TWI269817B - Sputtering target, transparent conductive oxide, and process for producing the sputtering target - Google Patents

Abstract

In a sputtering target comprising at least indium oxide and zinc oxide, the atomic ratio represented by In/(In+Zn) is set to a value within the range of 0.75 to 0.97, a hexagonal layered compound represented by In2O3(ZnO)m wherein m is an integer of 2 to 20 is contained, and the crystal grain size of the hexagonal layered compound is set to a value of 5 mum or less.

Description

1269817 Α7 Β7 V. INSTRUCTIONS (1) TECHNICAL FIELD (Please read the note on the back and fill out this page.) The present invention relates to a sputtering target (hereinafter sometimes referred to simply as a target), which is transparent by a ruthenium plating target. A conductive oxide and a method of producing a sputtering target. In particular, it is a transparent conductive oxide composed of such an IE, which is capable of suppressing projections generated when a transparent conductive oxygen film is formed by a sputtering method, and which can stably perform sputtering. The method of manufacturing the target. BACKGROUND OF THE INVENTION In recent years, display devices have been rapidly developed, and liquid crystal display devices (LCDs), electroluminescent display devices (ELs), or field emission displays (FEDs) have been used as control systems for personal computers, word processors, and the like. The display device is used. Each of these display devices has a layered structure in which a display element is held by a transparent conductive oxide. Such a transparent conductive oxide is, for example, Document 1: "Technology of Transparent Conductive Film" (share), published by the company, Japan Society for the Promotion of Science, Transparent Oxide, Optoelectronic Materials, No. 1 6 6th, 1 9 9 9 ) It is disclosed that indium tin oxide (hereinafter sometimes abbreviated as I Τ 0 ) formed by a sputtering target method, an ion plating method or a vapor deposition method is the mainstream. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives I Τ 0 is composed of a predetermined amount of indium oxide and tin oxide. It is excellent in transparency and conductivity, and can be processed by strong acid etching, and is excellent in adhesion to substrates. . For example, 曰本特开平3—50 1 48, special Kaiping 5 — 155651, JP-A-5-70943, JP-A-6- 2 3 4 5 6 5, etc., from the quantified indium oxide, tin oxide The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 2^7 mm) 1269817 A7 B7 V. Description of the invention (2) The target of the formation, the transparent electrode formed by the formation of this target (the following It is abbreviated as IZ 0 ) and can be processed by weak acid etching, and has good sinterability and transparency, and is widely used. (Please read the precautions on the back and fill out this page.) IT〇 or IZ 0 has the properties of a material with a transparent conductive oxide. However, when the target is formed by sputtering, the target surface is likely to be produced as shown in Figure 2. The protrusion shown in (photo). In particular, in the case of forming an amorphous I T 0 film for the purpose of improving etching properties, in order to introduce a small amount of water or hydrogen gas into the sputtering tank, the surface of the target is reduced, and projections are more likely to be generated. When such a projection is generated on the surface of the target, the protrusion is scattered due to the ionization force in the sputtering. Therefore, the scattering is likely to adhere to the film in the form of a foreign matter or to form a transparent conductive oxide. The protrusions generated on the surface of the target also become one of the causes of abnormal discharge. For the purpose of suppressing the occurrence of the projections of the target, for example, it is disclosed in Japanese Patent Application Laid-Open No. Hei No. Hei. In other words, although the theoretical relative density produces a target of 99%, it is impossible to completely avoid the occurrence of protrusions at this time. In the case of the situation, there is a need to develop a target that suppresses the occurrence of protrusions during sputtering and film formation and stabilizes sputtering. The present inventors have carefully reviewed the results in order to solve the above problems, and found that the protrusions generated on the surface of the target are excavated residuals during sputtering, and the reason for the excavation residual is the size of the crystal grain size of the metal oxide constituting the target. (For example, 1 0 // m or more) is closely related. In other words, when the surface of the target is sputtered, the paper size is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) due to the direction of the crystal surface. 1269817 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 B7 V (Invention) (3) The speed at which it is cut is different, and unevenness is generated on the surface of the target. Therefore, it was confirmed that the size of the dome was closely related to the crystal grain size of the metal oxide present in the sintering. Therefore, when a target composed of a sintered body having a large crystal grain size is used, it becomes larger as the unevenness of the surface of the target increases, and a projection is generated from the convex portion of the uneven portion. In other words, the object of the present invention is to provide a target capable of suppressing the occurrence of a projection when a transparent conductive oxide is formed by a sputtering method, and capable of stably performing sputtering, and a transparent conductive material composed of such a target. Sex oxides, and methods of making such targets. DISCLOSURE OF THE INVENTION [1] According to the present invention, a sputtering target comprising at least indium oxide and zinc oxide can be provided, wherein an atomic ratio represented by I n /( I η + Ζ η ) is Ο·75 Ο a number 値 within the range of 97, and a hexagonal layered compound represented by I Π 2 〇 3 (ZnO) m (but m is an integer of 2 to 20), and the crystal grain size of the hexagonal layered compound is 5 / m below the number of sputtering targets to solve the above problems. In other words, the size of the crystal grain size is limited to a specific range, and the size of the unevenness generated on the surface of the target is suppressed, and as a result, the occurrence of the protrusions can be effectively suppressed. [2] Further, when the sputtering target of the present invention is formed, it contains 6 7 to 3% by weight of indium oxide, 5 to 25% by weight of tin oxide, and 2 to 8% by weight of zinc oxide, and the atomic ratio of tin/zinc is 1 The above is ideal. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) !1 ————------------------Line#· (Please read the back first Note: Please fill in this page again) 1269817 A7 __ _B7 V. Inventive Note (4) In this configuration, the target becomes tight, and the occurrence of protrusions can be more effectively suppressed. By setting the atomic ratio of tin/zinc to 1 or more, The electric resistance after crystallization can be effectively reduced, and a transparent conductive oxide having excellent conductivity can be obtained. [3] Further, when the sputtering target of the present invention is formed, a hexagonal layered compound or a hexagonal layered compound and a spinel structure compound represented by η η 2 S η 〇 4 are substituted for the spinel structure compound. The crystal grain size is preferably 5 // m or less. According to this configuration, when the target is tight and the projections are more effectively suppressed, the transparent conductive oxide having excellent transparency or conductivity can be obtained by sputtering. [4] When the sputtering target of the present invention is further constituted, the body impedance is preferably 1 X 1 0 - 3 Ω · c m or less. Further, in this configuration, the abnormal discharge (spark discharge) during sputtering is reduced, and the sputtering film can be stably obtained. Conversely, when the bulk impedance is 1 X 1 0 _ 3 Ω • cm or more, the accumulated charge on the sputter surface is prone to abnormal discharge. [5] When the sputtering target of the present invention is further constituted, the density is preferably 6 · 7 g / c m 3 or more. According to this configuration, excellent mechanical properties can be obtained, and the target becomes dense, and the occurrence of projections can be more effectively suppressed. [6] Another aspect of the present invention is that the atomic ratio expressed by I n / (I η + Ζ η ) is Ο · 75 Ο Ο 97 range, and the paper size is applicable to the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) (Please read the notes on the back and fill out this page)

-·丨丨_丨丨丨定·丨—丨丨_丨-*5^I Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed 1269817 A7 B7 V. Invention Description (5) I Π2〇3 (Zn〇) m (but m is an integer of 2 to 20) represents a hexagonal layered compound, and the hexagonal crystal layered compound has a crystal grain size of 5 # m or less and a transparent conductive oxide (amorphous) Transparent conductive oxide). According to this configuration, an amorphous transparent conductive oxide excellent in transparency or conductivity can be obtained efficiently. [7] When the transparent conductive oxide of the present invention is further formed, the sputtering paste contains 6 to 3% by weight of indium oxide, 5 to 25 % by weight of tin oxide, and 2 to 8% by weight of zinc oxide. The atomic ratio of tin/zinc is preferably 1 or more. According to this configuration, an amorphous transparent conductive oxide excellent in transparency or conductivity can be obtained efficiently. [8] It is preferred that the transparent conductive oxide of the present invention is crystallized at a temperature of more than 2,300 tons. According to this configuration, a transparent conductive oxide excellent in transparency or conductivity can be obtained efficiently. At such a temperature, when forming on a substrate, there is no need to worry about the binding energy of the oxygen 1 S orbital as determined by X-ray photoelectron spectroscopy (XPS) when the damaged substrate [9] constitutes the transparent conductive oxide of the present invention. It is preferable that the width of the peak of the peak is 3 e V or less. According to this configuration, a transparent conductive oxide excellent in transparency or conductivity can be obtained efficiently. [10] When forming the transparent conductive oxide of the present invention, the paper size is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note before completing this page). · n ϋ Βϋ ·1 n ·ϋ 1« 如心,· ϋ 1* Μ·— ϋ· 11 ϋ ^1 I ^ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 B7 V. Invention Description (6) It is preferred on the substrate or on the colored layer disposed on the substrate. (Please read the precautions on the back and fill out this page.) In this configuration, transparent electrodes or transparent electrodes containing color filters can be effectively provided. [1 1] When the transparent conductive oxide of the present invention is further constituted, P-V値 measured in accordance with JIS B 0 0 0 1 is preferably 1 #m or less, and is preferably used for a transparent electrode or a color filter. When the transparent electrode of the light sheet or the like is used, the occurrence of disconnection or short circuit can be effectively prevented. [1 2] The other aspect of the present invention contains a hexagonal layered compound represented by I η 2 0 3 ( Ζ η〇) m (but m is an integer of 2 to 20), and the hexagonal layered compound The method for producing a sputtering target having a crystal grain size of 5 // m or less (hereinafter, the first production method) is characterized by comprising the following steps (1) to (3), (1) mixing indium oxide powder and a step of forming a zinc oxide powder having an average particle diameter of 2 //m or less, and (2) a step of forming a molded body having an atomic ratio of 0 η to 75 Å·97 as represented by I η / ( I n + Zn), (3) The step of sintering the formed body at a temperature of 14,000 ° C or higher is printed by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives. When the above steps are carried out, it is possible to suppress the formation of a transparent conductive oxide by sputtering. The occurrence of protrusions stabilizes the target of sputtering. [13] In carrying out the first production method of the sputtering target of the present invention, in the step (1), indium oxide powder is added in an amount of from 67 to 3% by weight, the tin oxide powder is in an amount of from 5 to 25 % by weight, and zinc oxide powder is used. 2~8wt%, the same as the paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 public) 1269817 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (7) The above steps ( In 2), it is preferable to form a molded body having an atomic ratio of tin/zinc of 1 or more. When the above steps are carried out, it is possible to provide a target which suppresses the occurrence of protrusions when a transparent conductive oxide is formed by sputtering, and stably performs sputtering. [14] The other aspect of the present invention contains a hexagonal layered compound 'I represents a η 2 〇 3 (· Zn 〇) m (but m is an integer of 2 to 20) and the crystal layer A method for producing a sputtering target having a crystal grain size of 5 // m or less (hereinafter, the second production method) is characterized by comprising the following steps (1) to (5), and (1) I n2 〇3 (Zn.〇)m (but m is an integer of 2 to 20) represents a step of forming a hexagonal layered compound, and (2) adjusting the particle size of the resulting hexagonal layered compound to 5 // m The following steps, (3) mixing and adjusting the hexagonal layered compound and the indium oxide powder after the particle size, (4) forming an atomic ratio represented by I n / (I η + Ζ η ) as 〇·75~0 - Step of molding a 97, (5) Step of sintering the formed body at a temperature of 140 ° C or higher 〇 When the above steps are carried out, a hexagonal layered compound having a particle diameter controlled in advance can be used, so that it is easier to control The average particle size in the target. [15] When the first and second production methods of the present invention are carried out, the step of sintering is preferably carried out under an oxygen atmosphere or under oxygen pressure. When the above steps are implemented, the occurrence of the protrusions can be controlled more, and the paper size can be provided. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) -1U - ---丨丨! - _ !| 订·1 !!-Line* (Please read the notes on the back and fill out this page) 1269817 A7 B7 V. INSTRUCTIONS (8) Targets to be sputtered. (Please read the precautions on the back and fill out this page.) [1 6] When the first and second manufacturing methods of the present invention are carried out, the average particle diameter of the indium oxide powder is in the range of 0·1 to 2//m. ideal. When the above steps are carried out, it is possible to provide a target in which the crystal grain size of the hexagonal layered compound is controlled to a predetermined range. [17] When the first and second production methods of the present invention are carried out, indium oxide powder and tin oxide powder may be simultaneously blended, and the average particle diameter of the tin oxide powder is in the range of 0·1 to 1 // m. ideal. When the above steps are carried out, it is possible to provide a target in which the crystal grain size of the hexagonal layered compound and the spinel structure compound is controlled within a predetermined range. [18] When the first and second production methods of the present invention are carried out, it is more preferable to further mix a spinel structure compound having a particle diameter of 5 // m or less when forming a molded body. When the above steps are carried out, a spinel structure compound having a particle diameter controlled in advance can be used, so that it is easier to control the average particle diameter in the target. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of the surface of the target (after sputtering) of the first embodiment. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives. Figure 2 is a photograph of the surface of a conventional target (after sputtering). Fig. 3 is a graph showing the relationship between the crystal grain diameter and the number of projections of the target (after sputtering) of the first embodiment. Fig. 4 is a graph showing the relationship between the crystal grain diameter and the number of projections of the target (after sputtering) of the second embodiment. Figure 5 is an X-ray diffraction pattern of a target containing a hexagonal layered compound. -11- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1269817 A7 ___ V. Description of invention (9) Figure 6 is an X-ray diffraction pattern of a target containing a spinel structure compound (please read the back of the page and fill out this page). Figure 7 is a graph showing the resistance stability of a transparent conductive oxide. Fig. 8 is a graph showing the light transmittance of a transparent conductive oxide. Fig. 9 is a graph showing the refractive index of a transparent conductive oxide. Fig. 10 is a graph showing the influence of the heat treatment temperature when a transparent conductive oxide is produced. Figure 11 is a diagram showing the manufacturing steps of the color filter. Fig. 12 is a graph showing the binding energy peak of the oxygen 1 S orbital of the transparent conductive oxide (1). Fig. 13 is a graph showing the binding energy peak of the oxygen 1 S orbital of the transparent conductive oxide (2 of them). Component Symbol Table] Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1〇: Substrate 12: Organic Colored Layer 14: Red Pixel 16: Green Pixel 18: Blue Pixel 2 0: Black Matrix 2 2: Transparent Conductive Film 2 4: Transparent Conductive film This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 ___JB7 V. Invention Description (10) The best embodiment for implementing the invention Embodiments 1 to 8 of the present invention (the inventions of the first to sixth aspects) will be specifically described with reference to the drawings. The drawings are only for the purpose of illustrating the size, shape and arrangement of the components of the present invention. The invention is therefore not limited to the illustrated examples. In the drawings, the cross-section of the cross-section is sometimes omitted: [Embodiment 1] The first embodiment relates to a sputtering target comprising at least indium oxide and zinc oxide. The atomic ratio expressed by I n / ( I η + Ζ η ) is 値 · 7 5~Ο · 9 7 in the range of 値, and contains I Π 2 〇 3 (Zn〇) m (but m is 2~) The integer of 20) is a hexagonal layered compound, and the crystal grain size of the hexagonal layered compound is a sputtering target of 5 # m or less. (1) In the composition of each of the metal oxides of the constituent components of the first embodiment, the atomic ratio expressed by I n /( I η + Ζ η ) must be 〇.75 to 0·97. The number within the range. For this reason, the atomic ratio expressed by I η / ( I η + Ζη) is 〇. When the ratio is 7.5 or less, the conductivity of the transparent conductive oxide obtained by sputtering is lowered. Further, when the atomic ratio expressed by I η / ( I η + Ζη) exceeds 0 · 97, the content of I η increases. 'The protrusion is likely to occur during sputtering. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -13 - (Please read the notes on the back and fill out this page)

1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees' Consumption Cooperatives Printing 5, Inventions (11) Therefore, when considering the balance between the conductivity of transparent conductive oxides and the prevention of protrusions, I n / ( I η + Ζ η ) indicates that the atomic ratio must be a number 0 in the range of 0 · 8 0~0 · 9 5 , more preferably a number 0 in the range of 0·85~0·95. (2) Crystal structure 1. The first embodiment is characterized in that the constituent component of the target contains a hexagonal layered compound represented by Ι·Π2〇3 (Zn〇)m (but m is an integer of 2 to 20). Indium oxide and zinc oxide. Indium oxide and zinc oxide are present not only in the form of a mixture but also in the crystal form of the hexagonal layered compound (crystal grain size of 5 μm or less), because the target can be made compact, the density of the target can be increased, and the density can be improved. The conductivity of the obtained transparent conductive oxide is obtained. When indium oxide and zinc oxide are contained in the crystal form of the hexagonal layered compound, the crystal growth of indium oxide can be suppressed, and as a result, sputtering can be suppressed during sputtering, and sputtering with good stability can be performed. The presence of the hexagonal layered compound represented by I η 2 〇 3 ( Ζ η 0 ) m was confirmed by X-ray diffraction analysis of the crystal structure. For example, when the X-ray diffraction analysis chart and the peak map shown in Fig. 5 (a) to (d) are obtained, the presence of the hexagonal layered compound represented by I η 2 〇 3 ( Ζ η 〇) m can be confirmed. . (3) Crystalline structure 2 1 crystal grain size This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)"! ·_________〆 (Please read the notes on the back and fill out this page) I*— 订-—1^------ Line ▲ 1269817 A7 B7 V. Inventive Note (12) In the first embodiment, the target The crystal grain size of the hexagonal crystal layered compound in the middle must be 5 // m or less. (Please read the precautions on the back and fill out this page.) The reason is that when the crystal grain size exceeds 5 # m, the protrusions are noticeable during sputtering. However, the crystal grain size is too small, sometimes the control is not easy, and the type of the raw material of the crucible is too limited. Therefore, the crystal grain size of the hexagonal layered compound in the target is preferably in the range of 0 · 1 to 4 // m, and the number in the range of 0 · 5 to 3 // m is more desirable. (2) Relationship between the size of the crystal grain size and the number of occurrences of the projections The relationship between the size of the crystal grain size of the hexagonal layered compound and the number of occurrences of the projections will be more specifically described with reference to Fig. 3. The horizontal axis of Fig. 3 is the size (//m) of the crystal grain size of the hexagonal layered compound, and the vertical axis is the number of protrusions per unit area and unit sputtering time (s/SHi's/gOOem2). Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives are easily understood from Figure 3. When the crystal grain size of the hexagonal layered compound is 5 or less, the number of protrusions occurring is //8H rs/ 9 0 0 # m 2 When the crystal grain size of the hexagonal layered compound exceeds 5 //m, the number of occurrences of the protrusions increases sharply, and protrusions of 8 to 32 / 8 Hr s / 900 / zm 2 occur. On the other hand, it is understood from Fig. 3 that in order to effectively prevent the occurrence of protrusions, the crystal grain size of the hexagonal layered compound must be 5 // m or less, and when the crystal grain size is 4 / zm or less, the protrusion can be surely prevented. The number of occurrences of things. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). 1269817 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Description of Invention (13) 3 Method for Determination of Crystalline Particle Size Hexagonal Layered The crystal grain size of the compound can be measured using an electron beam microanalyzer (hereinafter sometimes referred to as "Ε Μ A"). More specifically, after the target surface is honed and smoothed, the target surface is enlarged to 5000 times using a microscope, and a frame of 30 //mx 3 0 //m is placed at an arbitrary position, and used.最大 The maximum diameter of the crystal particles of the hexagonal layered compound observed in the PMA measurement frame. At least the maximum diameter of the crystal particles in the three places in the frame was measured, and the average enthalpy was calculated as the crystal grain size of the hexagonal layered compound. The crystal grain size of the hexagonal layered compound can be easily determined from the corresponding map (concentration distribution) of zinc of Ε Μ A, whereby it can be used as the measured crystal grain size. (4) Control of crystal grain size The crystal grain size of the hexagonal layered compound is selected by appropriately changing the type of the raw material powder constituting the target, the average particle diameter of the raw material powder, and the manufacturing conditions of the target can be controlled within a predetermined range. For example, the type and average particle diameter of the raw material powder may be set to 2 / m or less of the average particle diameter of the zinc oxide powder used for the production of the target. The reason is that when the average particle diameter of the zinc oxide powder exceeds 2 // m, zinc oxide is more likely to diffuse and move with respect to indium oxide, and as a result, it is difficult to control the crystal grain size of the hexagonal layered compound formed. On the contrary, when the average particle diameter of the zinc oxide powder is 2 // m or less, the indium oxide is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -It is compared with the paper scale with respect to the zinc oxide - ___________^___·- Order · 』__:______ Line win (please read the note on the back and fill in this page) 1269817 A7 B7 V. Description of invention (14) Easy to spread and move, crystallize the hexagonal layered compound The particle size is controlled to be less than 5 // m. However, the average particle diameter of the zinc oxide powder is too small, and it is sometimes difficult to use, or the mixing and pulverization treatment must be strictly performed to increase the cost. Therefore, the average particle diameter of the zinc oxide powder is in the range of 0.1 to 1 · 8.//m, and is preferably 〇·3~1.. It is a number within the range of 0·5~1·2#m. Further, the average particle diameter of the indium oxide powder is also substantially the same as the average particle diameter of the zinc oxide powder. Therefore, the average particle diameter of the indium oxide powder used for the production of the target is 2 // m or less, and the number in the range of 〇·1 to 1 · 8 // m is ideal, 0 · 3 to 1. 5 / zm The number within the range is more ideal, and the number within the range of 〇·5~1 · 2 // m is ideal. (4) Body impedance The body impedance of the target is preferably 1 X 1 0 — 3 Ω · c m or less. The reason is that when the body impedance is 1 X 1 0 - 3 Ω · c m or more, abnormal discharge occurs during sputtering, and as a result, protrusions may be generated on the surface of the target. When the bulk resistance is 0 · 5 Χ 10_3 Ω·cm or less, the obtained film quality may become crystalline. Therefore, the body impedance is ideally 0. 5 X 1 0 — 3 to 0. 9 X 10 — 3 Ω · The number of 値 in the range of cm, more preferably 0 · 6x 10~3~0 · 8χ10_3Ω·cm value. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

