metal group, and [In] represents indium. Represents the number of atoms.

Thus lanthanoid metal oxide, in the present invention, the composition of the lanthanoid-based metal oxide with respect to indium oxide, is the In / (In + lanthanide metal) = 0.005 to 0.2.

  This value is preferably 0.01 to 0.15, and more preferably 0.01 to 0.1.

  If the value of the above formula representing the composition of the lanthanoid metal oxide with respect to indium oxide is less than 0.005, the addition effect may not appear. That is, there may be a case where non-negligible contact resistance occurs between a metal thin film mainly composed of Al or Ag and a transparent conductive film (for example, constituting a transparent electrode or a pixel electrode).

  On the other hand, when the value is more than 0 or 2, when the specific resistance of the transparent conductive film of the present invention (for example, constituting a transparent electrode / pixel electrode) is increased, or in the manufacturing process, the transparent conductive film is etched. When it becomes difficult, there exists a possibility that etc. may arise.

W, Mo, Nb, Ni, Pt, Pd metal or metal oxide In the present invention, the composition of W, Mo, Nb, Ni, Pt, Pd metal or metal oxide is In / A configuration of (In + (W, Mo, Nb, Ni, Pt, Pd)) = 0.005 to 0.2 is employed. The value of this formula is more preferably 0.01 to 0.15, and even more preferably 0.01 to 0.1. The W, Mo, Nb, Ni, Pt, and Pd may be added in a metal state or may be added in a metal oxide state.

  If the value of the above formula is less than 0.005, the effect of adding W, Mo, Nb, Ni, Pt, and Pd may not appear. Specifically, a non-negligible contact resistance may occur between the transparent conductive film of the present invention (for example, constituting a transparent electrode / pixel electrode) and a metal thin film containing Al or Ag as a main component. is there.

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent conductive film (for example, transparent electrode / pixel electrode) of the present invention may increase. Furthermore, it may be difficult to etch the transparent conductive film in the manufacturing process.

Zn, Sn, Zr, Ga, Ge oxide In the present invention, as described above, the composition of one or more metal oxides selected from Zn, Sn, Zr, Ga, Ge oxide is oxidized. In / (In + (Zn, Sn, Zr, Ga, Ge)) = 0.005 to 0.2 with respect to indium.

  If the value of this formula is less than 0.005, the effect of addition is unlikely to appear. Specifically, there is a contact resistance with a non-negligible magnitude between the transparent conductive film of the present invention (for example, constituting a transparent electrode / pixel electrode) and a metal thin film mainly composed of Al or Ag. May occur.

  On the other hand, if the value of the above formula exceeds 0.2, the specific resistance of the transparent conductive film of the present invention (or a transparent electrode / pixel electrode using the transparent conductive film) may increase. Furthermore, when the value of the above formula is more than 0.2, it may be difficult to etch the transparent conductive film and form a transparent electrode or a pixel electrode in the manufacturing process.

Laminating Thus, a transparent conductive film composition as described above, and the metal thin film, by laminating, it is possible to provide a transparent conductive glass of lower resistance.

(18) Further, according to the present invention, the metal oxide selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. The transparent conductive glass substrate according to (16) or (17), wherein

  As described above, among lanthanoid metal oxides, it is more effective to use an oxide composed of at least one of Ce, Ho, and Er, which can be suitably used.

Specific Technique for Lamination As described above in (1) to (18), in the present invention, a configuration in which a metal oxide conductive film and a metal thin film are laminated may be employed. Hereinafter, this case will be described.

  There are various modes for laminating the metal oxide transparent conductive film and a metal thin film mainly composed of Al or Ag.

a. Metal oxide / Metal thin film mainly composed of Al or Ag / Metal oxide b. Metal oxide / Metal thin film mainly containing Al or Ag / Metal oxide / Metal thin film mainly containing Al or Ag / Metal oxide Are three layers, b. Is 5 layers. In addition, it is of course preferable to adopt a seven-layer structure or the like.

  In this case, the film thickness of the metal thin film mainly composed of Al or Ag is 1 to 20 nm. The film thickness is preferably 5 to 15 nm, more preferably 5 to 10 nm. When the film thickness is 1 nm 1 or less, the laminated metal film may not be a “thin film” but may have a sea-island structure, and the effects of the present invention may not be obtained. On the other hand, when the thickness of the metal thin film is 20 nm or more, the light transmittance of the laminated metal thin film may decrease. As a result, the “transparent” property of the transparent conductive film provided in an overlapping manner may be substantially affected.

  In the present invention, the transparent conductive film often made of a metal oxide and a metal thin film mainly composed of Al or Ag are laminated. This “lamination” is made of a metal metal oxide. The case where a part (not all) of the transparent conductive film is in contact with the metal thin film is also included. In this case, as the electrode configuration, for example, a case where a part of the metal thin film with a width of 20 μm is in contact and a transparent conductive film is in contact with the metal thin film to cover the whole is mentioned. In other words, both are superimposed in a plan view, but when viewed from a cross-sectional view, only a part is in contact.

  In such a case, the thickness of the metal thin film is 20 to 500 nm, preferably 30 to 300 nm, more preferably 50 to 200 nm. When the film thickness is 20 nm or less, the effect of reducing the resistance may be small. On the other hand, when the film thickness is 500 nm or more, the level difference of the thin film is large, and a contact failure with the transparent conductive film may occur.

  Although the width | variety of a metal thin film can be selected suitably, it is 1 micrometer-100 micrometers, for example. This value is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  If the width of the metal thin film is 1 μm or less, the resistance reduction effect may be too small. On the other hand, when the width of the metal thin film is 100 μm or more, the light transmittance (aperture ratio) may decrease. However, this is not the case when a laminate of a metal thin film and a transparent conductive film is used as the reflective electrode.

  The present invention has been made in view of the problems of the above-described conventional technology, and by using a transparent conductive material containing a specific metal for a pixel electrode / transparent electrode, without using a barrier metal or the like, The contact resistance between the Al gate / transparent electrode and the Al source / drain / pixel electrode can be kept small.

  As a result, since the number of manufacturing steps can be reduced, the manufacturing method of a TFT (thin film transistor) substrate can be simplified.

  In addition, even if the transparent conductive (film) material according to the present invention is directly contacted with an Al gate or an Al source / drain electrode, the contact resistance generated there can be reduced, and a halftone display is good. It is possible to provide a liquid crystal display device that can be performed in a simple manner.

  In the description of the present invention so far, there is a portion where the present invention is described from the relationship with Al. Even if Ag is used in place of Al in this explanation, substantially the same operations and effects are obtained. This point will be described again in a later embodiment.

  Hereinafter, the best mode for carrying out the present invention will be described.

[Tungsten] / ([Tungsten] + [Indium]) In ₂ O ₃ powder having an average particle diameter of 1 μm or less, WO ₃ powder having an average particle diameter of 1 μm or less, and CeO ₂ having an average particle diameter of 1 μm or less The atomic number ratio represented by [Cerium] / ([Cerium + Indium]) was adjusted so that the atomic ratio represented by the formula 0.02 was 0.03.

  Such atomic ratios are shown in Table 1. In this patent, W, Mo, Nb, Ni, Pt, and Pd are referred to as a first metal group and are collectively referred to as “M1”. This M1 is also used as a symbol meaning any one of W, Mo, Nb, Ni, Pt, and Pd. In Table 1, M1 is used as a symbol representing any metal among W, Mo, Nb, Ni, Pt, and Pd.

また、本特許では、ランタノイド系金属群を、第２金属群と呼び、「Ｍ２」と総称している。また、このＭ２は、いずれかのランタノイド系金属を表す記号としても用いられている。表１中でも、Ｍ２は、ランタノイド系金属を表しており、具体的なランタノイド系金属としてＣｅ、Ｈｏ、Ｅｒ、Ｃｅが示されている。

In this patent, the lanthanoid metal group is referred to as the second metal group and is collectively referred to as “M2”. This M2 is also used as a symbol representing any lanthanoid metal. In Table 1, M2 represents a lanthanoid metal, and Ce, Ho, Er, and Ce are shown as specific lanthanoid metals.