-If- 1269817 A7 _ B7____ V. INSTRUCTIONS (15) (5) Density The density of the target is preferably 6 · 7 g / c m 3 or more. The reason is that when the density of the target is 6 · 7 g / cm 3 or less, the occurrence of protrusions may increase. However, when the density of ¥E exceeds 7 · 1 g / cm 3 , the crucible itself becomes metallic, and the stability of sputtering cannot be obtained. As a result, a film having excellent conductivity or transparency may not be obtained. Therefore, the density of the target is desirably a number within the range of 6·8 to 7·Og/cm3. (Please read the precautions on the back and then fill out this page.) The first tin is the same in quantity, 3, the state is 9%-shaped ~ the amount is 7 heavy in 6 8 indium ~ Minghua 2 oxy zinc. 2 化化 m The oxygen content is in the 尙 and splashing%^' is the amount of ¥E _ state plating weight is morphologically splashed 5 1 shape is applied 2 is the actual state ~ than the real 2 shape 5 sub 2 Actualized ί 锌 锌!*1 订--'!----Line Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing (1) composition ratio D indium oxide second embodiment, the target component In the composition of each metal oxide, the content ratio of indium oxide must be a number within the range of 6 7 to 93 % by weight. For this reason, when the content ratio of indium oxide is 67% by weight or less, crystallization by heat treatment is difficult, and the conductivity of the obtained transparent conductive oxide is lowered. In addition, when the content ratio of indium oxide exceeds 93% by weight, the paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) -18 - 1269817 A7 B7 5. Invention Description (16), on the contrary, Crystallization 'Sometimes the subsequent film quality becomes crystallized by sputtering. (Please read the precautions on the back and fill out this page.) Therefore, when the balance between the conductivity and the crystallinity of the transparent conductive oxide is considered, the content of indium oxide is preferably 80 to 93% by weight, more preferably 7 A number in the range of 4 to 9 3 wt%. The content of tin oxide in the tin oxide target is a number in the range of 5 to 25% by weight. For this reason, when the content ratio of the tin oxide is 5% by weight or less, even if the heat treatment is crystallization, the conductivity cannot be improved, and the conductivity of the obtained transparent conductive oxide may be lowered. When the content of the tin oxide is more than 25 % by weight, the transparent conductive film does not crystallize when it is thermally treated, and the conductivity may be lowered, and protrusions may easily occur during sputtering. Therefore, when the balance between the conductivity of the transparent conductive oxide and the crystallinity and the occurrence of the P-stop projection is more excellent, the ratio of the content of the tin oxide is preferably 5 when the transparency of the transparent conductive oxide is considered. ～20% by weight, more desirably, a number within the range of 7 to 15% by weight. 2 The content of zinc oxide in the zinc oxide target is in the range of 2 to 8 wt%. For this reason, when the content ratio of zinc oxide is 2% by weight or less, the splashing -19 - the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 5. Inventive Note (17) The obtained transparent conductive oxide is easily crystallized, and the crystal grain size of the target is increased. In some cases, protrusions are likely to occur during sputtering. When the content of the zinc oxide is more than 8% by weight, the transparent conductive oxide may not crystallize even by heat treatment, and as a result, the conductivity of the transparent conductive oxide may not be improved. Further, when the proportion of zinc oxide is more than 8% by weight, the bulk resistance of the target may exceed 1 x 10 0 - 3 Ω · c m , and stable sputtering cannot be obtained. Therefore, considering the conductivity of the transparent conductive oxide, the balance between the bulk resistance of the target and the prevention of the occurrence of the protrusions is more excellent, and the content ratio of the zinc oxide is preferably 2 to 6 wt%, more preferably 3 to A number in the range of 5% by weight. 4 Tin/Zinc The atomic ratio of tin to all metal atoms is the same or higher than the atomic ratio of zinc to all metal atoms. Specifically, the atomic ratio of tin/zinc is preferably 1 or more. When the atomic ratio of tin/zinc is 1 or less, even if the diffusion movement of the heat-treated tin is reduced, the doping effect is lowered, and the conductivity of the obtained transparent conductive oxide is lowered. However, when the atomic ratio of tin/zinc is too large, unreacted tin remains in the form of ionic impurities, and so-called scattering due to ionic impurities 'conductivity is lowered. Therefore, the atomic ratio of tin/zinc is preferably in the range of 2 to 10, more preferably in the range of 3 to 5. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

1269817 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Β7 Β7 V. Description of Invention (18) 5 Weight of Tin Atom and Zinc Atom Percentage of Tin Atom to Total Metal Atom (S η / ( IN + Sn+Zn)xlOO The number 値 is at least greater than the weight percentage of zinc atoms to all metal atoms (Zn/(In + Sn + Zn) X · 1 0 0 ). The reason is that when the difference in weight percentage (%) is more than 3%, the doping effect of tin by heat treatment can be effectively extracted. Therefore, the conductivity of the obtained transparent conductive oxide can be improved. However, when the difference in weight percentage (%) is too large, the conductivity may be lowered due to scattering of ionic impurities as described above. Therefore, the weight percentage of the tin atom and the zinc atom is desirably 4 to 30%, more preferably 5 to 20%. (2) Crystal structure 1 The target of the second embodiment is also the same as the first embodiment, and is characterized by containing a hexagonal layer represented by I ΐ 2 〇 3 (Ζη〇) μ (but Μ is an integer of 2 to 2 〇). Indium oxide and zinc oxide of the compound. (3) Crystal structure 2 1 spinel structure compound Regarding the crystal structure of the second embodiment, the target is substituted with a hexagonal layered compound or a hexagonal layered compound and a general formula of η 2 S η〇4 Indicates the spinel structure compound' and the spinel structure is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). h·!------------- Order-丨'------Line* (Please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 ___B7__ V. Description of Invention (19) Crystalline Size of Compound It is the number below 5 # m. The reason is that the crystal form of the spinel structure compound represented by Z n2S η 〇4 contains tin oxide and zinc oxide, which increases the density of the target and improves the conductivity. Therefore, the use of such a target can improve the stability at the time of sputtering. The inclusion of these hexagonal layered compounds or spinel structure compounds suppresses the growth of indium oxide crystals, and as a result, the source plating target becomes a finer and dense crystal structure. The conductivity of the transparent conductive oxide can also be improved. 2 X-ray diffraction analysis The existence of the spinel structure compound represented by ζ η 2 S η 〇 4 was confirmed by X-ray diffraction analysis of the crystal structure. For example, when the X-ray diffraction analysis chart and the peak map shown in Fig. 6 (a) to (d) are obtained, the existence of the spinel structure compound represented by Ζ η 2 S η 0 4 can be confirmed. 3 Crystal grain size - The crystal grain size of the spinel structure compound is preferably 5 // m or less. When the crystal grain size of the reason is more than 5 # m, the protrusion is remarkably generated during sputtering. However, the crystal grain size is too small, sometimes the control is not easy, and the types of raw materials that can be used are too limited. Therefore, the crystal grain size of the spinel structure compound in the target is preferably in the range of 〇·1 to 4//m, and is in the range of 0·5~3//m (please read the back note first) Fill in this page again)

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -ZZ - 1269817 A7 B7 _ V. The invention description (2Q) is more ideal. K—— 丨------11^!丨丨1 order: (Please read the precautions on the back and fill out this page) The crystal grain size of the spinel structure compound is described in the first embodiment, and the hexagonal The crystal layered compound can be easily identified by using the corresponding map (concentration distribution) of zinc of Ε Μ A, whereby the crystal grain size can be measured. (4) Relationship between the size of the crystal grain size and the number of occurrences of the projections The relationship between the crystal grain size of the spinel structure compound and the hexagonal layer compound and the number of occurrences of the projections will be more specifically described with reference to Fig. 4. The horizontal axis of Fig. 4 is the size (μm) of the crystal grain size in the state in which the spinel structure compound and the hexagonal layered compound coexist, and the vertical axis is the number of protrusions per unit area and unit sputtering time. /8Hr s/ 9 Ο Ο Μ Μ 2 ). It is easy to understand from Fig. 4 that when the crystal grain size of the spinel structure compound and the hexagonal layered compound is 5 // m or less, the number of protrusions occurring is 0/8H rs/9 Ο 0ΜΜ2, and when When the crystal grain size of the spar structure compound and the hexagonal layered compound exceeds 5 // m, the number of occurrences of the protrusions increases sharply, and protrusions of 5 to 32 / 8 Hr s / 900 Μ Μ 2 occur. In contrast, in the figure of Figure 4, in order to effectively prevent the occurrence of protrusions, the crystal grain size of the spinel structure compound and the hexagonal layered compound must be 5 // m. Hereinafter, when the crystal grain size is 4 // m or less, the number of occurrences of the projections can be surely prevented. 5 Control of crystal grain size - Ζό - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1269817 A7 _ B7 V. Invention description (21) The crystal grain size of the spar structure compound can be controlled within a predetermined range by appropriately changing the kind of the raw material powder constituting the target, the average particle diameter of the raw material powder, the production conditions of the target, and the like. For example, the type and average particle diameter of the raw material powder are set such that the average particle diameter of the zinc oxide powder used for the production of the target is 2 // m or less and the average particle diameter of the tin oxide powder is set to be in the range of 0·〇1 to Ijm. The number is 値, and the average particle diameter of the tin oxide powder is lower than the average particle diameter of the zinc oxide powder. The reason is that the average particle diameters of the zinc oxide powder and the tin oxide powder are respectively limited to this range, and the diffusion movement can be controlled, and the crystal grain size of the hexagonal layered compound or the spinel structure compound in the target can be easily controlled. Therefore, the average particle diameter of the tin oxide powder is a number 値 in the range of 0·0 2~0 · 5 //m, and ideally, the number within the range of 〇· 〇3~0 · 3//m is optimal. It is a number within the range of 0.05 to 0.2 #m. Further, a hexagonal layered compound or a spinel structure compound is formed in advance to form a desired particle size, and then mixed with indium oxide powder to obtain a desired target (4) bulk impedance or density as described in the first embodiment, and the second embodiment The bulk impedance of the target is preferably 1 X 1 0 - 3 Ω · cm or less, and the density of the target is preferably 6 7 7 g/cm 3 or more. [Third Embodiment] This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -z4 - -------I------------ -------- Line · (Please read the note on the back and fill out this page) 1269817 Α7 Β7 5. Inventive Note (22) The third embodiment is an embodiment of the third invention, which is used I η / ( I n + Zn) represents an atomic ratio of 0 · 7 5~ (please read the back note before filling this page) 0 · 97 range, with I n2〇3 (Zn〇)M (However, Μ is an integer of 2 to 20) A hexagonal crystal layered compound, and the hexagonal crystal layered compound has a crystal grain size of 5 // m or less of a transparent conductive oxide obtained by a sputtering target. (1) Target In the third embodiment, the target used is the same as that of the first embodiment. Therefore, a target having an atomic ratio of I η / ( I n + Zn) in the range of 0 · 75 to 0 · 97 is preferably a target in the range of 〇 80 to 0.95, more preferably 0 · 8 Targets in the range of 5 to 0 · 9 5 . (2) Film thickness The film thickness of the transparent conductive oxide can be appropriately selected in accordance with the use or the material of the substrate on which the transparent conductive oxide is provided, and is usually in the range of 3 to 3, OOOnM. The reason for the printing of the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is that when the film thickness is 3 η Μ or less, the conductivity of the transparent conductive oxide is insufficient, and when it exceeds 3,0 0 η Μ, the light transmittance is lowered or the transparent conductive is manufactured. When the transparent conductive oxide material is deformed during the process of the oxide material or after the production, the transparent conductive oxide may be susceptible to cracking or the like. Therefore, the film thickness of the transparent conductive oxide is preferably 5~ The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 297 297 public) 1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (23) 1, the number within the range of OOOnM, more preferably the number within the range of 10~800 η Μ. Fig. 7 and Fig. 8 show the effect of the impedance change rate or film thickness of the transparent conductive oxide on the light transmittance curve. According to Fig. 7, even if the film thickness of the transparent conductive oxide (substrate PET) is changed to 68 Μ 曲线 (curve Α ), 1 0 0 η Μ (curve Β ) and 2 0 0 η Μ (curve C) At the 90 °C, 1,0 0 hour heating test, there was almost no difference in the rate of change in impedance. According to Fig. 8, when the film thickness of I ZO is changed to 1 OOnM (curve Β), 220 nM (curve C) and 310 nM (curve D), when the film thickness is increased, the light transmittance of each wavelength is somewhat lowered. tendency. (2) Substrate It is preferred to form a transparent conductive oxide on the substrate using a target. As such a substrate, for example, a glass substrate or a film made of a transparent resin or a sheet substrate can be used. More specifically, the glass substrate is, for example, a soda lime glass, lead glass, borosilicate glass, perrhenic acid glass, alkali-free glass or the like. Among these glass plates, an alkali-free glass plate is preferred because it does not diffuse alkali ions in the transparent conductive oxide. Further, the transparent resin is preferably a resin having a high light transmittance and excellent electrical insulating properties, and specifically, a polyester resin such as a polyethylene terephthalate resin, a polycarbonate resin, or a polyacrylic resin. Polyether resin This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -ZD - h-! —-----丨! Τι------ (Please read the note on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 _ B7 V. Invention Description (24), Acrylic Resin, Polyimide Resin , polyamine resin, maleic acid diamine resin, and the like. Among these resins, a polycarbonate resin, a polyacrylic resin, a polyethylene terephthalate resin or a polyether resin has heat resistance, and therefore it is very suitable. (4) heat treatment of the transparent conductive oxide of the third embodiment is After the film formation, heat treatment (including crystallization treatment) can improve conductivity. The heat treatment condition is a temperature range of 180 to 300 ° C, preferably a temperature range of 2 0 0 to 2 50 ° C, and the treatment time is in the range of 0 · 5 to 3 hours. Under such treatment conditions, for example, the film formation ratio can be reduced by 20 to 80%. (5) Specific resistance The specific resistance of the transparent conductive oxide is preferably 800 Ω / Ω · c m or less. When the specific resistance exceeds 80 ° @ Ω · cm, the use can be too narrow. Therefore, the specific resistance of the transparent conductive oxide is desirably 600 Ω Ω · cm or less, more preferably 3,000 Ω · cm or less. (6) Light transmittance The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -27 - (Please read the note on the back and fill in this page) --------- Tr·---------Line - 1269817 A7 ____Β7 V. Description of invention (25) One example of a transparent conductive oxide is the thickness of 1 Ο Ο η ,, as shown in the curve of Fig. 8 (ΙΖ 0 /7059 glass), the light transmittance (wavelength 5 Ο Ο η Μ or 5 5 Ο η Μ) is preferably more than 75 %, and more preferably 80% or more. Such a light transmittance can be applied to a transparent electrode of various display devices such as a liquid crystal display element or an electroluminescence element which requires high transparency and conductivity. The curve 第 in Fig. 8 is a transmittance curve of a glass substrate (7559 glass), and the curve C is an example of forming an IZ0 film of the third embodiment having a thickness of 2 2 Ο nM on a glass substrate, and the curve D is An example of the I Z0 film of the third embodiment having a thickness of 3 10 nM is formed on the glass substrate, and the curve E is an example of forming the I Τ〇 film of the third embodiment having a thickness of 2 2 Ο η 玻璃 on the glass substrate. (7) When the refractive index (wavelength 5 Ο Ο η Μ ) of the refractive index transparent conductive oxide is 90 Μ · Μ, the curve B (I Ζ〇 / 7 0 5 9 glass) is shown in Fig. 9. Show that 2 · 5 or less is ideal. Such a refractive index can be applied to a transparent electrode of various display devices such as a liquid crystal display element or an electroluminescence element which requires high transparency or antireflection. The curve 第 in Fig. 9 is an example of forming an I Z 0 film of the third embodiment having a thickness of 3 Ο η 玻璃 on a glass substrate (7559 glass). This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page). %----- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 B7 V. INSTRUCTIONS (26) (8) Surface roughness The index of surface roughness of transparent conductive oxide P - V (according to J ISB0601) is preferably 1/M or less. In the case of this P-V, even when it is used for a transparent electrode of various display devices such as a liquid crystal display element or an electroluminescence element, it is possible to effectively prevent occurrence of disconnection or short circuit. When expressed in terms of other surface roughness, R a (according to JISB0601) ΙΟΟηΜ is ideal, and RZ (according to J ISB0601) is preferably 500 nM or less. (9) Film forming method When a transparent conductive oxide film is formed on a substrate, a magnetron sputtering device, an electron beam device, an ion plating device, a laser ablation device, or the like can be used, wherein a magnetron sputtering device is used. ideal. For example, the conditions for film formation using such a magnetron sputtering device cause a slight variation in the output of the ion ions due to the area of the target or the film thickness of the transparent conductive oxide, but usually the ion output is 1 cm 2 per target area. In the range of 0.3 to 4 W, the film formation time is desirably 5 to 1 20 minutes. In such a film forming condition, a transparent conductive oxide having a desired film thickness can be easily obtained. (10) Application The preferred application of the third embodiment is, for example, a transparent electrode of a liquid crystal display element, a transparent electrode of an electroluminescence element, and a transparent electric paper of a solar cell. The Chinese National Standard (CNS) A4 specification (210) X 297 mm) (Please read the notes on the back and fill out this page) --------.丨_------% Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print A7 1269817 B7 Five (Invention) (27) A base material when the transparent electrodes are formed by an etching method, or a heater for preventing icing which is used for an antistatic film or a window glass. (Fourth Embodiment) (Fourth Embodiment) The fourth embodiment of the fourth embodiment of the present invention includes the indium oxide 6.7 to 9 in the sputtering target according to the third embodiment. 3 wt%, a transparent conductive oxide obtained by sputtering a target having a tin/zinc atomic ratio of 1 or more and 5 to 8% by weight of tin oxide and 2 to 8% by weight of zinc oxide. (1) Target The target used in the fourth embodiment can be the same as the target of the second embodiment. In other words, it is a target composed of indium oxide 6 7 to 93 % by weight, tin oxide 5 to 25 % by weight, and zinc oxide 2 to 8 % by weight. However, the target composition is preferably a composition comprising 7 to 3% by weight of indium oxide, 5 to 20% by weight of tin oxide, and 2 to 6% by weight of zinc oxide, more preferably 80 to 8.9 % by weight of indium oxide. The composition of the tin oxide is 8 to 15% by weight, and the zinc oxide is 3 to 5% by weight. In the target used in the fourth embodiment, the target of the fourth embodiment is similar to the second embodiment, and the atomic ratio of the tin atom of the tin oxide to the total metal atom of the constituent component of the transparent conductive oxide is greater than that of the oxidation. The atomic ratio of zinc to zinc atoms to all metal atoms, in other words, the tin/zinc ratio is preferably 1 or more. The target system used in the fourth embodiment is the same as that of the second embodiment, and it is preferable to use indium oxide and zinc oxide to form I η 2 〇 3 ( Ζ η〇) μ (μ This paper scale applies the Chinese National Standard (CNS) A4 specification. (210 χ 297 mm) ?3u - 1269817 A7 B7 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions (28) 2 2~2 0 )) The hexagonal layered compound, in the crystal of indium oxide An oxide target of a form in which a hexagonal layered compound is locally present. The number of Μ in the formula of the hexagonal layered compound is 2 to 20, preferably 2 to 8, more preferably 2 to 6. The target used in the fourth embodiment preferably has a purity of 98% or more. When the purity is 98% or less, the chemical stability of the obtained film is lowered due to the inclusion of impurities, or the conductivity is lowered, and the light transmittance is lowered. Therefore, the ideal purity is 99% or more, and the more desirable purity is 99.9% or more. When a target of a sintered body is used, the relative density (theoretical density) of the target is desirably 96% or more. When the relative density is 96% or less, the film formation rate is lowered or the film quality is lowered. Therefore, the relative density of the sintered target is desirably 97% or more, and more desirably 98% or more. The relative density (theoretical density) of the target is the total amount calculated from the density of each raw material and the amount of each addition (% by weight). (2) Crystallization treatment The transparent conductive oxide of the fourth embodiment is formed by sputtering the amorphous transparent conductive oxide by sputtering using the above-mentioned target, and then at a temperature of 2300 ° C or higher. It is desirable to produce crystallization. When the film is formed by the sputtering method as described above, the amorphous transparent conductive oxide is formed by the formation of the amorphous transparent conductive oxide even if the composition of the metal oxide constituting the transparent conductive oxide is the same. The characteristics are still better than the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public) - one • ul ^ ln.--------- '·---- ^---- -- Line i (please read the notes on the back and fill out this page) 1269817 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Print A7 Η ____ V. Inventions (29) Crystalline transparent conductive oxides. Then, the amorphous transparent conductive oxide is crystallized to form a transparent conductive oxide, and such a transparent conductive oxide can greatly improve conductivity. As shown in Fig. 7, such a transparent conductive oxide is excellent in stability at high temperature or under high humidity. The amorphous transparent conductive oxide is formed. The heat treatment temperature at the time of crystallization is preferably 2,500 t: or more, more preferably 2,800 ° C or more. The higher the heat treatment temperature, the faster the crystallization rate, but the temperature at which the transparent substrate does not thermally deform is preferable. Therefore, for example, when a resin as a substrate is used, a temperature of 250 ° C or lower is preferable, and when a glass substrate is used, a temperature of 500 ° C or lower is preferable. When the crystal form crystal obtained by the heat treatment is considered to have a heat treatment temperature, a double-tip crystal of indium oxide monomer is preferred. The reason is that when other hexagonal layered compounds or spinel compounds are contained, conductivity may be lowered by diffusion of ion impurities. The effect of the crystallization temperature will be described in more detail with reference to FIG. The horizontal axis of Fig. 10 is the heat treatment temperature (°C) of the crystallization temperature, and the vertical axis is the specific resistance (// Ω · c m ). It can be understood from the solution of Fig. 10 that when the heat treatment temperature is below 230 ° C, the specific resistance is as high as 3,200 / / Ω · cm, and conversely, when the heat treatment temperature exceeds 350 ° C, the specific resistance is 1,0 0 0 // Ω · cm ° Conversely, it is known from Fig. 10 that in order to effectively reduce the specific resistance, for example, to obtain a number of 0500 Ω·cm, the heat treatment temperature is 2 The number of temperatures in the range of 3 0 to 3 2 0 °C, the ideal heat treatment temperature is -"-VI Γ - IIII Νβ ϋ n 1 n ϋ (please read the notes on the back and fill out this page) The scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -0Z- 1269817 A7 ______jB7 V. Description of invention (30) 2 4 0~3 0 0 °C in the range of 値, more ideal heat treatment The temperature is in the range of 2 5 0 to 2 90 °C. (Please read the precautions on the back side and fill out this page.) (3) Uranium engraving treatment The transparent conductive oxide of the fourth embodiment is preferably formed into a shape by uranium engraving. In other words, the amorphous transparent conductive oxide formed by sputtering can be easily etched using, for example, an aqueous solution of oxalic acid having a concentration of 5% by weight. Increasing the etching process temperature can improve the etching characteristics. For example, when etching at 40 to 50 °C, the etching rate can reach Ο · 1 / m / min or more. Therefore, the amorphous transparent conductive oxide has a uranium enrichment using a strong acid such as hydrochloric acid or aqua regia as in the conventional IT film, and does not require a complicated operation such as providing a protective film on the wiring electrode, so that etching can be easily performed. Characteristics. Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. The etching solution is particularly suitable for the use of an aqueous solution of oxalic acid at a concentration of 3 to 10% by weight. When the concentration of the aqueous oxalic acid solution is less than 3% by weight, a sufficient etching rate may not be obtained, and when it exceeds 10% by weight, crystals may be generated in the solution. The temperature of the etching solution is desirably in the range of 30 to 90 °C. The reason is that when the temperature of the etching solution is 30 ° C or less, the etching rate is sometimes too low' and the temperature of the etching liquid exceeds 90 ° C, the management of the uranium engraving is difficult. Therefore, the temperature of the etching liquid is desirably in the range of 3 5 to 70 ° C. The temperature of the etching liquid is preferably in the range of 40 to 50 ° C. -Μ - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print i, invention description (31) (4) film thickness transparent conductivity The form of the oxide is not particularly limited, and for example, it is preferably a film. In this case, the film thickness can be appropriately selected in accordance with the use or the material of the substrate in which the transparent conductive oxide is provided, and is preferably in the range of 3 to 3, 〇〇〇nM, in the same manner as in the third embodiment. (5) In the multilayer composite transparent conductive oxide, a gas barrier layer, a hard coat layer, an antireflection layer, or the like is provided on the substrate surface on the other side of the surface on which the transparent conductive oxide is provided to form a multilayer composite. Preferably. As the material for forming the gas barrier layer, for example, an ethylene-vinyl alcohol copolymer or polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride, polyvinylidene fluoride or the like can be used. Further, as the material for forming the hard coat layer, for example, a titanium-based or cerium oxide-based hard coating agent, a polymer material such as polymethyl methacrylate or an inorganic polymer material such as Polyphosphazen can be used. The material for forming the antireflection layer can be, for example, a low refractive index polymer, a fluoride such as MgF 2 or CaF 2 , an oxide such as S i〇, Zn〇, Bi 2 , Al 2 , 3 or the like. Constitute. The transparent conductive oxide of the present invention may have an organic polymer film or an inorganic film on its surface. (6) Film formation method This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — ——— — — — — — — I — · 1111111 ^ 11111111 (Please read the notes on the back first. Fill in this page) 1269817 A7 B7 V. INSTRUCTIONS (32) 1 Film forming apparatus Next, the method for producing a transparent conductive oxide of the present invention can be performed by, for example, a sputtering target method, an ion plating method, an evaporation method, and a laser ablation method. Various methods such as law are used to manufacture. It is preferable to use a sputtering method when considering the performance of a transparent conductive oxide, productivity, and the like. The sputtering method can be, for example, a usual sputtering method (hereinafter referred to as direct sputtering) or reactive sputtering using R F magnetron sputtering or DC magnetic tube sputtering. In other words, the composition of the sputtering target to be used or the sputtering condition may be appropriately selected in accordance with the composition of the transparent conductive oxide. 2 Film Formation Conditions 1 The sputtering conditions when a transparent conductive oxide is provided on a transparent substrate by direct sputtering are different depending on the method of direct sputtering or the composition of the sputtering target, and the characteristics of the device to be used. When it is not possible to use the DC magnetron sputtering method, it is preferable to set, for example, the following. (Vacuum degree) The degree of vacuum of the direct sputtering method is preferably reduced to 1 X 1 〇 to 3 P a before the sputtering. The degree of vacuum during sputtering is preferably 1 · 3x10^~6 · 7Pa. For this reason, when the degree of vacuum during sputtering is greater than 1 · 3 X 1 0 — 2 P a, the stability of the plasma may decrease. When the degree is lower than 6 · 7 P a, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) % Ministry of Economic Affairs Intellectual Property Office Staff Consumption Co-operative printing -00 - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1269817 A7 ______B7__ V. Invention description (33) Sometimes it is impossible to increase the voltage applied to the target. Therefore, the degree of vacuum during sputtering is preferably 2·7xl 〇~2 1.3?3, more preferably 4.0乂102~6.7\1〇-1 Pa 〇 (applied voltage) > ideal for applying voltage to the target during sputtering It is a number within the range of 2 0 0~5 〇〇v. The reason is that when the applied voltage is 2 Ο Ο V or less, it is difficult to obtain a good film, or the film forming speed is limited, and when the applied voltage exceeds 5 Ο 〇v, abnormal discharge may occur. Therefore, the voltage applied to the target during sputtering is in the range of 2 3 0 to 4 5 Ο V, and more preferably in the range of 2 5 0 to 4 2 Ο V. (Splating gas) The sputtering gas (atmosphere gas) at the time of sputtering is preferably a mixed gas of an inert gas such as an argon gas and an oxygen gas. 001。 The mixing ratio (volume ratio) of the argon gas to the oxygen gas is preferably 0.6.0.4 to 0.999:0. 001. The partial pressure of oxygen is 1 · 4xl0_4 〜 6 · 7xl 〇 - iPa, ideally 3 X 1 0 - 4~1 X 1 0 - 1 P a, more preferably 4 · 0 X 10 - 4 ~ 7xlO_2Pa. When the mixing ratio or the oxygen partial pressure is not within the range, a transparent conductive oxide having low resistance and high light transmittance may not be obtained. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -36 - (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1269817 A7 ___B7 V. INSTRUCTIONS (34) 3 Film Formation Conditions 2 In the method of providing transparent conductive oxide on a transparent substrate by reactive sputtering, the sputtering target The crucible is composed of an alloy of indium, tin and zinc, and the alloy target can be obtained by, for example, dispersing a powder or a small piece of tin and zinc in molten indium and then cooling. The purity of the alloy target is 98% or more as the target for direct sputtering, and the purity is preferably 99% or more, and more preferably 9 9 · 9 % or more. The conditions of the reactive sputtering differ depending on the composition of the sputtering target or the characteristics of the device to be used, but the vacuum degree at the time of sputtering, the applied voltage and the substrate temperature are preferably the same as those of the direct sputtering of DC. The atmosphere gas is preferably a mixed gas of an inert gas such as an argon gas and an oxygen gas, but the ratio of the oxygen gas is preferably set to be higher than the ratio of the oxygen gas at the time of direct sputtering. When an inert gas of argon gas is used, the mixing ratio (volume ratio) of the argon gas to the oxygen gas is preferably 0 · 5 : 0 · 5 to 0 · 9 9 : 0.01 ° (7). The transparent conductivity of the fourth embodiment is used. Since the oxide has the above characteristics, it can be used, for example, as a transparent electrode of a liquid crystal display element, a transparent electrode of an electroluminescence element, a transparent electrode of a solar cell, or the like, or formed by etching----1----- -· I----丨丨tr----------Line. (Please read the notes on the back and fill out this page.) This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -ό(- 1269817 A7 B7 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Inventions (35) The base material of these transparent electrodes' or antistatic film or window glass to prevent icing (5th embodiment) The fifth embodiment is based on the transparent conductive oxide of the third to fourth embodiments, and is measured by X-ray photoelectron spectroscopy (XPS). The transparent conductive oxygen having a half-width of the combined energy peak of the oxygen 1 S orbital of 3 e V or less (1) Half-width of the binding energy peak of the oxygen 1 S orbital The transparent conductive oxide of the fifth embodiment can be formed by sputtering using the target of the first to second embodiments. Transparent conductive oxide The half-turn width of the binding energy peak of the oxygen 1 S orbital measured by X-ray photoelectron spectroscopy ( XPS ) is preferably 3 e V or less. The reason is that when the half-turn width exceeds 3 e V, the initial connection resistance may increase, or may be long-term. The connection resistance in use is significantly increased. When the width of the half turn is 1 e V or less, the width of the material that can be used is limited, and it is sometimes difficult to control the width of the half turn. Therefore, the width of the half turn is ideally 1 to 2 · 9 e V The range is more preferably a range of 2 · 〇 〜 2 · 8 e V. As described above, limiting the width of the half of the combined energy peak of the oxygen 1 S orbit to the specified range is based on the following findings. In other words, the film is formed by sputtering. The surface of the transparent conductive oxide (please read the back of the note first and then fill out this page) % *' Order l· — '------ Line wins the paper scale applicable to China National Standard (CNS) A4 specification ( 210 X 297 mm) 1269817 A7 B7 DESCRIPTION OF THE INVENTION (36) When the X-ray photoelectron spectroscopy method is used, the "two peaks appear" are the peaks generated by the metal oxide, and the elements other than the metal-oxygen-metal, for example, as shown in Fig. 3, hydrogen or The peak generated by the carbon bond. The peak generated by the bond of the element other than the metal-oxygen-metal, in other words, the transparent conductive oxide with a relatively large peak of the binding energy of the oxygen 1 s orbit as the transparent · conductive oxide and When the external connection of the liquid crystal drive circuit or the like is strictly connected, the connection resistance may increase, or the connection resistance may increase during long-term use. In the fifth embodiment, the half-turn width of the binding energy peak of the oxygen 1 S orbital measured by X-ray photoelectron spectroscopy (XPS) is limited to a predetermined enthalpy, and the initial connection resistance can be lowered and the long-term connection can be suppressed. The increasing tendency of the connection resistance in use. (2) Measurement method The half-turn width of the binding energy peak of the oxygen 1 S orbital measured by X-ray photoelectron spectroscopy (X P S ) on the surface of the transparent conductive oxide can be calculated from the oxygen 1 S orbital peak and its baseline. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives (please read the notes on the back and fill out this page). In other words, the combined energy peak of the oxygen 1 S orbital is obtained by X-ray photoelectron spectroscopy (XPS) as shown in Figure 12. Show an oxygen 1 s orbital peak. Then, in the oxygen 1 S orbital peak obtained, the Shirley type can be used to set the baseline. Find the length from the baseline to the peak, and set the position one half of its length. Secondly, the combined energy width of the oxygen 1 s orbit can be measured at a position half the length set, and this energy width can be used as the half width. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) Γ35Γ ---- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1269817 A7 _B7 V. Invention description (37) (3) Half width Controlling the amount of moisture in the vacuum chamber The amount of moisture in the vacuum chamber during sputtering can be easily controlled by the transparent conductive oxide using the X-ray photoelectron spectroscopy method to determine the half-width of the binding energy peak of the oxygen 1 S orbital. In other words, in order to obtain a transparent conductive oxide having a half-width of 3 e V or less, when the film is formed by sputtering, the amount of water in the vacuum chamber is preferably 1 X 1 0 - 5 〜 1 X 1 0 - 1QP a In the range. More preferably, the amount of water in the vacuum chamber is maintained in the range of 1 X 1 0 - 6 to 1 X 1 〇 - 1 ^ P a . 2 Applied voltage The half-turn width of the transparent conductive oxide can also be controlled by applying a voltage to the sputtering target when the film is formed by sputtering. For example, as in the fourth embodiment, the applied voltage is preferably a number within the range of 2 0 0 to 500 V. 3 Sputtering gas In order to easily control the half width of the transparent conductive oxide within a predetermined range, it is preferable to use a mixed gas of an inert gas such as an argon gas and an oxygen gas for the sputtering gas (atmosphere gas). When an inert gas of argon gas is used, the mixing ratio (volume ratio) of argon gas to oxygen gas is preferably 0 · 6 : 0 · 4~0 · 9 9 9 · This paper scale applies to China National Standard (CNS) A4 specification. (210 X 297 mm) (Please read the notes on the back and fill out this page)