  In this patent, as will be described later, Zn, Sn, Zr, Ga, and Ge are referred to as a third metal group and are collectively referred to as “M3”. This M3 is also used as a symbol meaning any one of Zn, Sn, Zr, Ga, and Ge. In Table 1, M3 is used as a symbol representing any metal among Zn, Sn, Zr, Ga, and Ge.

  Further, in this patent, the symbol [] is used as a symbol representing the number of atoms per unit weight / volume of the atoms. For example, [tungsten] and [W] represent the number of tungsten atoms. [Indium] and [In] represent the number of indium atoms. Therefore, the above-mentioned [tungsten] / ([tungsten] + [indium]) represents the atomic ratio of tungsten to indium. This is the same even if it is described as [W] / ([W] + [In]).

  Similarly, the above [cerium] / ([cerium] + [indium]) represents the atomic ratio of cerium to indium. This also has the same meaning when described as [Ce] / ([Ce] + [In]).

  Furthermore, a description method of [M1], [M2], and [M3] in which M1, M2, and M3, which are generic names of the above metal groups, are inserted in [] is also used. [M1] represents the number of one or more metal atoms appropriately selected from the first metal group, and [M2] is one or two atoms appropriately selected from the second metal group. The number of the above metal atoms is represented, and [M3] represents the number of one or more metal atoms appropriately selected from the third metal group.

After blending at the above ratio, it was put into a resin pot, pure water was further added, and wet ball mill mixing using a hard ZrO ₂ ball mill was performed. The mixing time was 20 hours. The obtained mixed slurry was taken out, filtered, dried and granulated. The obtained granulated product was molded by a cold isostatic press while applying a pressure of 294 MPa (3 t / cm ² ).

Next, this compact was sintered as follows. In the sintering furnace, sintering was performed at 1500 ° C. for 5 hours in an atmosphere in which oxygen was introduced at a rate of 5 L / min per furnace inner volume of 0.1 m ³ . At this time, the temperature was increased up to 1000 ° C. at 1 ° C./min and 1000 to 1500 ° C. at 3 ° C./min. Thereafter, the introduction of oxygen was stopped, and the temperature was decreased from 1500 ° C. to 1300 ° C. at 10 ° C./min. Then, in cut open air introducing argon gas at a rate of furnace capacity 0.1 m ³ per 10L / min, after holding the 1300 ° C. 3 h, allowed to cool. Thereby, a tungsten and cerium-containing In ₂ O ₃ sintered body having a relative density of 95% or more was obtained.

The specific calculated value of relative density was 96% as shown in Table 1. The theoretical density at this time was calculated from the weight fraction of In ₂ O ₃ crystal (bixbite type structure) free of oxygen defects, W oxide, and Ce oxide.

  The sputter surface of the sintered body was polished with a cup grindstone, processed to a diameter of 100 mm and a thickness of 5 mm, and bonded to a backing plate using an indium-based alloy to obtain a sintered body target 1.

In the first embodiment, it is preferable that tungsten is dispersed, and particularly substituted and dissolved in the indium sites of indium oxide. That is, the form in which the tungsten is contained in the target may be a form of tungsten oxide such as WO ₃ or WO ₂ and may be dispersed in the indium oxide sintered body, but may be in the form of In ₂ W ₃ O ₁₂ or the like. It may be in the form of a composite oxide between indium oxide and tungsten oxide and dispersed in the indium oxide sintered body.

  Further, cerium may be pseudo-collected only with cerium oxide, or a part thereof may be substituted and dissolved in the indium site of indium oxide. By dispersing in this manner, the average diameter of the cerium oxide crystal particles obtained by image processing was 2.1 μm. The aggregation of cerium oxide should be 5 μm or less, preferably 4 μm, more preferably 3 μm or less. If the dispersion is insufficient and cerium oxide of 10 μm or more is present, abnormal discharge may be induced during sputter discharge or nodules may be generated.

  Further, by dispersing in this way, the average crystal particle diameter of indium oxide was 3.4 μm as shown in Table 1. This diameter was obtained by image processing.

  Further, it is preferable that tungsten atoms are dispersed and dissolved in indium sites of indium oxide so that tungsten is dispersed at the atomic level in the indium oxide sintered body. By dispersing in this way, the discharge is stabilized in sputtering, and the resulting transparent conductive thin film has the effect of reducing the resistance.

In ₂ O ₃ powder having an average particle diameter of 1 μm or less, MoO ₃ powder having an average particle diameter of 1 μm or less, and Ho ₂ O ₃ having an average particle diameter of 1 μm or less were used as raw material powders. In ₂ O ₃ powder, MoO ₃ powder and Ho ₂ O ₃ powder were mixed in a resin pot at a predetermined ratio and mixed by a wet ball mill. At that time, hard ZrO ₂ balls were used and the mixing time was 20 hours. The mixed slurry was taken out, filtered, dried and granulated. The granulated product was filled into a circular mold and formed into a disk shape by applying a pressure of 3 ton / cm ² using a cold isostatic press.

  At this time, the composition ratio ([Mo] / ([Mo] + [In])) of Mo which is one of the first metal group M1 to 0.02 is 0.02, which is one of the second metal group M2. The composition ratio of Ho to indium ([Ho] / ([Ho] + [In])) is 0.04. Similar contents are shown in Table 1.

Next, the compact was placed in an atmosphere adjustment furnace and sintered. During sintering, sintering was performed at 1500 ° C. for 5 hours while introducing oxygen into the furnace at a rate of 5 liters / minute per 0.1 m ³ of the furnace volume. At this time, the temperature was raised from 1000 ° C. to 1 ° C./min and from 1000 ° C. to 1500 ° C. at a rate of 3 ° C./min. After the completion of sintering, the introduction of oxygen was stopped, and the temperature was decreased from 1500 ° C. to 1300 ° C. at a rate of 10 ° C./min. Then, Ar was introduced into the furnace at a rate of 10 liters / minute per 0.1 m ^{3 of} the furnace volume, held at 1300 ° C. for 3 hours, and then allowed to cool. Thereby, the sintered compact target 2 containing Mo with a density of 90% or more was obtained. The specific calculated value of relative density was 96% as shown in Table 1. The theoretical density at this time was calculated from the In ₂ O ₃ crystal (Bixbite type structure) free of oxygen defects, the weight fraction of the Mo oxide, and the weight fraction of the Ho oxide.

  Next, the surface used as the sputter surface of the obtained sintered body was polished with a cup grindstone and processed into a diameter of 152 mm and a thickness of 5 mm to obtain a target 2.

The form in which the molybdenum element is contained in the target may be a form in which molybdenum oxide such as MoO ₃ or MoO ₂ is dispersed in the indium oxide sintered body. However, InMo ₄ O ₆ and _In 2 _Mo 3 _{O 12, or,} In _ll Mo _{4 O 62} in the form of a composite oxide of indium and molybdenum may be in a form dispersed in the indium oxide sintered body, such as. Preferably, when the molybdenum atoms are substituted and dissolved in the indium sites of indium oxide and molybdenum is dispersed at the atomic level in the indium oxide sintered body, the discharge is more stable in sputtering, and it is manufactured by sputtering (transparent There is an effect of making the (conductive) film low resistance.

  Further, holmium may be aggregated only in holmium oxide, or a part thereof may be substituted and dissolved in the indium site of indium oxide. By dispersing in this manner, the average diameter of the holmium oxide crystal particles obtained by image processing was 1.8 μm. The aggregation of holmium oxide should be 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less. When the dispersion is not sufficiently performed and holmium oxide of 10 μm or more is present, abnormal discharge may be induced during sputter discharge, or nodule generation may be caused.

  By dispersing in this manner, the average crystal particle diameter of indium oxide was 3.6 μm as shown in Table 1. This diameter was determined by image processing.

As the raw material powder, In ₂ O ₃ powder, SnO ₂ powder, Nb ₂ O ₅ powder and Er ₂ O ₃ powder each having an average particle size of 1 μm or less were used. First, a predetermined amount of In ₂ O ₃ powder, SnO ₂ powder, Nb ₂ O ₅ powder, and Er ₂ O ₃ powder were weighed and mixed, and then placed in a resin pot and wet ball mill mixed using water as a medium. At that time, hard ZrO ₂ balls were used and the mixing time was 20 hours. Thereafter, the mixed slurry was taken out, filtered, dried and granulated. The obtained granulated product was put in a mold and molded into a predetermined shape by applying a pressure of 3 ton / cm ² with a cold isostatic press to obtain a molded body.

  At this time, the composition ratio ([Nb] / ([Nb] + [In])) of Nb which is one of the first metal group M1 to 0.03 is 0.03, which is one of the second metal group M2. The composition ratio of Er to indium ([Er] / ([Er] + [In])) is 0.05, and the composition ratio of Sn, which is one of the third metal groups M3, to indium ([Sn ] / ([Sn] + [In])) is 0.05. Similar contents are shown in Table 1.

  In this patent, Zn, Sn, Zr, Ga, and Ge are referred to as a third metal group and are collectively referred to as M3. This M3 is also used as a symbol meaning any one of Zn, Sn, Zr, Ga, and Ge. In Table 1, M3 is used as a symbol representing any metal among Zn, Sn, Zr, Ga, and Ge.

  In this patent, the symbol [] is used as a symbol representing the number of atoms per unit weight / volume of the atoms. For example, [niobium] and [Nb] represent the number of niobium atoms. [Indium] and [In] represent the number of indium atoms. Therefore, [Nb] / ([Nb] + [In]) described above represents the atomic ratio of tungsten to indium. This is the same even if it is described as [niobium] / ([niobium] + [indium]).

  Similarly, the above [Sn] / ([Sn] + [In]) represents the atomic ratio of tin to indium. This also has the same meaning when described as [tin] / ([tin] + [indium]).

  Furthermore, in this patent, [M3] is used as a symbol representing the number of one or more metals selected from the third metal group M3.

  Next, each of the obtained molded bodies was sintered by the following procedure.

First, oxygen was introduced into the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of} the furnace volume and held at 1500 ° C. for 5 hours. At this time, the temperature was increased up to 1000 ° C. at 1 ° C./min, and the temperature of 1000-1500 ° C. was increased at 3 ° C./min. Thereafter, the inflow of oxygen was stopped, and the temperature was lowered from 1500 ° C. to 1300 ° C. at 10 ° C./min. Thereafter, Ar was introduced at a rate of 10 liters / minute per 0.1 m ^{3 of} the furnace volume, held at 1300 ° C. for 3 hours, and then allowed to cool. The density of the obtained sintered body was measured according to the Archimedes method using water, and the relative density was calculated from the theoretical density. The theoretical density at this time was calculated from the weight fraction of oxides of In ₂ O ₃ crystal (Bixbite type structure) Sb, Nb, and Er without oxygen defects. The specific calculated value of relative density was 97% as shown in Table 1.

  Further, when the Sn, Nb, and Er contents in the sintered body were quantitatively analyzed by ICP emission analysis, it was confirmed that the charged composition at the time of mixing the raw material powder was maintained.

  Next, the sputter surface of the obtained sintered body was polished with a cup grindstone and processed into a diameter of 152 mm and a thickness of 5 mm to obtain a sintered compact target for a transparent conductive thin film. This was bonded to a backing plate using an In-based alloy to form a sputtering target 3.

The form in which tin, niobium and erbium are incorporated in the sputtering target is tin oxide (SnO, SnO ₂ , Sn ₃ O4), niobium oxide (Nb ₂ O ₅ , Nb ₂ O ₃ , NbO), erbium oxide (ErO, ErO). ₃ ) It is preferable to be dispersed. Further, it may be dispersed as a composite oxide between indium oxide-tin oxide, indium oxide-niobium oxide, and indium oxide-erbium oxide.

  Furthermore, a form in which tin, niobium, and erbium atoms are substituted and dissolved in the indium sites of indium oxide and dispersed at the atomic level in the indium oxide sintered body is very preferable. According to this dispersion mode, discharge is stable in sputtering, and a uniform low-resistance film can be obtained. By dispersing in this manner, the average crystal particle diameter of indium oxide was 3.7 μm as shown in Table 1. This diameter was obtained by image processing.

As the raw material powder, In ₂ O ₃ powder, ZnO powder, NiO powder, and CeO ₂ powder having an average particle diameter of 1 μm or less were used. First, a predetermined amount of In ₂ O ₃ powder, ZnO powder, and NiO powder were weighed and mixed, and then placed in a resin pot and wet ball mill mixed using water as a medium. At that time, hard ZrO ₂ balls were used and the mixing time was 20 hours. Thereafter, the mixed slurry was taken out, filtered, dried and granulated. The obtained granulated product was put in a mold and molded into a predetermined shape by applying a pressure of 3 ton / cm ² with a cold isostatic press to obtain a molded body. Next, each of the obtained molded bodies was sintered by the following procedure.

First, oxygen was introduced into the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of} the furnace volume and held at 1500 ° C. for 5 hours. At this time, the temperature was raised to 1000 ° C. at 1 ° C./min, and between 1000 to 1500 ° C. at 3 ° C./min. Thereafter, the inflow of oxygen was stopped, and the temperature was lowered from 1500 ° C. to 1300 ° C. at 10 ° C./min. Thereafter, Ar was introduced at a rate of 10 liters / minute per 0.1 m ^{3 of} the furnace volume, held at 1300 ° C. for 3 hours, and then allowed to cool.

  Note that the composition ratio ([Ni] / ([Ni] + [In])) of Ni, which is one of the first metal group M1, to 0.05 is 0.05, which is one of the second metal group M2. The composition ratio of Ce to indium ([Ce] / ([Ce] + [In])) is 0.03, and the composition ratio of Zn, which is one of the third metal groups M3, to indium ([Zn]). / ([Zn] + [In])) is 0.10. Similar contents are shown in Table 1.

Now, the density of the sintered body obtained as described above was measured according to the Archimedes method using water, and the relative density was calculated from the theoretical density. The theoretical density at this time was calculated from the weight fraction of In ₂ O ₃ crystal (bixbite type structure) free from oxygen defects and oxides of Zn, Ni, and Ce. The specific calculated value of relative density was 95% as shown in Table 1.

  Further, when the contents of Zn, Ni, and Ce in the sintered body were quantitatively analyzed by ICP emission analysis, it was confirmed that the charged composition at the time of mixing the raw material powder was maintained.

  Next, the sputter surface of the obtained sintered body was polished with a cup grindstone and processed into a diameter of 152 mm and a thickness of 5 mm to obtain a sintered compact target for a transparent conductive thin film. This was bonded to a backing plate using an In-based alloy to form a sputtering target 4.

The form in which zinc, nickel and cerium are incorporated in the sputtering target 4 may be dispersed as zinc oxide (ZnO), nickel oxide (NiO), cerium oxide (CeO ₄ , Ce ₂ O ₃ ), or indium oxide- it may be dispersed as a complex oxide of zinc oxide _{(in 2 Zn 2 O 5,} in 2 Zn 5 O 8, in 2 Zn 7 O 10, in 2 Zn 3 O 6, in 2 Zn 4 O 7).

Furthermore, it is very preferable that nickel or cerium atoms are substituted and dissolved in indium sites of indium oxide and dispersed at the atomic level in the indium oxide sintered body. According to this dispersion mode, the discharge during sputtering is stable, and a uniform low-resistance film is obtained as a result of sputtering. By dispersing in this way, the average crystal particle diameter of indium oxide is: As shown in Table 1, it was 3.4 μm. This diameter was obtained by image processing.