1269817 A7 B7 V. Inventive Note (38) 〇 · ο ο 1 ° When such a mixed gas is used, the obtained transparent conductive oxide has good conductivity and a transparent conductive oxide having high light transmittance can be obtained. (4) Substrate A base material for forming a transparent conductive oxide can be, for example, a glass substrate or a film or sheet substrate made of a transparent resin. The glass substrate is, for example, a transparent glass plate made of soda lime glass, lead glass, borosilicate glass, high phthalic acid glass, alkali-free glass or the like. Among these glass plates, an alkali-free glass plate is preferable because it does not diffuse ions in the transparent conductive oxide. Further, the transparent resin is preferably a resin having a high light transmittance and excellent electrical insulating properties, and specifically, a polyester resin such as a polyethylene terephthalate resin, a polycarbonate resin, or a polyacrylic resin. Polyether resin, acrylic resin, polyimide resin, polyamide resin, maleic acid resin, and the like. The transparent substrate used herein is a transparent glass substrate or a transparent resin substrate, and has a light transmittance of 70% or more, preferably 80% or more, more preferably 90% or more. The thickness of the transparent substrate can be appropriately selected in accordance with the use of the transparent conductive material or its material, and is usually a number within the range of 15 @ 3 to 3 mm, and is preferably a number within the range of 50 @ 1 to 1 MM. (5) Middle layer (please read the precautions on the back and fill in this page) ' · II l· II Lr ·ΓΙ.— — — — — — Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Print this paper scale for China Standard (CNS) A4 specification (210 X 297 mm) -41 - A7 1269817 B7_ V. INSTRUCTION DESCRIPTION (39) In the fifth embodiment, in order to improve the adhesion to the transparent conductive oxide, transparent conductivity is provided. An intermediate layer having a thickness of 0·5 to 10//m is preferably provided on the surface of the substrate on the side of the oxide. As the intermediate layer, a single layer structure composed of a metal oxide (oxide containing cerium), a metal nitride (nitride containing cerium), a metal carbide (carbide containing cerium), a crosslinkable resin, or the like can be used. Or a layer composed of a multilayer structure. These metal oxides are, for example, A 12〇3, S i Οχ (〇 < X ^ 2 ), Zn〇, Ti〇2 and the like. Further, the metal nitride is AIN, S i3N4, TiN or the like. The metal carbide is, for example, S i C, B 4 C or the like. The crosslinkable resin is, for example, an epoxy resin, a phenoxy ether resin, an acrylic resin or the like. When a substrate made of a transparent resin is used, such an intermediate layer is preferably in the form of a two-layer structure in which a crosslinkable resin and an inorganic layer are sequentially laminated. When a transparent glass substrate is used as the transparent substrate, it is preferred to sequentially laminate the two-layer structure of the crosslinkable resin and the inorganic layer. Because the two-layer structure is more dense than the single-layer structure. In either case, when the inorganic layer is disposed on the side where the transparent conductive oxide of the intermediate layer is in contact with each other, a transparent conductive material which is more excellent in thermal stability can be obtained. When the intermediate layer of the crosslinkable resin is provided on the surface of the transparent resin substrate, an adhesive layer or a gas barrier layer may be contained between the surface of the substrate and the crosslinkable resin. As the adhesive for forming such an adhesive layer, for example, an epoxy-based, urethane-based phenoxy ether-based adhesive or the like can be used. The gas barrier layer is made of transparent conductive material as the paper scale. It is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) l·---------------Γ---1— ^ ^------- (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Economy Ministry Intellectual Property Bureau Staff Consumer Cooperatives Print 1269817 A7 __B7_ V. Invention Description ( 4G) When used as a transparent electrode such as a liquid crystal display element, it prevents water vapor or oxygen from diffusing into the liquid crystal. (6) Transparent conductive oxide The transparent conductive oxide of the fifth embodiment is amorphous and excellent in etching characteristics. Therefore, the amorphous transparent conductive oxide has an etching solution using a strong acid such as hydrochloric acid or aqua regia as in the conventional I τ 0 film, and does not require a complicated operation such as providing a protective film on the wiring electrode, so that it can be easily performed. The characteristics of the etching. The etching solution for the amorphous transparent conductive oxide is preferably a oxalic acid aqueous solution having a concentration of 3 to 10% by weight of the wiring electrode of the uranium display device or the like. The reason is that when the concentration of the aqueous oxalic acid solution is less than 3% by weight, a sufficient etching rate may not be obtained, and when the concentration of the aqueous oxalic acid solution exceeds 10% by weight, crystals may be generated in the solution. 2 Heat treatment It is desirable to form an amorphous transparent conductive oxide by etching, and then heat-treat to crystallize it to improve electrical conductivity while achieving electrical stability under high temperature and high humidity. The heat treatment temperature for crystallization at this time is 260 ° C or higher, preferably 250 ° C or higher, more preferably 280 ° or higher. The higher the heat treatment temperature, the faster the crystallization rate, but the substrate does not produce the paper scale. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) nn an ϋ n ·ϋ 1 ϋ ϋ I 1 MM III MM IJI ·ϋ ·ϋ ϋ (Please read the notes on the back and fill out this page) 1269817 A7 B7 V. INSTRUCTIONS (41) The temperature below the thermal deformation is appropriate. For example, when a transparent resin substrate is used, the heat treatment temperature is preferably 250 ° C or lower, and when a glass substrate is used, the heat treatment temperature is preferably 500 ° t or less. 3 Film thickness The film thickness of the transparent conductive oxide can be appropriately selected depending on the application or the material of the substrate on which the transparent conductive oxide is provided, and is preferably the same as the third or fourth embodiment, and the film thickness is preferably 3 to 3, OOOnM. Within the scope. 4 Application This transparent conductive oxide exhibits excellent transparency, conductivity, or etching properties, and can be applied to, for example, a transparent electrode of a liquid crystal display element, a transparent electrode of an electroluminescence element, and a transparent electrode of a solar cell. [Embodiment 6] The sixth embodiment is a transparent conductive oxide formed on a coloring layer provided on a substrate. The following is an example of a color filter. (1) The color filter constituting the sixth embodiment is formed by sequentially laminating the organic colored layer 1 2 and the transparent conductive film (electrode) 24 on the substrate 10 as shown in Fig. 1(d). Color filter. The organic colored layer 1 2 is composed of RGB pixels (red pixels, green pixels, blue pixels) 1 4 ' 1 6 ' This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back Note: Please fill in this page) -ill·——--r Order;------Line* Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 7Τ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 _ B7 (Invention) (42) 18. The black matrix (light-shielding layer) 20 provided in the gap is composed of indium oxide 6 7 to 9.3 wt%, preferably 7 4 to 93 wt%, and contains tin oxide 5 ～25 wt%, desirably 5 to 20 wt%, and 2 to 8 wt% of zinc oxide, desirably 2 to 6 wt%, and having an atomic ratio of tin to all metal atoms higher than that of zinc to all metal atoms The composition of the atomic ratio is such that, when laminated, the amorphous transparent conductive film 2 2 is heat-treated at a temperature of 200 ° C or higher, more preferably in the range of 2 30 t to 300 ° t, and has a crystal. A color filter of the electrode of the transparent conductive film 24 is formed. (2) Transparent conductive film When the composition of the transparent conductive oxide constituting the transparent conductive film is a sintered body target composed of a transparent conductive oxide having a composition range as described above, it can be sputtered at a low temperature. In other words, even if the substrate temperature is 200 ° C or less, a transparent conductive film is formed from the sintered body target by sputtering, and a transparent conductive film having excellent uranium engraving characteristics can be formed on the organic colored layer. Therefore, the organic colored layer as the underlayer in the damage sputtering can be reduced. The thickness of the transparent conductive film is preferably in the range of 3 to 3, Ο Ο η η 如 as described in the first embodiment. (3) Substrate The substrate used for the color filter is a glass or a composite with excellent transparency (please read the back of the page and fill out this page) %

ρ •-V mmmMm I emmmw I mmae I JfJ0 mm I I mm I

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 -----B7 ___ V. Description of invention (43) Resin, for example, polycarbonate or poly(ethylene terephthalate) A film or sheet of ester (PE:T), polyallate, polyether or the like. (4) Colored layer The colored layer provided on the substrate can be formed directly on the substrate, or the pixels of the organic color layer can be planarly separated, and a light shielding layer (black matrix) is provided in the gap. As the organic colored layer adjacent to or adjacent to the light shielding layer, a composition composed of a colored color and a binder can be used. Such a coloring agent can be, for example, a camel pigment, a lake pigment, an azo pigment, a uquinone pigment pigment, an anthraquinone pigment, an anthraquinone pigment, an indanone pigment, and an indanone pigment. , phthalocyanine pigment, triphenylmethane-based dye, indanthrene pigment, indophenol pigment, cyanine pigment, dioxazine pigment, and the like. An ideal binder resin is preferred because it has heat resistance, and for example, an epoxy resin, a polyurethane, a urea resin, an acrylic resin, a polyvinyl alcohol resin, a polyimide resin, and a mixture thereof can be used. Among them, polyimine resins are particularly preferred because of their high heat resistance. The light-shielding layer is not particularly limited as long as it can prevent the interaction between the organic colored layers, and for example, a layer composed of a chromium film or a partially oxidized chromium film, an organic colored layer colored in black, or the like can be used. (5) Formation of the colored layer of the method 1 (please read the notes on the back and then fill out this page) • · I__ '—Order-I.--- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm): 46· Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1269817 A7 __B7___ V. Invention Description (44) As shown in Figure 11 (b), organic In the case of coloring the layer 12, each of the red, green, and blue colors selected by the coloring agent is mixed with a binder resin and dispersed in the solvent, and after the color paste is produced, RGB pixels are formed by photolithography. For example, a color paste is applied onto a substrate or processed into a strip-shaped light-shielding layer, and after semi-hardening, a long green organic colored layer (G pixel) corresponding to a pixel is formed by a photolithography method. Then harden it. The red or blue organic colored layer (R pixel and B pixel) can also be formed using the same method. A protective layer composed of a polyimide resin or the like may be formed on the organic colored layer as necessary. 2 Formation of an amorphous transparent conductive film, as shown in FIG. 1(c), forming an amorphous transparent conductive film on the protective layer provided on the organic colored layer or on the organic colored layer, The lower target is preferably formed to form the amorphous transparent conductive film, that is, the target contains 6 7 to 93 % by weight of indium oxide, preferably 7 4 to 9 3 % by weight, and contains 5 to 2 5 % by weight of tin oxide. , preferably 5 to 20% by weight, and 2 to 8% by weight of zinc oxide, desirably 2 to 6% by weight, and having an atomic ratio of tin to all metal atoms higher than that of zinc to all metal atoms, and The hexagonal crystal layered compound having a crystal grain size of 5 // m or less is a target. When forming a transparent conductive film on an organic colored layer or a protective layer, it is suitable for this paper scale to apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note before filling this page)

1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (45) using a magnetron device. Therefore, the condition for forming the amorphous transparent conductive film varies somewhat depending on the area or thickness of the target. However, the plasma output is usually in the range of 0·3 to 4 W per 1 c m 2 of the target area, and the film formation time is desirably 5 For ~120 minutes, an amorphous transparent conductive film having a desired film thickness can be obtained. The thickness of the amorphous transparent conductive film varies depending on the type of display device to be used, and is usually in the range of 3 to 3, OOOnM, preferably in the range of 20 to 600 nM, and more preferably in the range of 30 to 200 nM. 3 The etching of the amorphous transparent conductive film has an etching property superior to that of the crystalline transparent conductive film. Therefore, the etching treatment at the time of sputtering can use a weak acid which does not corrode the wiring material, for example, an aqueous oxalic acid solution having a concentration of 3 to 10% by weight. The amorphous transparent conductive film is used as an etching solution at a concentration of 5% by weight of an aqueous oxalic acid solution, for example, at an etching rate of 0 · 1 / / Μ / min or more under the conditions of 40 to 50 ° C. characteristic. 4 Crystallization of the transparent conductive film The amorphous transparent conductive film after the film formation is etched to form a pattern, and it is preferable that the heat treatment or the moisture resistance is excellent as shown in Fig. 1(d). A crystalline transparent conductive film. At this time, the heat treatment condition is above 2000 °C, ideally 2 3 0. The paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm). (Please read the notes on the back and fill out this page. )

1269817 A7 B7 V. Description of invention (46) Above °C, more preferably above 2500 °C, the processing time is 〇 5~3 hours. (Please read the following precautions and then fill out this page.) [Seventh Embodiment] The seventh embodiment relates to the manufacturing method of the first and second inventions. The embodiment includes I η 2〇3 ( Ζ η〇 a method for producing a sputtering target which has a hexagonal crystal layered compound represented by μ (but an integer of 2 to 2 0) and a crystal grain size of the hexagonal layered compound of 5 // m or less. The method for producing a sputtering target in the following steps (1) to (3). (1) a step of mixing an indium oxide powder with a zinc oxide powder having an average particle diameter of 2 // m or less, and (2) forming an atomic ratio represented by I η / ( I n + Zn) of 0·75 to 0·97. Step of forming a molded body, (3) Step of sintering the formed body at a temperature of 14,000 ° C or higher, and mixing step 1 with a manufacturing material for printing a target of a mixing and pulverizing machine of the Ministry of Economic Affairs Each metal oxide is preferably uniformly pulverized using a usual mixing pulverizer such as a wet ball mill or a glass bead mill, and an ultrasonic device. 2 Average particle size of the raw material powder In order to easily control the crystal grain size (5 // m or less) of the hexagonal layered compound of the target, the mixed pulverization of the raw material powder is pulverized to the finer the better, and the paper scale is applicable to the Chinese national standard ( CNS)A4 specification (21〇X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1269817 A7 ___B7 V. Invention description (47) Specifically, the mixing pulverization process makes the average of indium oxide powder or zinc oxide powder The particle diameter is 2/m or less, preferably in the range of 〇·1 to 1 . , more preferably in the range of 0 · 3 to 1 · 5 / / m, and most preferably in the range of 0 · 5 to 1 ·. Further, in order to form a spinel structure compound and to mix tin oxide powder, the average particle diameter of the tin oxide powder is in the range of 0 · 0 1 to 1. 1 //m, and is preferably 0 · 1 to 0 · 7 / / m The range is more preferably a range of 〇·3~0 · 5 // m. The reason for this is that the average particle diameter of the tin oxide powder is limited to such a range, and the crystal grain size (5 #m or less) of the hexagonal layered compound or the spinel structure compound in the target can be more easily controlled. 3 Types of Raw Material Powder The indium compound and zinc compound used as a raw material are preferably an oxide or a compound which is an oxide after firing, in other words, an indium oxide precursor or a zinc oxide precursor. Such indium oxide precursors or zinc oxide precursors are, for example, sulfides of indium and zinc, sulfates, nitrates, halides (chlorides, bromides, etc.), carbonates, organic acid salts (acetates, grasses). An acid salt, a propionate, a naphthate or the like), an alkoxide compound (a methoxide compound, an ethoxide compound, etc.), an organometallic complex (an acetoacetone complex, etc.), and the like. Among them, a carbonate, an organic acid salt 'alkate' organometallic complex compound, which is completely thermally decomposed even at a low temperature, is not preferable. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -DU - -I 11-1 I —'I .1.11' — — — — . ^^一 (Please read the notes on the back first) Fill in this page again) %

1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing V. Inventions (48) (2) Sinter-sintering step After obtaining a mixture of indium compound, zinc compound and tin compound, the mixture is subjected to pseudo-sintering at any step. ideal. The pseudo-sintering step is preferably carried out at a temperature of 50,000 to 1,200 ° C for 1 to 100 hours. The reason is that the thermal decomposition of the indium compound, the zinc compound, and the tin compound may be insufficient when the heat treatment condition is 500 ° C or less or 1 hour or less. Therefore, it is preferable to carry out heat treatment (false sintering) in a temperature range of 800 to 1, 200 ° C for 2 to 50 hours. The sinter obtained here is preferably pulverized before the forming and sintering. The pulverized ball mill of this sintered product, a roll mill, a particle mill, a jet mill or the like forms a particle diameter of 0 · 0 1 to 1 · 0 # m. (3) Forming step In the forming step, it is preferable to use the obtained pseudo-sinter as a target to form an appropriate shape. In the case of such a forming process, for example, mold forming, casting molding, injection molding, etc., in order to obtain a sintered body having a high sintered density, it is preferable to form a sintering treatment such as C I P (cooling water pressure). In the forming treatment, a forming aid such as polyvinyl alcohol or methyl cellulose, polyterpene or oleic acid may be used. (4) Firing step Next, after the obtained fine powder is granulated, it is formed by press forming (please read the back sheet and read the back sheet) -111·! — Ι·Γ «ΓΙΓΙΙΙ — ·

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -01 - 1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (49) The desired shape, after firing Η IP (hot hydrostatic) firing, etc. The firing conditions at this time are under oxygen gas atmosphere or oxygen gas pressure, usually 1,400~1,600 ° (:, ideally 1,430 ~ 1, 550 ° (:, more ideally 1,500 ~ 1,540 ° C., burned for 30 minutes ~ 7 2 hours, ideally 1 0 ~ 4 8 hours. Indium oxide powder and zinc oxide powder When the mixture is fired in an atmosphere containing no oxygen gas or fired at a temperature of 1,400 ° C or lower, the reactivity between indium oxide and zinc oxide is lowered, and crystals of the hexagonal layered compound may not be sufficiently formed. The density of the target produced may not sufficiently suppress the occurrence of protrusions during sputtering. The rate of temperature rise at this time is preferably 10 to 50 ° C / min. The indium oxide powder and zinc oxide powder are set to a predetermined ratio. The mixture is pressurized at 1,400 ° C under an oxygen gas atmosphere or an oxygen gas pressure When the temperature is calcined, the crystal of the hexagonal layered compound composed of indium oxide and zinc oxide is concentrated in the gap between the crystal particles of indium oxide, so that the crystal growth of indium oxide can be suppressed, and sintering with a fine crystal structure can be formed. In the above compounding step, at least zinc oxide having an average particle diameter of 2 // m or less is used, so that a sintered body having a crystal grain size of 5 // m or less can be obtained. (5) Reduction step to obtain a sintered body When the overall resistance of the body is uniformly formed, it is preferable to carry out the reduction treatment in the reduction step of any step. This reduction method can be carried out, for example, by using a reducing gas method or vacuum burning. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210). X 297 mm) -OZ - 丨丨丨 丨丨丨 ------- 丨丨 I - ^ 丨 丨 丨 . . . . . . 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请1269817 A7 B7 V. INSTRUCTIONS (50) Reduction of a gas or an inert gas, etc. When reducing a gas, hydrogen, methane, carbon monoxide or a mixed gas of these gases and oxygen, etc. may be used. When restoring Nitrogen, argon or a mixture of these gases and oxygen, etc. The reduction temperature is 100~800 °C, and the resolution is 200~8 0 CTC. The reduction time is 0 · 0 1~1 0 hours, ideally 〇· 0 5 ~5 hours. (6) Processing step The sintering system obtained by the above sintering is further processed into a shape suitable for mounting in a sputtering apparatus in the processing step, or it is preferable to form a sputtering target by mounting a fixture. The obtained sputtering target system has a composition of each metal oxide of each constituent component within the above range, and simultaneously uses particles of 2 // m or less, and is heated at 1,400 ° C under an oxygen gas atmosphere or an oxygen gas pressure. When the above temperature is fired, indium oxide and zinc oxide are present in a crystal form of a hexagonal layered compound. Therefore, the body resistance of the target is lowered, and a crystal structure having a crystal grain size of 5 // m or less is formed. Therefore, when a film is formed by sputtering using this target, the occurrence of protrusions can be suppressed. Since the protrusions are significantly reduced in scattering due to the plasma, sputtering with high stability can be performed, and as a result, a high-quality transparent conductive oxide having no foreign matter adhered can be obtained. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page) ill· — — ΙΓ - - ί 经济 经济 经济 经济 经济 经济 经济 经济 经济1269817 Α7 Β7 Ministry of Economic Affairs, Intellectual Property Office, Employees, Consumer Cooperatives, Printing, V. Illustrative (51) [Eighth Embodiment] The eighth embodiment is an embodiment of the manufacturing method according to the first and second aspects, and includes I η 2 〇3 ( Ζ η〇)μ (but Μ is an integer of 2 to 2 0), which is a hexagonal layered compound, and the hexagonal layered compound has a crystal grain size of 5 // m or less. The method is a method for producing a sputtering target comprising the following steps (1) to (5). (1) a step of forming a hexagonal layered compound represented by I n 2 〇 3 (Zn〇) M (but Μ is an integer of 2 to 20), and (2) adjusting a particle size of the produced hexagonal layered compound a step of 5 β m or less, (3) a step of mixing and adjusting the hexagonal layered compound and the indium oxide powder after the particle diameter, and (4) forming an atomic ratio represented by I η / ( I n + Zn) of 0.75~ The step of molding the molded body of 0.97, (5) the step of sintering the formed body at a temperature of 14,000 ° C or higher, such as the above-described sputtering target, can extremely strictly adjust the average of the hexagonal layered compound in the target. Particle size. Therefore, the use of the target can effectively prevent the occurrence of protrusions during sputtering. (1) Formation step of hexagonal layered compound When a hexagonal layered compound represented by I n 2 〇 3 (Zn〇) M (M is an integer of 2 to 20) is formed, oxidation of the raw material is the same as in the seventh embodiment. The powders of indium (I Π2〇3) and zinc oxide (Ζη〇) make this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -IIII —..I order — — — · *^ One (please read the notes on the back and fill out this page) %