  On the other hand, the method for producing the sintered compact target (sputtering target) of the present invention is not particularly limited except that a mixture of a predetermined amount of indium oxide, zinc oxide, nickel oxide, and cerium oxide is used. After the above four components are mixed, molded, and sintered by using, a sintered body target (sputtering target) can be produced by molding the sintered body. In addition, components other than the above-mentioned four components may be added to the sintered compact target within a range that does not impair the sun of the present invention.

As the raw material powder, In ₂ O ₃ powder, ZnO powder, PtO ₂ powder, and CeO ₂ powder having an average particle diameter of 1 μm or less were used. First, a predetermined amount of In ₂ O ₃ powder, ZnO powder, and PtO ₂ powder were weighed and mixed, and then placed in a resin pot and mixed with a wet ball mill using water as a medium. At that time, hard ZrO ₂ balls were used and the mixing time was 20 hours. Thereafter, the mixed slurry was taken out, filtered, dried and granulated. The granulated product thus obtained was put into a mold and molded into a predetermined shape by applying a pressure of 3 ton / cm ² with a cold isostatic press to obtain a molded body. Next, the obtained molded body was sintered (respectively) according to the following procedure.

Oxygen was introduced into the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of the} furnace volume and held at 1450 ° C. for 5 hours. At this time, 1 ° C./minute up to 1000 ° C., 1000-1450 ° C. The temperature was raised at 3 ° C./min. Thereafter, the inflow of oxygen was stopped, and the temperature was decreased from 1450 ° C. to 1300 ° C. at 10 ° C./min. Thereafter, Ar was introduced at a rate of 10 liters / minute per 0.1 m ^{3 of} the furnace volume, held at 1300 ° C. for 3 hours, and then allowed to cool.

  In addition, the composition ratio ([Pt] / ([Pt] + [In])) of Pt, which is one of the first metal group M1, with respect to indium is 0.02, which is one of the second metal group M2. The composition ratio of Ce to indium ([Ce] / ([Ce] + [In])) is 0.03, and the composition ratio of Zn, which is one of the third metal groups M3, to indium ([Zn]). / ([Zn] + [In])) is 0.10. Similar contents are shown in Table 1.

Now, the density of the sintered body obtained as described above was measured according to the Archimedes method using water, and the relative density was calculated from the theoretical density. The theoretical density at this time was calculated from the weight fraction of In ₂ O ₃ crystal (Bixbite type structure) free from oxygen defects and oxides of Zn, Pt, and Ce. The specific calculated value of relative density was 95% as shown in Table 1.

  Further, when the contents of Zn, Pt and Ce in the sintered body were quantitatively analyzed by ICP emission analysis, it was confirmed that the charged composition at the time of mixing the raw material powder was maintained.

  Next, regarding the obtained sintered body, the sputter surface was polished with a cup grindstone and processed into a diameter of 152 mm and a thickness of 5 mm to obtain a sintered sputtering target for transparent conductive thin film. The sputtering target 5 was formed by attaching this sputtering target to a backing plate using an In-based alloy.

Zinc, nickel, and cerium may be incorporated into the sputtering target as zinc oxide (ZnO), platinum oxide (PtO ₂ ), cerium oxide (CeO ₄ , Ce ₂ O ₃ ), or indium oxide- it may be dispersed as a complex oxide of zinc oxide _{(in 2 Zn 2 O 5,} in 2 Zn 5 O 8, in 2 Zn 7 O 10, in 2 Zn 3 O 6, in 2 Zn 4 O 7).

  Also, platinum and cerium atoms are substituted and dissolved in the indium sites of indium oxide and dispersed at the atomic level in the indium oxide sintered body, so that the discharge is stable in sputtering, and a uniform low resistance film by sputtering. Is particularly preferable.

  This is because cerium oxide is dissolved in indium oxide, so that valence tetravalent cerium occupies the trivalent indium position in the indium oxide film, thereby releasing carrier electrons. This is because the conductivity increases.

  Moreover, a part of cerium oxide may exist by a cerium oxide single-piece | unit. Thus, the presence of cerium oxide alone suppresses abnormal growth of the indium oxide crystal, and thus suppresses the generation of nodules and abnormal discharge.

  By dispersing in this manner, the average crystal particle diameter of indium oxide was 3.7 μm as shown in Table 1. The value of this average diameter was obtained by image processing.

  On the other hand, the method for producing the sintered body (sputtering) target of the present invention is not particularly limited except that a mixture of a predetermined amount of indium oxide, zinc oxide, platinum oxide, and cerium oxide is used. The sintered body (sputtering) target can be produced by mixing, forming, and sintering the above four components, and then forming the sintered body.

  In addition, components other than the above four components may be added to the sintered body (sputtering) target as long as the object of the present invention is not impaired.

As the raw material powder, In ₂ O ₃ powder, ZnO powder, PdO powder, and CeO ₂ powder having an average particle diameter of 1 μm or less are used. First, a predetermined amount of In ₂ O ₃ powder, ZnO powder, and PdO powder were weighed and mixed, and then placed in a resin pot and wet ball mill mixed using water as a medium. At that time, hard ZrO ₂ balls were used and the mixing time was 20 hours. Thereafter, the mixed slurry was taken out, filtered, dried and granulated. The obtained granulated product was put into a mold and molded into a predetermined shape by applying a pressure of 3 ton / cm ² with a cold isostatic press to obtain a molded body.

  Next, each of the obtained molded bodies was sintered by the following procedure.

Oxygen was allowed to flow into the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of the} furnace volume and held at 1450 ° C. for 5 hours. At this time, the temperature was raised to 1000 ° C. at 1 ° C./min, and between 1000 to 1450 ° C. at 3 ° C./min. Thereafter, the inflow of oxygen was stopped, and the temperature was lowered from 1450 ° C. to 1300 ° C. at 10 ° C./min. Thereafter, Ar was introduced at a rate of 10 liters / minute per 0.1 m ^{3 of the} furnace internal volume, kept at 1300 ° C. for 3 hours, and then allowed to cool.

  In addition, the composition ratio ([Pd] / ([Pd] + [In])) of Pd, which is one of the first metal group M1, to 0.05 is 0.05, which is one of the second metal group M2. The composition ratio of Ce to indium ([Ce] / ([Ce] + [In])) is 0.03, and the composition ratio of Zn, which is one of the third metal groups M3, to indium ([Zn]). / ([Zn] + [In])) is 0.10. Similar contents are shown in Table 1.

Now, the density of the sintered body obtained as described above was measured according to the Archimedes method using water, and the relative density was calculated from the theoretical density. The theoretical density at this time was calculated from the weight fraction of In ₂ O ₃ crystal (bixbite type structure) free from oxygen defects and oxides of Zn, Pd, and Ce. The specific calculated value of relative density was 95% as shown in Table 1.

  Further, when the contents of Zn, Pd, and Ce in the sintered body were quantitatively analyzed by ICP emission analysis, it was confirmed that the charged composition at the time of mixing the raw material powder was maintained. Next, the sputter surface of the obtained sintered body was polished with a cup grindstone and processed into a diameter of 152 mm and a thickness of 5 mm to obtain a sintered body (sputtering) target for transparent conductive thin film. This sintered body (sputtering) target was bonded to a backing plate using an In-based alloy to form a sputtering target 6.

The form in which zinc, palladium, or cerium is incorporated in the sputtering target may be dispersed as zinc oxide (ZnO), palladium oxide (PdO), or cerium oxide (CeO ₄ , Ce ₂ O ₃ ), or indium oxide. - it may be dispersed as a complex oxide of zinc oxide _{(in 2 Zn 2 O 5,} in 2 Zn 5 O 8, in 2 Zn 7 O 10, in 2 Zn 3 O 6, in 2 Zn 4 O 7). Palladium and cerium atoms are substituted and dissolved in the indium oxide indium sites and dispersed at the atomic level in the indium oxide sintered body. The discharge is stable during sputtering, and a uniform low resistance film is obtained by sputtering. This is preferable.

  Since cerium oxide is dissolved in indium oxide in this way, valence tetravalent cerium occupies the indium position where the valence is trivalent in the indium oxide film. This is because (the cerium) emits carrier electrons to increase the conductivity.

  A part of the cerium oxide may be present alone. Thus, the presence of cerium oxide alone suppresses abnormal growth of the indium oxide crystal, and thus suppresses the generation of nodules and abnormal discharge.

  By dispersing in this manner, the average crystal particle diameter of indium oxide was 3.6 μm as shown in Table 1. This average diameter was determined by image processing.

  On the other hand, the method for producing the sintered body (sputtering) target of the present invention is not particularly limited except that a mixture of a predetermined amount of indium oxide, zinc oxide, palladium oxide and cerium oxide is used, and a known method is used. A sintered body (sputtering) target can be manufactured by forming the sintered body after mixing, forming and sintering the above four components.

  In addition, components other than the above four components may be added to the sintered body (sputtering) target as long as the object of the present invention is not impaired.

In ₂ O ₃ powder having an average particle diameter of 1.0 μm or less, and GeO ₂ powder, WO ₃ powder, or CeO ₂ powder having an average particle diameter of 1 μm or less are used as raw material powders. First, In ₂ O ₃ powder and GeO ₂ were obtained so as to obtain a sintered body having a composition of [Ge] / [In] atomic ratio, [W] / [In], and [Ce] / [In] shown in Table 1. Powder, WO ₃ powder, and CeO ₂ powder were prepared at a predetermined ratio, put into a resin pot, and mixed by a wet ball mill. At this time, hard ZrO ₂ balls were used and the mixing time was 24 hours. After mixing, the slurry was taken out, filtered, dried and granulated. This granulated product was molded by applying a pressure of 3 ton / cm ² with a cold isostatic press.

Next, this compact was sintered at 1300 ° C. for 3 hours in an atmosphere in which oxygen was introduced into the atmosphere in the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of} the furnace volume. At this time, the temperature was raised at 1 ° C./min. When cooling after sintering, the introduction of oxygen was stopped, and the temperature was lowered to 1000 ° C. at 10 ° C./min.

  In addition, the composition ratio ([W] / ([W] + [In])) of W, which is one of the first metal group M1, is 0.01, and is one of the second metal group M2. The composition ratio of Ce to indium ([Ce] / ([Ce] + [In])) is 0.03, and the composition ratio of Ge, which is one of the third metal group M3, to indium ([Ge] / ([Ge] + [In])) is 0.03. Similar contents are shown in Table 1.

  Now, when the fractured material of the sintered body obtained as described above was pulverized and subjected to powder X-ray diffraction measurement, only the diffraction peak due to the indium oxide phase and cerium oxide of the bixbite type structure was observed. . Therefore, the obtained sintered body is an oxide sintered body having the characteristics of the present invention.

  As shown in Table 1, the calculated value of the relative density of the obtained sintered body was 97%.

Further, from the EPMA analysis of the microstructure of the sintered body, it was confirmed that germanium and tungsten oxide were dissolved in the indium oxide phase. Moreover, it was confirmed that cerium oxide has both a part existing alone and a part dissolved in indium oxide. By dispersing in this way, the average crystal particle diameter of indium oxide was 3.8 μm as shown in Table 1. The average diameter was determined by image processing. The sintered body was processed into a diameter of 101 mm and a thickness of 5 mm, and the sputter surface was polished with a cup grindstone (sputtering) to obtain a target. This was bonded to a backing plate made of oxygen-free copper using metallic indium to form a sputtering target.

Germanium Well, if germanium oxide particles are present in the sputtering target, the specific resistance of the germanium oxide particles is high, so that the argon ions irradiated from the plasma are charged and arcing occurs. This tendency becomes more prominent as the target input power is increased and the argon ion irradiation amount is increased.

  On the other hand, in the sputtering target according to the present invention (in this example), both the indium oxide in which germanium is substituted and dissolved in the indium site and the indium germanate compound have low specific resistance. That is, since there is no high-resistance particle in the sputtering target, arcing hardly occurs even when the input power is increased. For this reason, according to this embodiment, high-speed film formation with high input power is possible.

  The reason for including the germanium (Ge) element in the oxide sintered body of the present invention (in this example) is that when a thin film is produced by sputtering from a sputtering target containing a germanium (Ge) element, This is because germanium having a valence of 4 occupies an indium position having a valence of 3 in the indium oxide film, thereby releasing carrier electrons, thereby increasing the conductivity of the thin film.

  Moreover, as already stated, in this invention, the germanium element in a sputtering target is prescribed | regulated in the range of 0.005 or more and 0.2 or less by Ge / In atomic ratio. The reason for defining such a numerical range is that the resistance value of the obtained thin film increases when the value deviates from the above range.

Tungsten In addition, it is preferable that tungsten is dispersed in the sputtering target of this embodiment. In particular, it is preferable that tungsten is substituted and dissolved in an indium site of indium oxide.

That is, the form in which the tungsten is contained in the target may be a form of tungsten oxide such as WO ₃ or WO ₂ and dispersed in the indium oxide sintered body. Moreover, indium oxide including In ₂ W ₃ O ₁₂ - in the form of a composite oxide between tungsten oxide, preferably also form dispersed in the indium oxide sintered body. Particularly preferably, tungsten atoms are dispersed and dissolved in the indium sites of indium oxide so that tungsten is dispersed at the atomic level in the indium oxide sintered body. Dispersion at the atomic level in this way stabilizes the discharge in sputtering. Further, the dispersion at the atomic level is effective for reducing the resistance of the obtained transparent conductive thin film.

Since cerium cerium oxide is dissolved in indium oxide, the valence tetravalent cerium occupies the indium position where the valence is trivalent in the indium oxide film. As a result, in this embodiment, the valence tetravalent cerium emits carrier electrons and the conductivity of the thin film increases.

  Moreover, a part of cerium oxide may exist by a cerium oxide single-piece | unit. Thus, the presence of cerium oxide alone suppresses abnormal growth of the indium oxide crystal, and thus suppresses the generation of nodules and abnormal discharge.

In ₂ O ₃ powder having an average particle size of 1 μm or less, Ga ₂ O ₃ powder having an average particle size of 1 μm or less, WO ₃ powder, and La ₂ O ₃ were used as raw material powders. First, in order to obtain a sintered body having a Ga / In atomic ratio, W / In, and La / In composition ratio shown in Table 1, an In ₂ O ₃ powder, a GaO ₂ powder, a WO ₃ powder, and a La ₂ O ₃ powder Were mixed at a predetermined ratio, put in a resin pot, and mixed by a wet ball mill. At this time, hard ZrO ₂ balls were used and the mixing time was 24 hours. After mixing, the slurry was taken out, filtered, dried and granulated. This granulated product was molded by applying a pressure of 3 ton / cm ² with a cold isostatic press.

Next, the compact was sintered at 1450 ° C. for 3 hours in an atmosphere in which oxygen was introduced into the atmosphere in the sintering furnace at a rate of 5 liters / minute per 0.1 m ^{3 of} the furnace volume. At this time, the temperature was raised at 1 ° C./min. When cooling after sintering, the introduction of oxygen was stopped, and the temperature was lowered to 1000 ° C. at 10 ° C./min.

  In addition, the composition ratio ([W] / ([W] + [In])) of W, which is one of the first metal group M1, is 0.02, and is one of the second metal group M2. The composition ratio of La to indium ([La] / ([La] + [In])) is 0.03, and the composition ratio of Ga, which is one of the third metal group M3, to indium ([Ga] / ([Ga] + [In])) is 0.03. Similar contents are shown in Table 1.

  When the fractured material of the sintered body thus obtained was pulverized and subjected to powder X-ray diffraction measurement, a diffraction peak attributed to the indium oxide phase having a bixbite structure and a diffraction peak attributed to cerium oxide were found. Observed.