1269817 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (52) It is better to use wet ball mill or glass bead mill, or ultrasonic equipment to evenly mix. When a hexagonal layered compound is obtained, it is preferred to carry out the heat treatment at a temperature of from 12,000 to 1300 ° C for 30 minutes to 3 hours. In the particle size adjustment step described later, in order to control the average particle diameter of the hexagonal layered compound, in the step of forming the hexagonal layered compound, indium oxide powder or zinc oxide having an average particle diameter of 2 // m or less is not necessarily required. powder. (2) Particle size adjusting step of hexagonal layered compound The average particle diameter of the resulting hexagonal layered compound is 5 # m or less. When the particle diameter of the hexagonal layered compound is adjusted as described above, the use of the obtained target can effectively prevent the occurrence of protrusions. The average particle size of the hexagonal layered compound is too small, the control is difficult or the yield is lowered, and it is not economical. Therefore, the average particle diameter of the hexagonal layered compound is in the range of 0 · 1 to 4 // m, and is preferably in the range of 0 · 5 to 3 A m . The method of adjusting the particle diameter of the hexagonal layered compound is not particularly limited. Μ If the wet ball mill or the glass bead mill is used, or the ultrasonic device is uniformly pulverized, the sieve is used to adjust the particle diameter. (3) Mixing step of indium oxide powder The steps of adjusting the particle size of the hexagonal layered compound with the indium oxide powder are mixed. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) l·.— ^-----------------^丨----- ( Please read the precautions on the back and fill out this page.) 1269817 A7 B7 Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printing 5, Inventions (53) In other words, mixing indium oxide powder into the shaped body, I η / ( I η + Ζη) indicates an atomic ratio of 〇. 75~0 · 97. 〇 It is preferable to add an indium oxide powder and a spinel structure compound at the same time. In other words, the zinc oxide (ζη〇) and the tin oxide (S η〇2 ) are heated at a temperature range of 80 ° 0 to 1 2 0 0 ° C for 30 minutes to 3 hours, and the particle size is adjusted. It is also possible to add a spar structure compound at this stage of 5 // m or less. (4) Forming step of the molded body The molding conditions similar to those of the seventh embodiment are preferably used. In other words, in order to obtain a compact target, it is preferable to form a molded body by using C I P (cool water pressure) or the like in advance. (5) Sintering step The same molding conditions as in the seventh embodiment are used. In other words, it is preferable to fire the molded body obtained in (4) under the conditions of an oxygen gas atmosphere or an oxygen gas at a temperature of 1,400 ° C, 1 000 ° C, and 30 minutes to 72 hours. . EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. [Embodiment 1] <Please read the notes on the back and fill out this page.) -------, w.tT·丨 I------Line

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 gong 1269817 A7 B7 5. Invention description (54) (1) Manufacture and evaluation of sputtering target 1 Manufacture and mixing of target The average particle size of raw material is 1 #m of indium oxide and an average particle size of 1 oxidized, such that the atomic ratio of indium [I η / ( I n + Ζ η )] is 〇 · 8 3 , the mixture is supplied to a wet ball mill. After pulverizing for 7 hours, a raw material micropowder is obtained. The obtained raw material micropowder is granulated, and then pressed into a diameter of 10 cm and a thickness of 5 mm, and this is placed in a firing furnace, and under an oxygen gas pressure, 1 is obtained. The sintered body (target) made of a transparent conductive material was obtained by firing at 4 5 0 ° C for 3 hours. 2 Evaluation of the target density of the target, bulk resistance 値, X-ray diffraction analysis, crystallization Particle size and various physical properties. The resulting density was 6.8 g / cm 3 , and the volume resistance 値 measured by the four-probe method was 0.91 x 10 Ω·cm. The sample taken from the sintered body was observed by X-ray diffraction. The crystalline state of the transparent conductive material, and as a result, it was found that the target produced contained I η 2 0 3 (Ζ 〇 〇) μ denotes a hexagonal layered compound composed of indium oxide and zinc oxide. The obtained sintered body is embedded in a resin, and the surface thereof is honed with aluminum particles having a particle diameter of 〇·〇5 /zm. J ΧΑ - 8 6 2 1 MX (manufactured by JEOL Ltd.) is enlarged to 500 square inches of the surface of the sintered body at a frame of 3 0 Mmx 3 0 //m square, and the hexagonal layer observed This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page). · Department of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 B7 Ministry of Economics The property bureau employee consumption cooperative printed 5, the invention shows the maximum diameter of the crystalline particles of the compound (55). Calculate the average 値 of the largest particle diameter measured in three places in the frame, and the crystal grain size of the sintered body is 3 . 0 # m 〇The sintered body obtained by 1 is cut into a sputtering target [A 1] having a diameter of 1 〇C m 'thickness 5 Μ ,, and the physical properties are measured. (2) The film formation of the transparent conductive oxide (1) The resulting sputtering target [A1] is mounted on a DC magnetron sputtering On the device, a transparent conductive oxide is formed on the glass substrate at room temperature. The sputtering condition is to mix an appropriate amount of oxygen gas into the argon gas, and the sputtering pressure SxlO-iPa reaches the pressure 5x10-4Pa, the substrate temperature. At 25 ° C, the electric power was supplied at 100 W, and the film formation time was 20 minutes. As a result, a transparent conductive glass having a transparent conductive oxide having a film thickness of about 1 2 η Μ on the glass substrate was obtained. (3) The number of protrusions is not limited except that the sputtering target [A1] prepared in (1) is mounted on a DC magnetron sputtering device, and a mixed gas of 3% hydrogen gas is added to the argon gas, Under the conditions of the above (1), sputtering was carried out for 8 hours, and then the surface of the target after sputtering was observed by a stereoscopic microscope at a magnification of 30 times. The average number of protrusions above 20 0 m in the field of view of 0 0 0 m 2 was measured at three points on the target, and the average enthalpy was calculated. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) l· I ^-----I----------Lr ^ > Γ I Γ I (please first Read the notes on the back and fill in this page.) 1269817 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Inventive Note (56) Results The surface of the sputter target [A1] prepared in (1) above is shown in Figure i. As shown (photograph), no protrusions were found at all. (4) Evaluation of Physical Properties of Transparent Conductive Oxide The conductivity of the transparent conductive electrical oxide on the transparent conductive glass obtained in the above (2) was measured by a four-probe method to determine the specific resistance, and 2 5 was measured. X 1 〇 - 4 Ω · cm. This transparent conductive oxide was found to be amorphous by X-ray diffraction analysis. For the smoothness of the film surface, P - V 値 (according to J I S B 0 6 0 1 ) is 5 η Μ, and it is found that the smoothness is good. The transparency of the transparent conductive oxide is such that the light transmittance of light having a wavelength of 5 Ο Μ Μ is 82% by a spectrophotometer, and the transparency is also excellent. [Examples 2 to 3] (1) Production of sputtering target Example 2 was an indium oxide and zinc oxide which were mixed as a raw material in the same manner as in Example 1 to make an atomic ratio of indium [I n / (I η + ζ) η)] is Ο · 9 3 , and Example 3 uses indium oxide and zinc oxide which are the same as those of the first embodiment, and the atomic ratio of indium [I n /(I η +Ζη)] is 〇· In addition to the above, the target [Β 1] and [C 1] were obtained in the same manner as in the above (1). The measurement results of the composition and physical properties of the targets [Β 1] and [C 1] prepared are shown in Table 1, respectively. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1· *n ϋ H -ϋ ϋ ϋ ϋ ϋ I* n · n ϋ ml· n 1 ί^ιβ 一 ^, · ϋ ν ·— I (please read the notes on the back and fill out this page) I AM ···霸1269817 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed Β7 Β7 5, invention description (57) (2) target and transparent conductivity Evaluation of the oxide was carried out in the same manner as in Example 1, and the transparent conductive oxide was formed into a film from the obtained targets [B1] and [C1], respectively, and the target and the transparent conductive oxide were evaluated. The results are shown in Table 2. [Comparative Examples 1 to 2] (1) Production of sputtering target The influence of the atomic ratio represented by I η / (I n + Zn) in the target was examined. In other words, Comparative Example 1 used indium oxide and zinc oxide which were the same as in Example 1 in which the raw material was mixed so that the atomic ratio represented by [I n / (I η + Ζ η )] was Ο. 2 is the same as indium oxide and zinc oxide which are the same as that of the first embodiment, and the atomic ratio represented by [I η / (I n + Zn)] is 〇·6, and the examples are the same as the examples. 1 (1) is identical to the target [D 1] and [Ε 1]. The results of the measurement of the composition and physical properties of the targets [D 1 ] and [Ε 1] prepared are shown in Table 1, respectively. (2) Evaluation of Target and Transparent Conductive Oxide In the same manner as in Example 1, the transparent conductive oxide was formed into a film from the obtained targets [D1] and [Ε1], respectively, and the target and the transparent conductive oxide were evaluated. . The results are shown in Table 2. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) • · II —r II 1^1 0 1269817 A7 ____B7 V. Description of the invention ( 58) [Comparative Example 3] (1) Production of a sputtering target The influence of the atomic ratio represented by I n /( I n + zn ) and the influence of the sintering temperature in the target was examined.

In other words, a mixture of indium oxide and tin oxide mixed as a raw material is used, and an atomic ratio of [In/(In + Sn)] is 〇·90, and a sintered body obtained from these raw materials has a sintering temperature of 1, 4 The target [F 1 ] was obtained in the same manner as in (1) of Example 1 except for 0 0 °C. The measurement results of the composition and physical properties of the target [F 1] produced are shown in Table 1. (2) Evaluation of target and transparent conductive oxide In the same manner as in Example 1, a transparent conductive oxide was formed into a film from the obtained target [F 1], and the target and the transparent conductive oxide were evaluated. The results are shown in Table 2. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed on this paper scale Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 V. Description of invention ( 59) Example 1 Example t 匕 Comparative Example 1 2 3 1 2 3 In/(In + Zn) 0.83 0.93 0.95 0.98 0.60 Two In/(In + Sn) Surface • 0.90 Sintered body density (g/cm3) 6.8 6.8 6.9 6.9 6.3 6.9 Body resistance (m Ω cm) 0.91 0.94 0.97 2.1 5.4 0.62 Crystal grain size (M m ) 3.0 3.8 4.6 7.8 9.8 18.0 Target mark A1 B1 C1 D1 E1 F1 ____:____I — 士°° (Please read the back first Note: Please fill out this page again) % Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -DZ - A7 1269817 B7 V. Invention Description (6Q ) 突起 mark protrusion (/8Hrs/ 900mm2) transparent conductive acid film specific resistance (β Ω · cm) crystallinity 1 A1 0 250 amorphous application 2 B1 0 .230 amorphous example 3 C1 0 180 Amorphous ratio 1 D1 18 320 Microcrystalline compared to 2 E1 8 680 Non Crystalline Example 3 F1 32 420 Crystalline quality—________ (Please read the note on the back side and fill out this page) Order [Example 4] (1) Production of sputtering target The average particle size as a raw material is 1 μm. The indium oxide powder has a zinc oxide powder having an average particle diameter of 1 and a tin oxide powder having an average particle diameter of 1, and the ratio thereof is 75% by weight of indium oxide, 5 · 5 % by weight of zinc oxide, and 1 9 · 5 of tin oxide. The % by weight ' was then supplied to a wet ball mill separately, followed by mixing and pulverizing for 7 hours to obtain a fine powder of the raw material. After the obtained raw material micropowder is granulated, it is pressed into a diameter of 10 cm and a thickness of 5 Μ ,, and this is placed in a firing furnace under the pressure of oxygen gas at 1,450 ° C, 3 6 The condition of the hour is fired to obtain a sintered body composed of a transparent conductive material. The density of the sintered body was 6 · 8 g / c m 3 ', and the volume resistance 値 measured by the four-probe method was 0 · 84 χ 10 _ 3 Ω · cm. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 297 297 mm)

Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed -63 - 1269817 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed Α7 Β7 V. Inventive Note (61) The sample taken from the sintered body was observed by X-ray diffraction method for transparent conductive materials. As a result of the crystallization state, as shown in Fig. 6, it was confirmed that the indium oxide and the zinc oxide were represented by 尖 η 2 S η 0 4 as a spinel structure compound. The obtained sintered body was embedded in a resin, and the surface thereof was honed with aluminum particles having a particle diameter of 0 〇5 //m, and then the surface of the sintered body enlarged to 50.0 〇 was measured using Ε ( (3 0 // m The maximum diameter of the largest crystalline particles of the hexagonal layered compound and the spinel structure compound in the square frame. Similarly, the average 値 of the maximum diameter of the largest crystal particle diameter at three positions in the frame was measured. As a result, the crystal grain size of the hexagonal layered compound and the spinel structure compound was 4. 1 // m. The sintered body obtained above was cut into a sputtering target [A 2] having a diameter of 10 m and a thickness of 5 Μ. The measurement results of the composition and physical properties of the target [A 2] produced are shown in Table 3. (2) Film Formation of Transparent Conductive Oxide The sputtering target [A 2] obtained by (l.) is mounted on a DC magnetron sputtering apparatus, and a transparent conductive oxide is formed at room temperature at room temperature. On the glass substrate. The sputtering conditions were carried out by mixing an appropriate amount of oxygen gas into an argon gas, a sputtering pressure of 3×10 − iPa , a pressure of 5×10 −4 Pa, a substrate temperature of 25 t: a power of 100 W, and a film formation time of 20 minutes. As a result, a transparent conductive glass in which a transparent conductive oxide having a film thickness of about 1 2 η Μ was formed on the glass substrate was obtained. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -64 - 卜 rl. —----------------- Order ΓΙ---- -- (Please read the notes on the back and fill out this page) 1269817 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (62) (3) the number of protrusions in addition to (1) The sputtering target [A2] is mounted on a DC magnetron sputtering device, and a mixture of 3% hydrogen gas is added to the argon gas, and the same is carried out for 8 hours under the conditions of the above (2). The surface of the target after sputtering was then observed by a stereo microscope at a magnification of 3 〇. The average 値 is calculated by measuring the number of occurrences of protrusions above 2 〇 // m in the field of view 9 Ο Ο Μ Μ 2 at 3 points on the target. As a result, no protrusion was observed on the surface of the sputtering target [A2] obtained in the above (1). The results of the number of occurrences of this projection are shown in Table 4. (4) Evaluation of Transparent Conductive Oxide The conductivity (specific resistance) of the transparent conductive oxide film obtained in the above (2) was measured by a four-probe method of 2 · 8 X 1 0 - 4 Ω · cm . This transparent conductive oxide was found to be amorphous by X-ray diffraction analysis. For the smoothness of the film surface, P - V 値 was 5 η Μ as measured by the surface roughness super, and it was found that the smoothness was excellent. The transparency of the transparent conductive oxide is measured by a spectrophotometer (wavelength 5 Ο Ο η Μ ), and as a result, the light transmittance is 82%, and the transparent conductive oxide film is transparent. Excellent also. (5) Heat treatment of transparent conductive oxide The transparent conductive glass obtained in the above (2) was subjected to heat treatment. This heat (please read the note on the back and fill out this page) ^mi— ί 订-f This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -65 - 1269817 A7 B7 V. Invention Explanation (63) The treatment conditions were a temperature increase rate of 20 ° C / min under an argon gas atmosphere, and the temperature was raised to 2 15 ° C, and the temperature was maintained for 1 hour. As a result, the transparent conductive oxide film obtained was amorphous, but its specific resistance was 2 · 1 x 10 - 4 Ω·cm. Therefore, it was confirmed that the specific resistance of the transparent conductive oxide film can be lowered by about 25 % by this heat treatment. The change in specific resistance of the transparent conductive oxide film due to heat treatment is shown in Table 4. (6) Etching Processability of Transparent Conductive Oxide Film Next, the etching processability of the transparent conductive oxide film was evaluated. In other words, a portion of the transparent conductive oxide film on the transparent conductive glass is partially etched into a line width of 10 0 to 1 0 0 // m using an aqueous solution of oxalic acid (5 wt%) at 40 ° C to The cross section of the boundary portion between the etched portion and the non-etched portion was observed with an electron microscope. As a result, the transparent portion of the transparent conductive oxide film remaining in the non-etched portion was found to have a cross-sectional shape that was smoothly inclined toward the uranium-etched portion in the etched portion. Therefore, the obtained transparent conductive oxide was obtained. The film has excellent etching workability. The etching processability of the transparent conductive oxide film was evaluated according to the following criteria: ◎: The line width of 10 0 / m was etched, and no residue was found at all. 〇·· can be engraved with 50 〆 The line width of m is completely undiscovered. △: The line width of 1 0 0 // m can be engraved, but a part of the residue is found. X ··etching 1 0 0 //The line width of m is difficult, there are Obvious residue. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) * 0 ϋ I Ml· ft — #·0, · Economy Ministry of Intellectual Property Bureau employee consumption cooperative printing _ bD _ 1269817 A7 _____B7 V. Inventive Note (64) [Examples 5 to 8] (1) The influence of the blending ratio of the raw materials on the manufacture of the sputtering target. In other words, in addition to the examples 5 series indium oxide 73% by weight, tin oxide 20% by weight and oxidation The blending ratio of 7% by weight, Example 6 is a blending ratio of indium oxide 78% by weight, tin oxide 1% by weight, and zinc oxide 3% by weight. Example 7 is indium oxide 88% by weight, tin oxide 1 〇 weight The blending ratio of % and zinc oxide 2% by weight, and Example 8 are the ratio of the indium oxide 91% by weight, the tin oxide 7 wt%, and the zinc oxide 2 wt%, and the same as in Example 4, respectively, to obtain the target [B 2 ], [C 2 ], [D2] & [E2] The measurement results of the composition and physical properties of the target [B2], [C 2 ], [〇2] and [$2] are shown in Table 3. (2) The evaluation of the target and the transparent conductive oxide film was the same as in Example 4, and the transparent targets were oxidized from the obtained targets [B 2 ], [ C 2 ], [D 2 ] and [E 2 ], respectively. The film was formed, and the transparent conductive oxide was evaluated. The results are shown in Table 4. [Comparative Example 4] (1) Production of a sputtering target In other words, oxidation using an average particle diameter of 3 // m as a raw material was used. Zinc powder, and the mixing ratio of raw materials is 90% by weight of indium oxide. The standard of zinc oxide is applicable to Chinese national standard (CNS). )A4 size (210 X 297 mm) (Please read the note on the back and fill out this page) i I L____ '丨定·ί ·

Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed -67 - 1269817 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed Α7 Β7 V. Invention Description (65) 1% by weight, the same as Example 4, the target [F2] . The measurement results of the composition and physical properties of the target [F 2 ] produced are shown in Table 3. (2) Evaluation of target and transparent conductive oxide film In the same manner as in Example 4, a transparent conductive oxide was formed from the obtained target [F 2 ], and the target and the transparent conductive oxide were evaluated. The results are shown in Table 4. [Comparative Examples 5 to 7] (1) Production of sputtering target The influence of the mixing ratio of raw materials was examined. In other words, the blending ratio of the raw materials is as follows: Comparative Example 5 is a blending ratio of 90% by weight of indium oxide and 1% by weight of tin oxide, and Comparative Example 6 is 8 wt% of indium oxide, 1% by weight of tin oxide, and 3 parts by weight of zinc oxide. The mixing ratio of % by weight, Comparative Example 7 is a mixing ratio of 90% by weight of indium oxide, 5% by weight of tin oxide, and 5% by weight of zinc oxide. Next, in Comparative Example 5 and Comparative Example 7, the targets [G 2 ] and [I 2 ] were obtained in the same manner as in Example 4. Comparative Example 6 except that the sintering temperature of the formed body was changed to 1,1 〇 〇. Further, the target [Η 2] was obtained in the same manner as in Example 4. The results of the composition and physical properties of the targets [G 2 ], [ Η 2 ] and [I 2 ] prepared separately are shown in Table 3. (2) Evaluation of Target and Transparent Conductive Oxide Film In the same manner as in Example 4, the transparent conductive oxide was formed into a film from the obtained targets [G 2 ], [ Η 2 ] and [I 2 ], respectively. And the transparent paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) <Please read the note on the back and fill out this page), _ _ ΓΙΓ 1269817 A7 _B7__ V. Invention description (66 ) Electrical oxides. The results are shown in Table 4. The target [Η 2] of Comparative Example 6 was observed by X-ray diffractometry, and a hexagonal layered compound represented by I η 2 〇 3 (Ζη〇) μ (but Μ is an integer of 2 to 20) was not found. (Please read the precautions on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Cooperatives, Printed Table 3 _· Example. Comparative Example 4 5 6 7 8 4 5 6 7 I η 2〇3 (% by weight 75 73 87 88 91 90 90 87 90 S η〇2 (% by weight) 19.5 20 10 10 7 0 10 10 5 Ζη〇 (% by weight) 5.5 7 3 2 2 10 0 3 5 Sintered body density (g/cm3) 6.8 6.8 6.9 6.9 7.0 6.9 7.0 6.3 6.4 Body resistance (m Ω cm) .84 • 94 .87 .83 • 87 2.1 • 87 4.3 1.5 Crystal size (// m) 4.1 3.4 3.8 4.5 4.8 4.2 18 7.4 4.8 Target mark A2 B2 C2 D2 E2 F2 G2 H2 12 -69 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 V. Invention description (67 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing The number of protrusions of the fourth target mark is the number of the transparent conductive acid film formed and then the specific resistance (μΩ · cm) after the heat treatment. Crystalline etchability specific resistance (μΩ · cm) Crystallinity 4 A2 0 280 Amorphous 210 Crystallization 5 B2 0 290 Amorphous ◎ 230 Amorphous Example 6 C2 0 270 Amorphous 〇180 Microcrystal 7 D2 0 260 Amorphous 〇170 Microcrystalline 8 E2 0 240 Amorphous Δ 170 Microcrystalline ratio 4 F2 0 380 Amorphous ◎ 380 Amorphous than 5 G2 32 260 Amorphous X 190 Crystalline 6 H2 18 320 amorphous Δ 250 crystalline 7 12 21 260 amorphous Δ 880 crystalline (please read the back of the note first)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ^70-=· 1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (68) [Example 9] ( 1) Production of a conductive transparent film A biaxially stretched polyester film (polyethylene terephthalate film) having a thickness of 100 μm/m of a transparent resin substrate using a hexagonal layered compound on the film (crystal grain size 4 · 0 / m or less) · 1 ri2 〇 3 (Zn〇) 3, I Π 2 〇 3, Sn 〇 2 composed of sintered body [In / (In + Zn) = 〇.93, A target of Sn/(In + Zn + Sn) = 〇· 08, relative density = 98%] was formed by a sputtering method to form a transparent conductive oxide film, thereby producing a conductive transparent film. In other words, the polyester film is mounted on an RF sputtering apparatus, and after decompressing the pressure in the vacuum chamber to 1×10 −3 Pa or less, a mixed gas of argon gas (purity of 9 9 · 9 9%) and oxygen gas is introduced (oxygen gas) Concentration = 0 · 28%] up to lxlO_1Pa (oxygen partial pressure: 2 · 8 X 1 〇 ' 4 P a ) , RF output 1 · 2 W/cm 2 , substrate temperature 2 5 . Under the condition of (:, a transparent conductive oxide film having a film thickness of 2,500 Å was formed. - (2) Evaluation of a conductive transparent film 1 The film thickness was determined by using the DEKTA Κ 3 0 3 0 by Sloan Co., Ltd. The film thickness of the obtained transparent conductive oxide film was measured. 2 X-ray diffraction measurement The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note and fill out this page) - ill - I - 1269817 A7 B7 V. Inventive Note (69) The transparent conductive oxide film was measured by X-ray diffraction using Rotarflex RU-200B (manufactured by Rigaku Corporation). The film is amorphous. 3 Inductively coupled plasma luminescence spectroscopic analysis. Inductively coupled plasma luminescence spectroscopic analyzer SPS -1 500VR (manufactured by Seiko Electronics Co., Ltd.) was used to measure the transparent conductive oxide film I n / ( I η + Ζ η ) and S n / ( I η +

The atomic ratio of Zn + Sn). As a result, the atomic ratio I n / ( I n + Zn) was 〇. 93, and Sn / (In + Zn + Sn) was 〇· 〇 8ο 4 UV spectroscopic measurement using the u V spectrometer U - 3 2 1 0 (Hitachi, Ltd. The light transmittance (light wavelength 5 0 0 or 5 5 0 η Μ ) of the transparent conductive oxide film was measured. 5 Surface resistance and specific resistance The Ministry of Economics and the Intellectual Property Office of the Consumers Co., Ltd. printed and measured the surface resistance (initial surface resistance) of the transparent conductive oxide film using the resistance measuring device Rolester FP (manufactured by Mitsubishi Chemical Corporation), and measured by the four-terminal method. Specific resistance (initial specific resistance R q ). As a result, the initial surface resistance was 1 〇 · 4 Ω / □, and the initial specific resistance (R〇) was 2 · 6X10 - 4 Ω·cm. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 V. Invention description (70) 6 Carrier mobility (please read the back note before filling this page) Using Hall The coefficient measuring device RESITEST 8200 (measuring device of the vanderpauw method, manufactured by Toyo Technic Co., Ltd.) measures the mobility of the carrier. As a result, the mobility of the carrier of the transparent conductive oxide film was 27 cm 2 /V * sec 〇 7 Heat resistance test The obtained conductive transparent film was divided into 2 pieces, and 1 piece was subjected to a heat resistance test. In other words, the conductive transparent film was placed in the atmosphere at 90 ° C for 1 hour, and then the specific resistance (Riqqci) of the transparent conductive oxide film was measured. The ratio of the specific resistance (R 1 0 0 Q ) and the initial specific resistance (R Q ) after the heat resistance test was calculated [R i . 〇 Q / R Q] The rate of change in resistance is defined as a low rate of change 値1,·1 0. 8 Etchability Evaluation Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed another piece of conductive transparent film produced at a temperature of 40 ° C, with a concentration of 5% by weight of oxalic acid aqueous solution as uranium engraving, evaluation of its engraving characteristic. As a result, the etching rate (initial etching rate) of the transparent conductive oxide film was 0 · 2 / / m / min. [Example 1 0] The paper scale was applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) except for the use of a transparent substrate of #7 0 5 9, 1269817 A7 _B7 V. Description of the invention ( 71) An electroconductive transparent glass was obtained in the same manner as in Example 9 except that the alkali-free glass substrate was used. The film formation conditions and the atoms of the constituent metal of the transparent conductive oxide film are shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent glass obtained as described above are shown in Table 6. The obtained conductive transparent glass was divided into three test pieces, and two of them were measured in the same manner as in Example 9 to measure the initial surface resistance of the transparent conductive oxide film, initial specific resistance (R 〇), carrier mobility, and resistance change rate. And initial etching speed. One of the remaining sheets was heated at 200 Torr for 1 hour, and the surface resistance and the etch rate of the transparent conductive oxide film were measured in the same manner as in Example 9. The specific resistance of the heated transparent conductive oxide film was calculated. The evaluation results of these heated transparent conductive oxide films are shown in Table 7. [Example 1 1] A conductive transparent glass was obtained in the same manner as in Example 1 except that the substrate temperature was 2 15 °C. Film Formation Conditions and Composition of Transparent Conductive Oxide Film The atom of the metal is shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent glass obtained are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are shown in Table 7. [Example 1 2] The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) ιδι· Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative 1269817 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Invention Description (72) The transparent substrate uses the same polyester film as in Example 9 'The simultaneous sputtering target uses a hexagonal layered compound (crystal size 3 · 8 / m or less) I Π 2 〇 3 (Zn 〇) 3, I n2 〇 3 and Sn 〇 2 composed of sintered body [In / (In + Zn) =0 · 96 ' Sn / ( I n + A conductive transparent film was produced by a target of Zn + Sn) = 〇·18, relative density = 97%. In addition to the argon gas (purity 99 · 99%) and oxygen gas mixed with the sputtering gas (concentration of oxygen gas = 0.5 〇%) until 1 xiO_1Pa (oxygen partial pressure · 5xlO_4Pa), In the same manner as in Example 9, a transparent conductive oxide film was formed on the polyester film. The film forming conditions and the atoms constituting the metal of the transparent conductive oxide film obtained here are shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent glass obtained are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are shown in Table 7. [Example 1 3] A conductive transparent glass was obtained in the same manner as in Example 12 except that the substrate temperature was the same as that of the alkali-free glass substrate of Example 10. The film formation conditions herein and the atoms of the constituent metal of the obtained transparent conductive oxide film are shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent glass obtained above are shown in Table 6. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). rl·! —-----——.——订·ΓΙ 一------ (Please read the back Note: Please fill out this page again) 1269817 A7 ____B7___ V. INSTRUCTIONS (73) The evaluation results of the transparent conductive oxide film after heating are as shown in Table 7. (Please read the note on the back and fill in this page) Example 1 4] The same alkali-free glass substrate as in Example 10 was used except for the transparent substrate, and the sputtering target used was a hexagonal layered compound (crystal size of 3 · 6 // m ) of I n 2 〇 3 (Zn〇). 3, I n2〇3 and Sn〇2 constitute a sintered body target [In / (In + Zn) = 〇 · 91, Sn / (In + Zn + Sn) = 0 · 10, relative density = 97%] The conductive transparent glass was produced in the same manner as in Example 9 except for the rest. The atomic ratio of the film forming conditions and the constituent metal of the obtained transparent conductive oxide film is as shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent glass obtained are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are as shown in Table 7 [Example 15] The polyester film printed in the same manner as in Example 9 was printed on the transparent substrate printed by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumers' Cooperatives. An epoxy resin layer having a thickness of 1 // m was provided on the surface by a spin coating method, and the epoxy resin was hardened by UV irradiation to form a crosslinkable resin layer. Next, a transparent conductive oxide film was provided on the crosslinkable resin layer in the same manner as in Example 14 to obtain a conductive transparent film. The film forming conditions here and the atoms of the constituent metal of the transparent conductive oxide film produced are, for example, 5 -76 - the paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Bureau employee consumption cooperative printed 1269817 A7 B7 V. Invention description (74) Table. The evaluation results of the transparent conductive oxide film of the conductive transparent film obtained are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are shown in Table 7. [Example 16] The same polyester film as in Example 9 was used for the transparent substrate, and the sputtering target used was a ri2〇3 (Zn) having a hexagonal layered compound (crystal size of 3 · 8 // m ).烧结)3, I Π2·〇3 and Sn〇2 constitute a sintered body target [In/(In + Zn)=〇·95,Sn/( I n + Zn + Sn) = 〇· 10, relative density = 98%] A conductive transparent film was produced. The film formation conditions herein and the atoms of the constituent metals of the transparent conductive oxide film obtained are shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent film obtained are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are shown in Table 7. [Example 1 7] As the transparent substrate, the same polyester film as in Example 9 was used, and a layer of Si 〇 2 having a thickness of ΙΟΟηΜ was formed thereon by electron beam evaporation. Next, a transparent conductive oxide film was formed on the surface of this layer of Si 2 as in Example 12 to prepare a conductive transparent film. This paper scale applies to China National Standard (CNS) A4 specification (21〇 X 297 mm) (please read the notes on the back and fill out this page) ----r--.L—Book·! 1269817 Α7 Β7 V. DESCRIPTION OF THE INVENTION (75) The film formation conditions and the composition of the obtained transparent conductive oxide film are as shown in Table 5. The evaluation results of the transparent conductive oxide film of the conductive transparent film obtained are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are shown in Table 7. [Example 1 8] The same alkali-free glass substrate as in Example 1 was used except for the transparent substrate, the temperature of the glass substrate was 2 15 ° C, and the amount of oxygen gas in the mixed gas at the time of sputtering was 3 Conductive transparent glass was obtained in the same manner as in Example 9 except that % (oxygen partial pressure: 3 x 10 Å - 3 Pa). The film formation conditions and the constituents of the obtained transparent conductive oxide film are as shown in Table 5, for example. The evaluation results of the transparent conductive oxide film of the conductive transparent glass obtained above are shown in Table 6. The evaluation results of the transparent conductive oxide film after heating are shown in Table 7. [Comparative Example 8] A non-glass-like substrate similar to that of Example 1 was used except for the transparent substrate, and a hexagonal layered compound represented by I η 2 〇 3 ( Ζ η 〇 ) 3 was used as the sputtering target (crystal grain size 1) 2 // m ) and ί η 2 〇3 constitute a sintered body target [I n / ( I η + Ζ η ) = 0 · 9 5 , relative density = 8 0 This paper scale applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) (Please read the notes on the back and fill out this page) - ϋ ϋ 1· —ινϋ Ν t§ . Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed Economy Ministry Intellectual Property Bureau Staff Consumption Cooperatives printed 1269817 A7 B7 V. Inventive Note (76) %] The same as in Example 9, the conductive transparent glass was produced. The film formation conditions and the constituents of the obtained transparent conductive oxide film are as shown in Table 5, for example. The obtained conductive transparent glass was evaluated in the same manner as in Example 9. The results are shown in Table 6. - The transparent conductive oxide film of the transparent conductive oxide film formed by the heat treatment, and the indium oxide-containing junction was observed by X-ray diffraction analysis [Comparative Example 9] In addition to the use of the transparent substrate, and Example 1 A conductive transparent glass was produced in the same manner as in Example 1 except that the sputtering target was an IT target (I η 2 〇 3 / 5 at · % S η 〇 2 ). The transparent conductive oxide film of the conductive transparent glass obtained was found to contain crystals of indium oxide by X-ray diffraction analysis. The film formation conditions and the constituents of the obtained transparent conductive oxide film are as shown in Table 5, for example. The evaluation results of the conductive transparent glass are shown in Table 6. [Comparative Example 10] The same alkali-free glass substrate as in Example 10 was used as the transparent substrate, and the sputtering target was a hexagonal layered compound (crystal grain size of 8 // m ) of I n 2 〇 3 (Zn〇). 3, I Π2〇3 and Sn〇2 consist of sintered body [In/(In + Zn) =0 · 98,Sn/(In this paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ) -79 - -III·-------I — l·------------- (Please read the notes on the back and fill out this page) A conductive transparent glass was produced in the same manner as in Example 1 except that the consumer cooperative printed 1269817 A7 __ B7 V, invention description (77) + Zn + Sn) = 〇· 05, relative density = 94%. The transparent conductive oxide film of the conductive transparent glass obtained was found to contain crystals of indium oxide by X-ray diffraction analysis. The film forming conditions herein and the atoms of the metal to be formed of the transparent conductive oxide film obtained are shown in Table 5. The evaluation results of the produced conductive transparent glass are shown in Table 6. μ rl· I,-----------.---"-Booking Γ (Please read the note on the back and fill in this page) Material substrate temperature of the 5th substrate rc ) Oxygen Partial pressure (Pa) In / (In + Zn) Sn / (In + Zn + Sn) Film thickness (mm) 9 PET 20 2.8 X 10'4 0.93 0.08 250 10 Glass 20 2.8 X 10·4 0.93 0.08 200 11 Glass 215 2.8 X 10'4 0.93 0.08 100 Real 12 PET 20 5.0 X 10·4 0.96 0.18 300 Application 13 Glass 20 5.0 X 10*4 0.96 0.18 250 Example 14 Glass 20 5.0 X 10·4 0.91 0.10 210 15 PET 20 5.0 X 10·4 0.91 0.10 200 16 PET 20 1.0 X 10·4 0.95 0.10 100 17 PET 20 5.0 X 10·4 0.95 0.10 100 18 Glass 215 3.0 X 10·4 0.95 0.10 100 than 8 Glass 215 2.8 X 10·4 0.95 A 100 to 9 glass 20 2.8 X 10·4 1.00 0.05 100 Example 10 Glass 215 2.8 X 10·4 0.98 0.05 100 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -80 - 1269817 A7 B7 V. INSTRUCTIONS (78) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 6 Light Transmittance (%) Initial Surface Resistance (Ω〇 Initial Specific Resistance (x104Qcm) Mobility ( Cm2/V · sec) Resistance change rate etching rate ("m/min) 9 88 10.4 2.6 27 1.10 0.20 10 89 12.5 2.5 20 1.12 0.20 11 91 19.0 1.9 31 1.27 0.19 Real 12 87 9.3 2.8 25 1.29 0.18 Apply 13 89 10.8 2.7 27 1.18 0.18 Example 14 89 12.8 2.7 28 1.18 0.19 15 88 14.0 2.8 28 1.14 0.19 16 89 24.0 2.4 20 1.15 0.19 17 88 22,0 2.2 31 1.11 0.19 18 91 18.0 1.8 34 1.05 0.17 than 8 79 43.2 4.3 18 1.14 Can't compare with 9 89 17.5 1.8 32 One can't be 10 89 640 64.0 — One can't (please read the back note first and then fill in this page) This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 V. INSTRUCTIONS (79) Table 7 Initial surface resistance (Ω / □) Initial specific resistance (X ΙΟ * 4 Ω cm) Etching speed (// m / min) 9 _ _ A 10 10.0 7.0 0.19 · 11 19.0 1.9 . 0.18 12 _ I - Real 13 8.4 2.1 0.18 Application 14 9.0 1.9 0.18 Example 15 _ One - 16 _ — A 17 _ One 18 18.0 1.8 0.17 (Please read the notes on the back and fill out this page) - --------*i order