  Therefore, the oxide sintered body of the present example is an oxide sintered body having the characteristics of the present invention. Further, from the EPMA analysis of the microstructure of the sintered body, it was confirmed that gallium was dissolved in the indium oxide phase. By dispersing in this manner, the average crystal particle diameter of indium oxide was 3.7 μm as shown in Table 1. This average diameter was determined by image processing.

  Further, as shown in Table 1, the specific calculated value of the relative density of the oxide sintered body of this example was 97%.

  This sintered body was processed into a size of 101 mm in diameter and 5 mm in thickness, and the sputtered surface was polished with a cup grindstone (sputtering) to obtain a target. This was bonded to a backing plate made of oxygen-free copper using metallic indium to form a sputtering target.

Gallium Now, when gallium oxide particles are present in the sputtering target, the specific resistance of the gallium oxide particles is high, so that charging may occur with argon ions irradiated from plasma, and arcing may occur. This tendency increases as the target input power is increased and the irradiation amount of argon ions is increased.

  On the other hand, in the sputtering target according to the present invention (in this example), both the indium oxide in which gallium is substituted and dissolved in the indium site and the indium gallate compound have low specific resistance (that is, high resistance particles). Therefore, arcing is less likely to occur even if the power applied to the plasma is increased. Therefore, in this embodiment, high-speed film formation with high input power is possible.

Tungsten In this example, tungsten is dispersed in the sputtering target. In particular, it is preferable that tungsten is substituted and dissolved in an indium site of indium oxide.

That is, the form in which the tungsten is contained in the sputtering target may be a form of tungsten oxide such as WO ₃ or WO ₂ and dispersed in the indium oxide sintered body. Further, it may be in the form of a composite oxide between indium oxide and tungsten oxide such as In ₂ W ₃ O ₁₂ and dispersed in the indium oxide sintered body.

  Particularly preferably, tungsten atoms are dispersed and dissolved in the indium sites of indium oxide, so that tungsten is dispersed at the atomic level in the indium oxide sintered body. Thus, by dispersing at the atomic level, the discharge during sputtering is stabilized, and the transparent conductive thin film obtained by sputtering can be made to have a lower resistance.

Lanthanum or a part of lanthanum may exist as lanthanum oxide alone. Thus, the presence of lanthanum oxide alone suppresses the abnormal growth of indium oxide crystals, thereby suppressing the generation of nodules and abnormal discharge.

  In this example, the measurement results of contact resistance are shown.

In the case of glass / Al / transparent electrode First, as shown in FIG. 2 (1), a first film formation mask 102 (Kapton tape) was applied to the slide glass 100 to form a film of Al with a thickness of 200 nm. Thereafter, the aforementioned mask was lifted off to form a predetermined Al pattern 104 (see FIG. 2 (2)).

  Next, the sputtering target obtained in Example 1 to Example 8 described above was attached to a DC sputtering apparatus. Then, a second film formation mask 106 (also Kapton tape) was applied (see FIG. 3A). And it sputter | sputtered using each sputtering target obtained in the said Examples 1-8, and formed the thin film (transparent electrode) 108 by 200 nm thickness. Thereafter, the second film formation mask 106 was lifted off to obtain a first contact resistance measurement substrate 110 (see FIG. 3B). Since this substrate is prepared for measuring the contact resistance, it is referred to as a (first) contact resistance measurement substrate 110 in the ninth embodiment.

  Although the contact resistance measuring substrate 100 has a substantially rectangular shape, terminals are provided at both ends, and the resistance of the surface when laminated like a glass / Al / transparent electrode is measured. This is shown in FIG. 4 (1). For example, the resistance value when a transparent electrode was produced using the sputtering target produced in Example 1 was 32.5Ω. Table 1 shows numerical values when other Examples 2 to 8 are used.

  In Example 9, since the transparent conductive film was used as an “electrode”, it was called a transparent electrode.

In the case of glass / transparent electrode / Al In addition, the second contact resistance measurement for measuring the contact resistance when the film formation order is the order of transparent electrode / Al, that is, when laminated like glass / transparent electrode / Al. A substrate 120 was obtained. The second contact resistance measurement substrate 120 is different only in the stacking order of the Al pattern 104 and the metal oxide 108. The measurement results of the second contact resistance measurement substrate 120 are also shown in Table 1. The measurement method and the like are the same as those of the first contact resistance measurement substrate 110, and the state is shown in FIG.

When a transparent electrode is formed on Al, the Al surface is oxidized to produce Al ₂ O _3, and thus the measured resistance value is generally large.

  A preferred embodiment 10 of the present invention will be described with reference to FIG.

  First, metal Al (99% Al1% Nd) is deposited on the light-transmitting glass substrate 1 by high frequency sputtering to a film thickness of 1500 angstroms. This is etched by a photo-etching method using a phosphoric acid-acetic acid-nitric acid aqueous solution as an etchant to form gate electrodes 2 and gate wirings having desired shapes. Next, a silicon nitride (SiN) film for forming the gate insulating film 3 is deposited to a thickness of 3000 angstroms by glow discharge CVD. Subsequently, an amorphous-Si: H (i) film 4 is deposited to a thickness of 3500 angstroms. Further, a silicon nitride (SiN) film 5 serving as a channel protective layer is deposited by 3000 angstroms.

At this time, as the discharge gas, SiN films 3 and 5 use SiH ₄ —NH ₃ —N ₂ mixed gas, and amorphous-Si: H (i) film 4 uses SiH ₄ —N ₂ mixed gas. Each was used. This SiN film 5 forms a desired channel protective layer 5 by dry etching using CHF gas. Subsequently, an amorphous-Si: H (n) film 6 is deposited with a film thickness of 3000 Å using a mixed gas of SiH ₄ —H ₂ —PH ₃ system.

  Next, a Cr / Al bilayer film was deposited thereon. This two-layer film is obtained by depositing 0.1 μm thick Cr and 0.3 μm Al in this order by vacuum vapor deposition or sputtering. FIG. 1 shows that the source electrode 7 and the drain electrode 8 are composed of these two layers.

Al in this bilayer film is photoetched using an H ₃ PO ₄ —CH ₃ COOH—HNO ₃ —H ₂ O-based etchant, while Cr in the bilayer film is an aqueous solution of ceric ammonium nitrate. Was used for photoetching. A desired source electrode 7 pattern and drain electrode 8 pattern were formed by such photo-etching.

Furthermore, the amorphous-Si: H film having a desired pattern of amorphous SiH (i) is obtained by using dry etching using CH 2 _F gas and wet etching using a hydrazine (NH ₂ NH ₂ .H ₂ O) aqueous solution in combination. The pattern of the film 4 and the pattern of the amorphous-Si: H (n) film 6 were formed.

Next, a silicon nitride (SiN) film for forming the insulating film 10 is deposited to a thickness of 3000 angstroms by glow discharge CVD. Thereafter, a contact hole is formed between the source electrode 7 and the drain electrode 8 and the transparent electrode and the pixel electrode 9 by a dry etching method using CH 2 _F gas.

Now, on the substrate on which the pattern of the source electrode 7 and the drain electrode 8 made of metal Al is formed, the amorphous material mainly containing indium oxide, zinc oxide / nickel oxide, and cerium oxide obtained in Example 4 is used. A transparent conductive film is deposited by sputtering. As the discharge gas, pure argon gas or argon gas mixed with a trace amount of O ₂ gas of about 1 vol% was used. In this way, a transparent electrode film (transparent conductive film) 9 was deposited to a thickness of 1200 Å. When this In ₂ O ₃ —ZnO—NiO—CeO ₂ film was analyzed by X-ray diffraction, no peak was observed and it was an amorphous film. Further, the specific resistance of this film is about 6.25 × 10 ⁻⁴ Ω · cm, and it can be used as an electrode sufficiently.

  This transparent conductive film was etched by a photoetching method using an aqueous solution of 3.5% by weight of oxalic acid as an etchant to form a pixel electrode 9 having a desired pixel electrode pattern. The pattern of the pixel electrode 9 is a pattern in which the pixel electrode 9 is electrically connected to the source electrode 7 having at least a predetermined pattern. By such etching, a pixel electrode 9 having a predetermined pixel electrode pattern was formed. The pixel electrode 9 is a desired amorphous electrode.

  At this time, the Al source electrode 7 and the drain electrode 8 were not eluted by the etching solution. The electrode lead-out portions of the gate line and source / drain line are also covered with a transparent electrode.

  Note that the substrate at this stage corresponds to an example of the translucent glass substrate in the claims.

  Thereafter, a light shielding film having a predetermined light shielding film pattern was formed to complete an amorphous-Si TFT active matrix substrate.

  Using this amorphous-SiTFT active matrix substrate, a TFT-LCD type flat display was manufactured. This TFT-LCD type flat display is capable of halftone display (gradation display) without any problem, and exhibits good display performance.

  In addition, although the sputtering target produced in Example 4 was utilized in the example mentioned above, a favorable result was obtained even if it utilized the sputtering target produced only in Examples 1-3, 5-8, and it was as a transparent electrode. It was confirmed that it was fully available. Table 1 shows specific resistance values of the transparent conductive film in the case of using the sputtering target in other examples other than Example 4.

-Comparative example-
Hereinafter, a comparative example will be described. In each of the following comparative examples, a sputtering target having the composition shown in Table 1 was created, and the same evaluation as in Example 9 was performed.

Comparative Example 1
Sputtering targets were produced in the same manner as in Examples 1 to 8 above, using In ₂ O ₃ powder having an average particle size of 1 μm or less and SnO ₂ powder having an average particle size of 1 μm or less as raw material powders.

  In addition, the composition ratio ([Sn] / ([Sn] + [In])) of Sn which is one of the third metal group M3 to indium is 0.10. This is also shown in Table 1.

  As shown in Table 1, the average crystal particle diameter of indium oxide was 12.8 μm. This average diameter was determined by image processing. Further, as shown in Table 1, the calculated value of the specific relative density of the oxide sintered body of this comparative example was 99%.

Contact Resistance with Al Also in this comparative example, the contact resistance with Al was measured in the same manner as in Example 9 in the configuration of glass / Al / transparent electrode and glass / transparent electrode / Al. The results are shown in Table 1.

Specific Resistance of Transparent Electrode Also in this comparative example, a liquid crystal display device was prepared by the same method as in Example 10, and the specific resistance of the transparent electrode was measured in the process. The measurement results are also shown in Table 1.

"Comparative Example 2"
Sputtering targets were prepared in the same manner as in Examples 1 to 8 above, using In ₂ O ₃ powder having an average particle size of 1 μm or less and ZnO powder having an average particle size of 1 μm or less as raw material powders.

  In addition, the composition ratio ([Zn] / ([Zn] + [In])) of Zn which is one of the third metal groups M3 to indium is 0.16. This is also shown in Table 1.

  The average crystal particle diameter of indium oxide was 3.8 μm as shown in Table 1. This average diameter was determined by image processing. Further, as shown in Table 1, the calculated value of the specific relative density of the oxide sintered body of this comparative example was 98%.

Contact resistance with Al Also in this comparative example, the contact resistance with Al was measured in both the “glass / Al / transparent electrode” and “glass / transparent electrode / Al” configurations in the same manner as in Example 9. . The results are shown in Table 1.

Specific Resistance of Transparent Electrode Also in this comparative example, a liquid crystal display device was prepared by the same method as in Example 10, and the specific resistance of the transparent electrode was measured in the process. The measurement results are also shown in Table 1.

Comparative Example 3
A sputtering target was prepared in the same manner as in Examples 1 to 8 above using In ₂ O ₃ powder having an average particle size of 1 μm or less and WO ₃ powder and CeO ₂ powder having an average particle size of 1 μm or less as raw material powders. .

  In addition, the composition ratio ([W] / ([W] + [In])) of W, which is one of the first metal group M1, is 0.25. Further, the composition ratio ([Ce] / ([Ce] + [In])) of Cen, which is one of the second metal groups M2, to 0.25 is 0.25. These are also shown in Table 1.

  The average crystal particle diameter of indium oxide was 15 μm as shown in Table 1. This average diameter was determined by image processing. Moreover, as shown in Table 1, the calculated value of the specific relative density of the oxide sintered body of this comparative example was 84%.

Contact resistance with Al Also in this comparative example, the contact resistance with Al was measured in both the “glass / Al / transparent electrode” and “glass / transparent electrode / Al” configurations in the same manner as in Example 9. . As shown in Table 1, the results were all 1 MΩ or more.

Specific Resistance of Transparent Electrode Also in this comparative example, a liquid crystal display device was prepared by the same method as in Example 10, and the specific resistance of the transparent electrode was measured in the process. The measurement result was 1 MΩcm or more as shown in Table 1.

Comparative Example 4
Sputtering targets in the same manner as in Examples 1 to 8 above, using In ₂ O ₃ powder having an average particle size of 1 μm or less and WO ₃ powder, CeO ₂ powder, SnO ₂ powder having an average particle size of 1 μm or less as raw material powders Was made.

  The composition ratio ([W] / ([W] + [In])) of W, which is one of the first metal group M1, is 0.25, which is one of the second metal group M2. The composition ratio of Ce to indium ([Ce] / ([Ce] + [In])) is 0.25, and the composition ratio of Sn, which is one of the third metal group M3, to indium ([Sn] / ([Sn] + [In])) was 0.4. These are also shown in Table 1.

  Further, as shown in Table 1, the calculated value of the specific relative density of the oxide sintered body of this comparative example was 60%.

Contact resistance with Al Also in this comparative example, the contact resistance with Al was measured in both the “glass / Al / transparent electrode” and “glass / transparent electrode / Al” configurations in the same manner as in Example 9. . As shown in Table 1, the results were all 1 MΩ or more.

Specific Resistance of Transparent Electrode Also in this comparative example, a liquid crystal display device was prepared by the same method as in Example 10, and the specific resistance of the transparent electrode was measured in the process. The measurement result was 1 MΩcm or more as shown in Table 1.

-Modification 1-
In the above-described embodiment, the example in which the oxides of W, Mo, Nb, Ni, Pt, and Pd of the first metal group M1 are used as the constituent elements has been described. It is also preferable to use as it is, and the same effects as in the above embodiments can be obtained.

-Modification 2-
In Examples 9 and 10 described above, an example using Al is shown. However, it is of course preferable to use Ag instead of Al. When Ag is used, the same action and effect as in the case of Al can be obtained.

In summary , preferred examples 1 to 12 and comparative examples 1 to 4 of the present invention have been described.

  As described above, when the transparent conductive film according to the present embodiment is used as a transparent electrode or a pixel electrode, the contact resistance between the Al gate electrode and the transparent electrode and between the Al source / drain electrode and the pixel electrode can be kept small. Can do. As a result, if this transparent electrode or pixel electrode is used, a liquid crystal display device capable of displaying halftones satisfactorily can be obtained.