IhN· i I '1 IIIII Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative [Example 1 9] (1) Preparation of transparent conductive material Indium oxide powder with an average particle size of 1 // m, average particle size 1 The zinc oxide powder and the tin oxide powder having an average particle diameter of 〇······· are supplied to the wet ball mill to form a ratio of 80% by weight of indium oxide, 5% by weight of zinc oxide and 15% by weight of tin oxide, followed by mixing. The raw material fine powder was obtained by pulverizing for 7 hours. Subsequently, the mixture was pelletized, pressed into a shape of a target, and fired at 1,450 ° C to obtain a sintered body. The relative density of the obtained sintered body (crystal size 4 · 0 / zm or less) is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 _B7___ V. Invention description (8Q) 98%, the volume resistance is Ο · 83ΜΩ· cm. (Please read the precautions on the back and fill out this page.) This sintered body is mounted on a jig for a sputtering device and used as a target. This target uses a size of 10 · 16 cm in diameter. Using this target, a transparent conductive oxide film was formed by sputtering on an alkali-free glass substrate #7059 (manufactured by Corning Co., Ltd.). In other words, the alkali-free glass substrate #7 0 5 9 is mounted on the RF magnetron sputtering device, and after the pressure in the vacuum chamber is reduced to 5 X 1 0_4P a or less, a mixed gas of argon gas and oxygen gas is introduced until 3xl〇. - For the "Pa", the RF output is 100W, and the substrate temperature is kept at room temperature, and a transparent conductive oxide film is formed by sputtering to obtain a transparent conductive glass. (2) Evaluation of target and transparent conductive oxide film The composition, relative density, bulk resistance, and crystallinity of the sintered body (target) obtained in the above (1) were evaluated. These results are shown in Table 8. Using the sintered body (target) obtained in the above (1), the transparent conductive oxide obtained by sputtering and maintaining the temperature of the transparent substrate while being kept at room temperature and sputtering was maintained at 200 Torr. The specific resistance and crystallinity of the film. These results are shown in Table 9. The crystallinity of the transparent conductive oxide film produced by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs was determined by X-ray diffraction pattern using Rotroflex RU-200B (manufactured by Rigaku Corporation) of the X-ray diffraction measuring device. The conductive oxide film is amorphous. The composition analysis of the transparent conductive oxide film uses an inductively coupled plasma luminescence spectroscopic analyzer SPS — 1 500VR (Seiko Electronics Industry Paper Scale Applicable to China National Standard (CNS) A4 Specification (210x297 mm) 1269817 A7 B7 V. Invention Description (81) Social system). (Please read the following precautions and then fill in this page.) The light transmittance of the transparent conductive oxide film (light wavelength of 50 〇 or 55 〇 nM) is based on the UV spectrometer U-3210 (manufactured by KK) Determination. The surface resistance of the transparent conductive oxide film (hereinafter referred to as initial surface resistance) was measured using a resistance measuring device, Rolester FP (manufactured by Mitsubishi Chemical Corporation), and the specific resistance was measured by a four-terminal method. The film thickness of the transparent conductive oxide film was measured by a stylus method using DEKTAK3030 (manufactured by Sloan Co., Ltd.). (3) Heat treatment of transparent conductive oxide film In the case of the transparent conductive glass obtained in the above (1), the transparent conductive oxide film formed by filming the temperature of the transparent substrate at room temperature is heat-treated at 280 °C. The transparent conductive oxide film formed at a temperature of 200 ° C for 1 hour and at a temperature of 200 ° C was heat-treated at 250 ° C for 1 hour, and then the specific resistance and crystallinity were evaluated. The results of these evaluations are shown in Table 9. [Embodiment 2 0 to 2 2] Printing by the Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives (1) Manufacturing of sintered body and transparent conductive oxide film except that the mixing ratio of raw materials is changed as shown in Table 8 2 0 to 2 2 A sintered body was produced in the same manner as in Example 19. Next, the sintered body obtained in each of the examples was used to produce a transparent conductive oxide film in the same manner as in Example 19. The temperature of the transparent substrate at the time of sputtering is as shown in Table 9. -δ4: This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 __B7 V. Description of invention (82) (2) Evaluation film 9 of sintered body and transparent conductive oxide film, The 8 oxygen is as good as the electric fruit. The price and the evaluation line are combined with the same phase.} 2 2ly /V- 1 (9) 1 The above example is applied. For the actual display and the system of oxygen production} On the surface of the heat of the film, the temperature is the same as the temperature s$. The heat point shows that the heat is in the form of the same phase. The examples of Ming and Dingyu (please read the notes on the back and fill out this page). Displayed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives [Comparative Example 1 1~1 5] (1) Sintered body and The production of the transparent conductive oxide film was carried out in the same manner as in Example 19 except that the mixing ratio of the raw materials was changed as shown in Table 8, and the sintered body was produced in the same manner as in Example 19. The average particle diameter was 3 // Indium oxide powder of m, zinc oxide powder having an average particle diameter of 3 /im, and tin oxide powder having an average particle diameter of 3 / m. Using the sintered body obtained in each of the examples, the transparent conductive material was produced in the same manner as in Example 19. Oxide film. The temperature of the transparent substrate during sputtering is as shown in Table 9. (2) Sintered body and transparent conductive oxygen Evaluation of the film of the film The sintered body and the transparent conductive oxide film obtained in the above (1) were evaluated in the same manner as in (1) of Example 19. As a result, the paper size was applied to the Chinese National Standard (CNS). ) A4 size (210 X 297 mm) 1269817 Δ7 Άί Β7 V. Description of invention (83) Table (3) Heat treatment of transparent conductive oxide film For the transparent conductive material obtained in the above (1), The heat treatment was carried out in the same manner as in (9) of Example 19 except for the heat treatment temperature shown in Table 9. The results are shown in Table 9. (Please read the back note first and then fill in this page) --- ---- SI 订--------- Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed Table 8 Example Comparative Example 19 20 21 22 11 12 13 14 15 I η 2〇3 (% by weight) 80 84 87 88 90 90 94 90 78 Sn〇2 (% by weight) 15 12 10 10 10 — 5 5 15 Zn〇 (% by weight) 5 4 3 2 A 10 1 5 7 Relative density (%) 98 97 98 99 98 98 97 96 97 Body resistance (m Ω cm) • 83 • 84 • 70 .65 .87 2.4 .87 2.1 2.4 Target mark * A4 B4 C4 D4 E4 F4 G4 H4 14 Paper ruler Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 V. Description of invention (84) Table 9 target mark transparent substrate temperature CC) After film formation, transparent conductive oxide film is heat-treated Transparent conductive acid film specific resistance (β Ω · cm) Crystallization heat treatment temperature °C specific resistance (// Ω · cm) · Crystalline solid 19 A4 Room temperature 290 Amorphous 280 180 Crystalline application A4 200 280 Non Crystal 250 160 Crystalline Example 20 B4 Room Temperature 280 Amorphous 250 190 Crystalline 21 C4 Room Temperature 230 Amorphous 230 190 Crystalline 22 D4 Room Temperature 260 Amorphous 230 200 Crystalline Ratio 11 E4 Room Temperature 550 Non Crystalline * 230 180 Crystalline compared to 12 F4 200 380 Amorphous 300 1400 Amorphous Example 13 G4 Room Temperature 270 Amorphous * 300 190 Crystalline G4 200 200 Crystalline _ — A 14 H4 Room Temperature 220 Amorphous 250 3200 Crystalline H4 200 3600 Crystalline _ I-15 H4 200 380 Amorphous 230 370 Crystalline* Includes Microcrystals-------------------- --------. (Please read the notes on the back and fill out this page) The production bureau employee consumption cooperative printed this paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1269817 A7 B7 V. Invention description (85) [Example 2 3] (1) The transparent conductive oxide film is formed so that an indium oxide powder having an average particle diameter of 1 / m, a zinc oxide powder having an average particle diameter of 1 / m, and an average particle diameter of 0 · 5 / m The ratio between the tin oxide powders was indium oxide 8 4 · 8 wt% 'zinc oxide 5 · wt% and tin oxide 1 0 · 0 wt%, and the powder of these metal oxides was mixed and pulverized by a wet ball mill. Then, it was granulated, pressed into a shape of a target, and fired at 1,450 °C to obtain a sintered body (crystal particle diameter: 3 · 7 // m or less). This sintered body is mounted on a jig for sputtering apparatus and used as a sputtering target. This target uses a size of 1 0 · 16 6 m in diameter. This target is used for sputtering. As the transparent substrate, an alkali-free glass substrate (manufactured by Connng Co., Ltd.: #7059) was used. The sputtering apparatus uses a parallel plate type magnetron sputtering device to evacuate the vacuum inside the device to 5 X 1 0 - 5 P a. The amount of water in the vacuum chamber at this time was measured by a mass spectrometer, and 8 X 1 0 - 6 P a was measured. An argon gas having a ratio of oxygen-containing gas of 1% by volume was introduced into the apparatus, and the sputtering pressure was adjusted to 0 · 3 P a to perform sputtering to form a transparent conductive oxide film on the glass substrate. The thickness of the obtained transparent conductive oxide film was 1 · 2 η Μ. The binding energy peak of the oxygen 1 S orbital was measured by X-ray photoelectron spectroscopy. The ESCA540 〇 'X ray source system of the company A 1 b a k f y was used to use M g - K α. The detector uses an electrostatic hemispherical type 'passing energy of 35 · 75 eV. The benchmark of the crest is set to 3d5/2 of indium. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) > · II l· ϋ Mmmmmm mmmmm^-WJ1 mi· ημ I Mm· I mm Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 B7 V. Inventive Note (86) For 4 4 4 · 4 e V to measure. The half width obtained here is set using the Shirley type and then the number is calculated. As a result, the binding energy of the oxygen 1 S orbital was measured by X-ray photoelectron spectroscopy to have a half-width of 2.6 eV. The surface of the transparent conductive oxide film measured here was measured for the binding energy peak of the oxygen 1 S orbital by X-ray photoelectron spectroscopy, as shown in Fig. 12. (2) Evaluation of Transparent Conductive Oxide Film The crystallinity, light transmittance, specific resistance and etching property of the transparent conductive oxide film obtained in the above (1) were evaluated. The crystallinity of the transparent conductive oxide film was confirmed by measuring X-ray diffraction using Rotarflex RU _ 2 Ο Ο B (manufactured by Rigaku Corporation) of an X-ray diffraction measuring apparatus. The light transmittance (light wavelength of 50,000 or 550 nM) of the transparent conductive oxide film was measured by UV spectrometry using a UV spectrometry apparatus U-3210 (manufactured by Toray Industries, Inc.) to measure the glass substrate by U V spectrometry. The surface resistance of the transparent conductive oxide film was measured by a four-terminal method using a resistance measuring device Rolester FP (manufactured by Mitsubishi Chemical Corporation). The etching characteristics were measured using a 3.4% by weight aqueous solution of oxalic acid as a contact liquid at a temperature of 40 °C. (3) Measurement of the connection resistance The transparent conductive oxide film obtained in the above (1) is etched into a strip having a pitch of 1 1 0 // m and a gap of 2 0 // m. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - Γρ Γ - 1 1_1 n ·1 I ϋ a- · ϋ n Lm I «I hit 0, d- ϋ ·ϋ (please read first Note on the back page again) 1269817 A7 _B7 _ V. Inventive Note (87) (Please read the note on the back and fill out this page) Overlap the anisotropic conductive film on the conductive oxide film to 1 800 The junction resistance between these transparent conductive oxide films and the anisotropic conductive film was measured by thermocompression bonding at °C. The average 値 of this resistor is 8 Ω. In order to confirm the long-term stability of the connection resistance, the anisotropic conductive film was overlaid on the transparent conductive oxide film, and the hot-pressed test piece was placed in an oven maintained at 90 ° C for 120 hours, and then The connection resistance of the test piece was measured. Even after this long-time heat treatment, this test piece showed no change in the connection resistance. The composition and evaluation results of the obtained transparent conductive oxide film are shown in Table 10. [Example 2 4] The same as in Example 2, except that the mixing ratio of the metal oxide component of the raw material was changed to indium oxide 87. 3 wt%, tin oxide 9.5 wt%, and oxidation number 3.2 wt%. A target is produced while forming a transparent conductive oxide film. At this time, the amount of water in the vacuum box is 7 X 1 0 — 6 P a 0 - The oxygen 1 S orbit of the transparent conductive oxide film prepared by X-ray photoelectron spectroscopy is printed by the Ministry of Economic Affairs and Intellectual Property Office. The width of the combined energy peak is 2.5 volts. The composition and evaluation results of the obtained transparent conductive oxide film are shown in Table 10. [Example 2 5] In addition to the proportion of the metal oxide component of the raw material changed to indium oxide, the paper scale is applicable to China National Fresh (CNS) A4 specification (210 X 297 public hair) _ 90 - " -- 1269817 A7 B7 economy The Ministry of Intellectual Property's employee consumption cooperative printed five, invention description (88) 81 · 6 wt%, tin oxide 12 · 2 wt% and zinc oxide 6 · 2 wt%, the same as the example 2 3 to make the target, while A transparent conductive oxide film is formed. At this time, the amount of water in the vacuum chamber is 9 X 1 〇 6 Pa 〇 The half-degree of the binding energy peak of the oxygen 1 S orbital of the transparent conductive oxide film obtained by X-ray photoelectron spectroscopy is 2 · 7 eV. The composition and evaluation results of the transparent conductive oxide film are shown in Table 10 [Comparative Example 16] In addition to the use of an indium oxide powder having an average particle diameter of 3 // m, an oxidation of an average particle diameter of 3 // m Tin powder and zinc oxide powder with an average particle diameter of 3 //m, and the proportion of the mixture is changed to indium oxide 8 8 · 7 wt%, tin oxide 1 0 · 1 wt% and zinc oxide 1.2 · wt%, and the rest Example 2 3 A target (crystal grain size of 1 5 // m) was produced in the same manner to form a transparent conductive oxide film. At this time, the amount of water in the vacuum box is 9x10_6Pa. The half-turn width of the binding energy peak of the oxygen 1 S orbital of the transparent conductive oxide film obtained by X-ray photoelectron spectroscopy is 2. 9 e V. The etching rate of the obtained transparent conductive oxide film was as low as 4.4 A/sec. The composition and evaluation results of this transparent conductive oxide film are shown in Table 1. [Comparative Example 1 7] The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -91- (Please read the notes on the back and fill out this page)

1269817 A7 B7 V. INSTRUCTIONS (89) In addition to the use of indium oxide powder having an average particle diameter of 3 // m, tin oxide powder having an average particle diameter of 3 /zm and zinc oxide powder having an average particle diameter of 3 //m, At the same time, the mixing ratio was changed to indium oxide 84.8% by weight, tin oxide 1.0% by weight, and zinc oxide 5.2% by weight, and the same target as in Example 23 was prepared (crystal grain size 1 1 μm). .

Then, except that the vacuum exhaust gas at the start of sputtering is discharged to 2 X 1 0 - 5P a, and the argon gas containing 1% by volume of oxygen gas is adjusted to 0 · 3 Pa, the amount of water in the vacuum chamber is 9 x 10 - 4 Pa. The same as in Example 23, a transparent conductive oxide film was formed. The half-turn width of the binding energy peak of the oxygen 1 S orbital of the transparent conductive oxide film obtained by X-ray photoelectron spectroscopy was 3 · 3 e V. The heat resistance of the obtained transparent conductive oxide film was greatly increased after heat treatment at 95 ° C for 120 hours. The composition and evaluation results of this transparent conductive oxide film are shown in Table 10. [Comparative Example 1 8] In addition to using an indium oxide powder having an average particle diameter of 3 # m, a tin oxide powder having an average particle diameter of 3 μm and a zinc oxide powder having an average particle diameter of 3 // m, and the proportion was changed to A target (crystal grain size of 1 4 // m ) was formed in the same manner as in Example 23 except that indium oxide 8 3 · 4% by weight, tin oxide 4 · 3 % by weight, and zinc oxide 12 2 · 3 % by weight, and transparent was formed. Conductive oxide film. At this time, the amount of water in the vacuum box is 1 X 1 0 — 7 P a 透明 The transparent conductive oxide obtained by X-ray photoelectron spectroscopy is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 gong).厘) (Please read the note on the back and fill out this page) ir Book----'· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 B7 V. Invention Description (9Q) The half-turn width of the combined energy peak of the oxygen 1 S orbital of the membrane is 3 · 8 e V. The binding energy peak of the oxygen 1 S orbital on the surface of the transparent conductive oxide film measured by X-ray photoelectron spectroscopy is as shown in Fig. 13. The heat resistance of the obtained transparent conductive oxide film was greatly increased after heat treatment at 95 ° C for 120 hours. The composition and evaluation results of this transparent conductive oxide film are shown in Table 10. [Comparative Example 1 9] In addition to using an indium oxide powder having an average particle diameter of 3 // m and a tin oxide powder having an average particle diameter of 3 // m, the mixing ratio was changed to indium oxide of 90·0% by weight and tin oxide. A target (crystal grain size of 1 8 // m) was produced in the same manner as in Example 2 except that 10% by weight. Then, except that the vacuum exhaust gas at the start of sputtering is discharged to 2 X 1 0 - 5P a, and the argon gas containing 1% by volume of oxygen gas is adjusted to 〇·3 Pa, the amount of water in the vacuum chamber is 9×10 −4 Pa, and the rest. A transparent conductive oxide film was formed in the same manner as in Example 2 3. The half-turn width of the binding energy peak of the oxygen 1 S orbital of the transparent conductive oxide film obtained by X-ray photoelectron spectroscopy was 3.4 eV. The heat resistance of the obtained transparent conductive oxide film was greatly increased after heat treatment at 95 ° C for 120 hours. The composition and evaluation results of this transparent conductive oxide film are shown in Table 10. This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -93 - (Please read the note on the back and fill out this page), - book · 1269817 A7 B7 V. Invention description (%) Economy Ministry of Intellectual Property Office Staff Consumer Cooperatives Printed Form 1 Table Example Comparative Example 23 24 25 16 17 18 19 Group Im〇3 (% by weight) 84.8 87.3 81.6 88.7 84.8 83.4 90.0 into Sn〇2 (% by weight) 10.0 9.5 12.2 10.1 10.0 4.3 · 10.0 Zn〇 (% by weight) 5.2 3.2 6.2 . 1.2 5.2 12.3 Water content 8 7 9 9 20 0.1 900 (X 106Pa) Half 値 width 2.6 2.5 2.7 2.9 3.3 3.8 3.4 (eV) Crystal evaluation amorphous amorphous Amorphous amorphous amorphous amorphous light transmittance (%) 81 81 82 81 81 80 81 Specific resistance (μ Ω m) 240 220 240 280 490 370 560 Etching speed 0.09 0.06 0.09 0.03 0.10 0.11 0.06 (β m/ 60 sec) Initial contact resistance 8 10 12 11 14 16 34 (Ω) Contact resistance after heat treatment 8 10 12 11 38 54 78 (Ω ) * Amorphous evaluation of amorphous means amorphous.