It is sectional drawing showing the amorphous-SiTFT vicinity in the stage which the pattern formation of the pixel electrode was complete | finished in the manufacturing process of the liquid crystal flat display in preferable embodiment of this invention. It is explanatory drawing which shows the mode of the 1st film-forming in the present Example 9. FIG. It is explanatory drawing which shows the mode of the 2nd film-forming in the present Example 9. FIG. It is explanatory drawing which shows the mode of the contact resistance measurement in the present Example 9.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Translucent glass substrate 2 Gate electrode 3 SiN gate insulating film 4 Amorphous-Si: H (i) film 5 Channel protective film 6 Amorphous-Si: H (n) film 7 Source electrode 8 Drain electrode 9 Pixel electrode 10 Insulating film DESCRIPTION OF SYMBOLS 100 Slide glass 102 1st film-forming mask 104 Al pattern 106 2nd film-forming mask 108 Metal oxide 110 1st contact resistance measurement board | substrate 120 2nd contact resistance measurement board | substrate

Claims (18)

Mainly composed of indium oxide,
W, Mo, Nb, Ni, Pt, 1 or more kinds of metal selected from the 1 a metal group M1 a consisting of Pd, or, W, Ni, Pt, from the 1b metal group M1b made of Pd One or more selected metal oxides; and
An oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal;
Sputtering target containing. One or more metals selected from the first a metal group M1 a composed of W, Mo, Nb, Ni, Pt, Pd , or the first b metal group M1b composed of W, Ni, Pt, Pd The value of [M1] / ([M1] + [In]), which is a composition of indium oxide, of one or more metal oxides selected from is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is The sputtering target according to claim 1, wherein the sputtering target is 0.005 to 0.2. Here, the [M1], the number of one or two or more metal atoms selected from the first 1 a metal group M1 a, or, one or two species selected from the 1b metal group M1b [M2] represents the number of one or more metal atoms selected from the second metal group, and [In] represents the number of indium atoms. Represents a number.   The oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more metals selected from La, Ce, Ho, and Er. The sputtering target according to claim 1 or 2. Mainly composed of indium oxide,
W, Mo, Nb, Ni, Pt, 1 or more kinds of metal selected from the 1 a metal group M1 a consisting of Pd, or, W, Ni, Pt, from the 1b metal group M1b made of Pd One or more selected metal oxides;
An oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal;
Furthermore, an oxide of one or more metals selected from the third metal group M3 made of Zn, Sn, Zr, Ga, Ge,
A sputtering target comprising: One or more metals selected from the first a metal group M1 a composed of W, Mo, Nb, Ni, Pt, Pd , or the first b metal group M1b composed of W, Ni, Pt, Pd The value of [M1] / ([M1] + [In]), which is a composition of indium oxide, of one or more metal oxides selected from is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is 0.005 to 0.2,
[M3] / ([M3] + [In] is a composition of indium oxide of an oxide of one or more metals selected from the third metal group consisting of Zn, Sn, Zr, Ga, and Ge. ]) Is 0.005-0.2, The sputtering target of Claim 4 characterized by the above-mentioned. Here, [M1] is the number of one or more metal atoms selected from the first a metal group M1a, or one or more metals selected from the 1b metal group M1b. [M2] represents the number of one or more metal atoms selected from the second metal group, and [M3] represents the third metal group. Represents the number of atoms of one or more metals selected from [In], and [In] represents the number of atoms of indium metal.   5. The oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. 5. The sputtering target according to 5. Mainly composed of indium oxide,
W, Mo, Nb, Ni, Pt, 1 or more kinds of metal selected from the 1 a metal group M1 a consisting of Pd, or, W, Ni, Pt, from the 1b metal group M1b made of Pd One or more selected metal oxides; and
An oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal;
A transparent conductive film comprising: One or more metals selected from the first a metal group M1 a composed of W, Mo, Nb, Ni, Pt, Pd , or the first b metal group M1b composed of W, Ni, Pt, Pd The value of [M1] / ([M1] + [In]), which is a composition of indium oxide, of one or more metal oxides selected from is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is The transparent conductive film according to claim 7, which is 0.005 to 0.2. Here, [M1] is the number of one or more metal atoms selected from the first a metal group M1a, or one or more metals selected from the 1b metal group M1b. [M2] represents the number of one or more metal atoms selected from the second metal group, and [In] represents the number of indium atoms. Represents.   The oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is an oxide of at least one of La, Ce, Ho, and Er, or 7 or 8. The transparent conductive film according to 8. Mainly composed of indium oxide,
W, Mo, Nb, Ni, Pt, 1 or more kinds of metal selected from the 1 a metal group M1 a consisting of Pd, or, W, Ni, Pt, from the 1b metal group M1b made of Pd One or more selected metal oxides;
An oxide of one or more metals selected from the second metal group M2 made of a lanthanoid metal;
Furthermore, an oxide of one or more metals selected from the third metal group M3 made of Zn, Sn, Zr, Ga, Ge,
A transparent conductive film comprising: One or more metals selected from the first a metal group M1 a composed of W, Mo, Nb, Ni, Pt, Pd , or the first b metal group M1b composed of W, Ni, Pt, Pd The value of [M1] / ([M1] + [In]), which is a composition of indium oxide, of one or more metal oxides selected from is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is 0.005 to 0.2,
[M3] / ([M3] + [In] is a composition of indium oxide of an oxide of one or more metals selected from the third metal group consisting of Zn, Sn, Zr, Ga, and Ge. ]) Is 0.005-0.2, The transparent conductive film of Claim 10 characterized by the above-mentioned. Here, [M1] is the number of one or more metal atoms selected from the first a metal group M1a, or one or more metals selected from the 1b metal group M1b. [M2] represents the number of one or more metal atoms selected from the second metal group, and [M3] represents the third metal group. Represents the number of one or more metal atoms selected from
[In] represents the number of indium atoms.   The oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. 12. The transparent conductive film according to 12. A glass substrate;
One or two or more metals selected from the first a metal group M1 a , which is provided on the glass substrate and contains indium oxide as a main component and is composed of W, Mo, Nb, Ni, Pt, and Pd , or One or more oxides of one or more metals selected from the 1b metal group M1b made of W, Ni, Pt, Pd, and one or two kinds selected from the second metal group M2 made of a lanthanoid metal A transparent conductive film comprising the above metal oxide,
A metal thin film mainly composed of Al or Ag provided on the glass substrate;
A transparent conductive glass substrate comprising: One or more metals selected from the first a metal group M1 a composed of W, Mo, Nb, Ni, Pt, Pd , or the first b metal group M1b composed of W, Ni, Pt, Pd The value of [M1] / ([M1] + [In]), which is a composition of indium oxide, of one or more metal oxides selected from is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is The transparent conductive glass substrate according to claim 13, which is 0.005 to 0.2. Here, [M1] is the number of one or more metal atoms selected from the first a metal group M1a, or one or more metals selected from the first b metal group M1b. [M2] represents the number of one or more metal atoms selected from the second metal group.   The oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er. 14. The transparent conductive glass substrate according to 14. A glass substrate;
One or two or more metals selected from the first a metal group M1 a , which is provided on the glass substrate and contains indium oxide as a main component and is composed of W, Mo, Nb, Ni, Pt, and Pd , or One or more oxides of one or more metals selected from the 1b metal group M1b made of W, Ni, Pt, Pd, and one or two kinds selected from the second metal group M2 made of a lanthanoid metal A transparent conductive film comprising the above metal oxide, and one or more metal oxides selected from the third metal group M3 composed of Zn, Sn, Zr, Ga, and Ge;
A metal thin film mainly composed of Al or Ag provided on the glass substrate;
A transparent conductive glass substrate comprising: One or more metals selected from the first a metal group M1 a composed of W, Mo, Nb, Ni, Pt, Pd , or the first b metal group M1b composed of W, Ni, Pt, Pd The value of [M1] / ([M1] + [In]), which is a composition of indium oxide, of one or more metal oxides selected from is 0.005 to 0.2,
The value of [M2] / ([M2] + [In]), which is a composition of one or more metals selected from the second metal group M2 made of the lanthanoid metal, with respect to indium oxide is 0.005 to 0.2,
[M3] / ([M3] + [In] is a composition of indium oxide of an oxide of one or more metals selected from the third metal group consisting of Zn, Sn, Zr, Ga, and Ge. ]) Is 0.005-0.2, The transparent conductive glass substrate of Claim 16 characterized by the above-mentioned. Here, [M1] is the number of one or more metal atoms selected from the first a metal group M1a, or one or more metals selected from the 1b metal group M1b. [M2] represents the number of one or more metal atoms selected from the second metal group, and [M3] represents the third metal group. Represents the number of one or more metal atoms selected from [In], and [In] represents the number of indium atoms.   The oxide of a metal selected from the second metal group M2 made of a lanthanoid metal is an oxide of one or more of La, Ce, Ho, and Er, or 17. The transparent conductive glass substrate according to 17.

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