订·ί·------ (Please read the notes on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269817 A7 B7 V. Description of the invention ( 92) [Example 2 6] (1) Formation of Organic Colored Layer of Substrate A glass substrate was used, and a light-shielding layer made of chromium oxide was formed on the surface. The light shielding layer is formed by sputtering, and the thickness of the chromium oxide is 0 · 1 // m 〇 and then one of the above light shielding layers is processed into a distance of 1 1 0 //m by lithography lithography. Then, it is processed into a grid of 3 3 0//m with a line width of 3 0#m. Then, the green pigment was applied to a grid-like chromium oxide layer by using a phthalocyanine green pigment (Color Index No. 74160 Pigment Green 36) and a paste which was dispersed and mixed in a transparent polyimide precursor solution Semikofine SP-190 (manufactured by Toray Industries, Inc.). After the semi-hardening, a strip of green organic colored layer having a width of 9 0 // m corresponding to the pixel and a pitch of 3 3 0 // m is formed, and then hardened. The green organic colored layer has a thickness of 1 · 5 // m. The red pigment is a quinophthalone pigment (Color Index No. 73905 Pigment Red 209), and the blue pigment is a sapphire blue pigment (Color Index No. 7416 Pigment Blue 5-4 ), and the paste obtained by dispersing and mixing these in the polyimine precursor solution is the same as described above. A red organic colored layer and a blue organic colored layer are formed. The above polyimine precursor solution was coated on these organic colored layers and hardened to obtain a protective layer having a thickness of 2 // m. (2) Formation of transparent conductive film The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) I丨·Economics Bureau of Intellectual Property Printed by the Consumer Co., Ltd. 1269817 A7 B7 V. Inventive Note (93) On the organic colored layer of the glass-based plate having the organic colored layer obtained in the above (1), a transparent conductive film (transparent conductive oxide film) is formed by sputtering. ). The sputtering target used was produced as follows. In other words, a mixture of 80% by weight of indium oxide powder, 15% by weight of tin oxide powder, and 5% by weight of zinc oxide was mixed and pulverized by a wet ball mill. Then, it is granulated and press-formed in a firing furnace, and calcined under the condition of oxygen gas at 1,450 ° C for 36 hours to obtain a target having a crystal grain size of 4 · 0 # m [A 6] The target [A6] manufactured by 〇 is mounted on a DC magnetron sputtering device, and a transparent conductive film is formed on the organic colored layer of the glass substrate by sputtering, and the atmosphere of the sputtering condition is appropriate. The oxygen gas was mixed with argon gas, and the sputtering pressure was 3 X 1 0 _ 1 P a , the pressure reached 5 X 10 - 4 Pa, the substrate temperature was 25 ° C, and the electric power was supplied to 100 W, and the film formation time was 20 minutes. As a result, a transparent conductive film in which a transparent conductive oxide having a film thickness of about 1 2 η Μ was formed on the glass substrate was obtained. The transparent conductive film was observed to have crystallinity by an X-ray diffraction method, and it was confirmed to be amorphous. Further, on the organic colored layer of the glass substrate, a transparent conductive film was formed under the condition that the substrate temperature at the time of sputtering was 180 °C. This transparent conductive film is also amorphous. The material composition and physical properties of the transparent conductive film are shown in Table 1. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) • · II l· II 1-1 · · ί ι·---- -- Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Printing 1269817 A7 B7 V. Inventive Note (94) (3) Evaluation of etching characteristics of transparent conductive film The uranium engraving of the transparent conductive film obtained by evaluation. In other words, a portion of the transparent conductive film formed on the organic colored layer was etched using an aqueous solution of oxalic acid (5 wt%) at 40 ° C, and the cross section of the interface portion between the uranium engraved portion and the non-etched portion was observed with an electron microscope. As a result, no transparent conductive film remained in the etched portion, and the edge portion of the transparent conductive film remaining in the non-etched portion was found to have a smooth cross-sectional shape toward the etched portion. Therefore, it has been found that the obtained transparent conductive film has excellent processability even if it is etched using a weak acid. When the etching processability of the transparent conductive film was evaluated, the evaluation criteria of the examples were used. The evaluation results are shown in Table 2. (4) Crystallization of heat treatment of the transparent conductive film Next, the transparent conductive film formed on the organic colored layer of the glass substrate obtained in the above (2) is subjected to heat treatment. The heat treatment was carried out under the argon gas atmosphere at a temperature elevation rate of 20 ° C / min, and heated to 203 ° C, and maintained at this temperature for 1 hour. As a result, the transparent conductive oxide film was crystalline, and the specific resistance measured by the four-probe method was 230 Χ 10 6 Ω·cm. The transparency of the transparent conductive oxide film is such that the light transmittance at a wavelength of 50,000 nM is 82% by a spectrophotometer, and the transparency is excellent. This heat treatment did not find adverse effects such as thermal deterioration of the organic colored layer. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Γ^Γ (please read the notes on the back and fill out this page) ___I. n ϋ I^-aJ· n ϋ -kn ϋ Economy Ministry of Intellectual Property Office Staff Consumer Cooperative Printed 1269817 A7 B7 V. Inventive Note (95) [Embodiment 2 7] (1) The formation of a transparent conductive film was prepared in the same manner as in (1) of Example 26. On the organic colored layer of the glass substrate of the organic colored layer, except for the sputtering target, a mixture of 84% by weight of indium oxide powder, 12% by weight of tin oxide powder, and 4% by weight of zinc oxide is used as a raw material. 2 6 (2) The same target [B 6] (crystal size 4 · 0 // m) was formed to form a transparent conductive film. The raw material composition and physical properties are shown in Table 11. (2) Evaluation of etching characteristics of the transparent conductive film The etching characteristics of the transparent conductive film obtained in the above (1) were evaluated in the same manner as in (3) of Example 26. The result is shown in Table 12. (1) Crystallization of heat treatment of transparent conductive film and evaluation of transparent conductive film The transparent conductive film obtained in the above (1) was subjected to heat treatment in the same manner as in (4) of Example 26 to obtain a transparent conductive film. The results are as shown in Fig. 2 [Example 28] (1) The transparent conductive film was formed on the organic colored layer of the glass substrate having the organic colored layer obtained in the same manner as in (1) of Example 26, In addition to the sputtering target system, indium oxide powder is used in an amount of 87% by weight, tin oxide powder is 1% by weight, and zinc oxide is used. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first) Note: Please fill out this page again. - Order ------- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1269817 A7 B7 V. Invention Description (96) The mixture of weight % is raw material, and the rest is the same as Example 2 6 (2) The same prepared 粑 [C 6] (crystal grain size: 4.1 //m) forms a transparent conductive film. The raw material composition and physical properties are shown in Table 11. (2) Evaluation of etching characteristics of transparent conductive film The etching characteristics of the transparent conductive film obtained in the above (1) were evaluated in the same manner as in (3) of Example 2-6. The result is shown in Table 12. (3) Crystallization of heat treatment of the transparent conductive film The transparent conductive film obtained in the above (1) was subjected to heat treatment in the same manner as in (4) of Example 26. The result is shown in Table 12. [Example 2 9] (1) Formation of a transparent conductive film On an organic colored layer of a glass substrate having an organic colored layer obtained in the same manner as in (1) of Example 26, except for a sputtering target system The target [D 6] (crystal grain size) obtained by the same as the mixture of the indium oxide powder (80% by weight, 10% by weight of the tin oxide powder, and 2% by weight of the zinc oxide) was used as the raw material. A transparent conductive film is formed as 4 · 0 // m ). The raw material composition and physical properties are shown in Table 11. (2) Evaluation of uranium engraving characteristics of transparent conductive film This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) -· I ϋ —l · ϋ ϋ n»r« I (0, Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing 1269817

V. Inventive Description (97) The etching characteristics of the transparent conductive film obtained in the above (1) were evaluated in the same manner as in (3) of Example 2-6. The result is shown in Table 12. (3) Crystallization of heat treatment of the transparent conductive film The transparent conductive film obtained in the above (1) was subjected to heat treatment in the same manner as in Example (6). The result is shown in Figure 12. [Comparative Example 20] (1) Formation of a transparent conductive film On an organic colored layer of a glass substrate having an organic colored layer obtained by the same procedure as in (1) of Example 26, indium oxide powder 9 was used. 〇% by weight, 10% by weight of tin oxide powder as raw material, leather containing no zinc oxide powder E [E6] (crystal size is 12 //m), forming a transparent conductive film, its raw material composition and physical properties such as the first 1 The table shows. (2) Evaluation of etching characteristics of transparent conductive film The etching characteristics of the transparent conductive film obtained in the above (1) were evaluated in the same manner as in (3) of Example 2-6. The result is shown in Table 12. (3) Crystallization of heat treatment of transparent conductive film The transparent conductive film obtained in the above (1) was subjected to heat treatment in the same manner as in (4) of Example 26. The result is shown in Table 12. (Please read the note on the back and fill out this page) -ai al· «ϋ Β — · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) 00- ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ (1) On the organic colored layer of the glass substrate of the organic colored layer obtained by the same preparation, except for the sputtering target, 90% by weight of the indium oxide powder and 10% by weight of the zinc oxide powder having an average particle diameter of more than 3 are used. The mixture of % was used as the raw material, and the target [F 6] (crystal grain size: 18; m) prepared in the same manner as in (2) of Example 26 was formed to form a transparent conductive film. The transparent conductive film obtained was obtained by X. The crystallinity was observed by a ray diffraction method, and it was confirmed to be amorphous. The raw material composition and physical properties thereof are shown in Table 1. (2) Evaluation of the etch characteristics of the transparent conductive film was evaluated in the same manner as in Example 2 (3). The etching characteristics of the conductive film. The results are shown in Table 12. (3) Crystallization of heat treatment of transparent conductive film The transparent conductive film obtained in the above (1) was subjected to heat treatment in the same manner as in (4) of Example 26. The results are shown in Table 12. [Comparative Example 2 2] (1) The transparent conductive film was formed on the organic colored layer of the glass substrate having the organic coating layer prepared in the same manner as in (1) of Example 26, except that the sputtering target system was used to flatten and the particle diameter exceeded 3 // Indium oxide powder of m is 9.4% by weight, and the average particle size exceeds the paper size. It is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) μΓ l·—.-------9^^___ ( Please read the notes on the back and fill out this page.)

1269817 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed A7 B7 V. INSTRUCTIONS (99) Mixture of 5 wt% of tin oxide powder of 3 //m and 1 wt% of zinc oxide powder with an average particle size of more than 3 //m The target [G 6 ] (crystal grain size: 1 5 // m) obtained in the same manner as in (2) of Example 26 was used as a raw material to form a transparent conductive film. The obtained transparent conductive film was observed to have crystallinity by an X-ray diffraction method, and it was confirmed that it was amorphous. Using this target [G6], the substrate temperature at the time of sputtering was 200 °C to form a transparent conductive film. The raw material composition and physical properties are shown in Table 11. (2) Evaluation of etching characteristics of the transparent conductive film The etching characteristics of the transparent conductive film obtained in the above (1) were evaluated in the same manner as in (3) of Example 2-6. The result is shown in Table 12. (3) Crystallization of heat treatment of transparent conductive film The transparent conductive film formed by the substrate temperature of the above (1) at room temperature was subjected to heat treatment in the same manner as in (4) of Example 26. The result is shown in Figure 12. [Comparative Example 2 3] (1) The transparent conductive film was formed on the organic colored layer of the glass substrate having the organic colored layer obtained in the same manner as in (1) of Example 26, except that the sputtering target system was used. The paper size of the indium oxide powder having an average particle diameter of more than 3 //m is 90% by weight, the 5% by weight of the tin oxide powder having an average particle diameter of more than 3, and the average particle diameter exceeding 3 are applicable to the Chinese National Standard (CNS) A4 specification (210). X 297 mm) - TO2 - · n ϋ Lm I 1 π · ϋ ϋ fi 1- (Please read the note on the back and fill out this page) 1269817 Made by 丨 丨 A A A7 V. Description of invention (10 °) A mixture of 5% by weight of zinc oxide powder was used as a raw material, and the same procedure as in (2) of Example 26 (?) (crystal diameter: 1 7 am) was carried out to form a transparent conductive film. The obtained transparent conductive film was observed to have crystallinity by an X-ray diffraction method, and it was confirmed that it was amorphous. Use this 耙 [Η 6]' The substrate temperature at the time of sputtering is 2 〇 〇 ν & into a transparent conductive film. The obtained transparent conductive film is crystalline. The original physical properties are shown in Table 11. (2) Evaluation of etching characteristics of the transparent conductive film The etching characteristics of the above-mentioned conductive film were evaluated in the same manner as in (3) of Example 2-6. The results are shown in Table 12. (3) Crystallization of heat treatment of the transparent conductive film The transparent guide formed by the temperature of the substrate of the above (1) is room temperature. @ @ The medium is heat treated in the same manner as in the case of Example 2 (4). (Please read the note on the back and fill out this page.) Ministry of Economics The property bureau employee consumption cooperative printed this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1269817 _B7 V. Invention description (1〇1) Table 1 1 Table of Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Printed Example Comparative Example 26 27 28 29 20 21 22 23 I η 2〇3 (% by weight) 80 84 87 88 90 90 94 90 S η〇2 (% by weight) 15 12 10 10 10 -5 5 Ζη〇( Weight %) 5 4 3 1 , a 10 1 5 Relative density (%) 98 97 98 99 98 98 97 96 Body resistance (m Ω cm) 0.83 0.84 0.70 0.65 0.87 2.43 0.87 2.1 Target mark A6 B6 C6 D6 E6 F6 G6 H6 (Please read the note on the back and fill in this page) D.. The paper size is suitable China National Standard (CNS) A4 specification (210 X 297 mm) 1269817 Α7 Β7 V. Invention description (1〇2) No. 1 2 target mark The transparent conductive film after heat treatment of the transparent conductive film after lamination of the substrate Crystal etching characteristics temperature ratio resistance crystal CO (β Ω · cm) rc) (β Ω · cm) real 26 A6 room temperature 290 amorphous 〇 230 230 crystallization application A6 180 280 amorphous 〇 · 230 210 crystallization example 27 B6 room temperature 280 Amorphous 〇 230 220 ί 曰曰 28 C6 Room Temperature 230 Amorphous 〇 230 210 曰曰 曰曰 29 D6 Room Temperature 260 Amorphous 〇 250 200 $ Port ratio 20 E6 Room temperature 550 Amorphous * Δ 230 180 Crystallization compared to 21 F6 200 380 Amorphous 〇250 370 Amorphous Example 22 G6 Room Temperature 270 Amorphous Δ 250 230 erg G6 200 200 Crystallization X One-to-one 23 H6 Room Temperature 220 Amorphous Δ 250 3200 H6 200 3600 Crystalline X _ — — * Amorphous in the evaluation of crystal refers to amorphous. The quality of the crystal is not the price of the crystal. (Please read the note on the back and fill out this page) _____ ·

1— n *1 I ϋ ϋ ϋ I Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed on this paper scale Applicable to China National Standard (CNS) A4 Specification (210 297 297 mm) 1269817 A7 Β7 V. Invention Description (1〇3 Industrial Applicability As described in detail above, according to the present invention, by controlling the size of the crystal grain size to a predetermined number or more, it is possible to effectively suppress the occurrence of protrusions when the transparent conductive oxide film is formed by sputtering. It can stabilize the beach plating for a long time. According to the method for producing a sputtering target of the present invention, it is possible to provide a target capable of suppressing the occurrence of projections when the transparent conductive oxide film is formed by a sputtering method. According to the transparent conductive oxide of the present invention, excellent electrical conductivity or transparency and smooth surface characteristics can be obtained. (Please read the precautions on the back and fill out this page.) ------ Department of Economics, Intellectual Property Bureau, Staff and Consumer Cooperatives Printed This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) _ IU0

Claims (1)

1269817 A8 B8 C8 D8 Patent application scope Patent Application No. 89 1 25063 Revision of Chinese Patent Application - Ben ~ Republic of China Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1 · A sputtering target consisting of at least sputtering containing indium oxide and zinc oxide a target characterized by; [n / (I η + Ζ Π) represents an atomic ratio of 0 _ 7 5 〇. 9 7 in the range of 値, and contains I n2 〇 3 (Zll 〇) m (however, m is an integer of 2 to 20) represents a hexagonal layered compound, and the hexagonal crystal layered compound has a maximum crystal grain size of 5 // m or less. 2. The sputtering target according to claim 1, wherein the indium oxide is 6-7 to 3% by weight, the tin oxide is 5 to 25% by weight, and the zinc oxide is 2 to 8% by weight, and the atomic ratio of tin/zinc is It is 1 or more. 3. The sputtering target according to claim 1 or 2, wherein the hexagonal layered compound or a hexagonal layered compound and a spinel structure compound represented by η η 2 S η 〇 4 are substituted, and the The maximum crystal grain size of the spinel structure compound is 5 // m or less. 4. A sputtering target according to claim 1 or 2, wherein the body impedance is less than 1 x 1 〇 _ 3 Ω · cm. 5 · A sputtering target according to claim 1 or 2, wherein the density is 6.7 g/cm 3 or more. 6. A transparent conductive oxide film characterized in that it comprises 6 to 3% by weight of indium oxide, 5 to 25 % by weight of tin oxide, and 2 to 8% by weight of zinc oxide, and the atomic ratio of tin/zinc is 1 or more, the atomic ratio expressed by I η / ( I n + Zn) is 0. 7 5~ (Please read the notes on the back and fill out this page) 卜订”. #本纸标准逋 Chinese National Standard (CNS) A4 Specification (21〇><297 mm) 1269817 H C8 D8 VI. The scope of the patent application range is 0.97, which also contains In2〇3 (ZnO) m (but m is an integer of 2 to 2 0) represents a hexagonal layered compound, and the hexagonal crystal layered compound has a maximum crystal grain size of 5 // m or less, and is sputtered. Forming a film, and then crystallization is carried out at a temperature of from 2 3 0 ° C to 3 2 0 t. 7 · A transparent conductive oxide film characterized by oxidizing using indium oxide 6 7 to 93 % by weight 5 to 25% by weight of tin and 2 to 8% by weight of zinc oxide, the atomic ratio of tin/zinc is 1 or more, and the atomic ratio expressed by I η / ( 1 η + Ζη) is 〇 75 to 0 · 97, a hexagonal layered compound represented by I n 2 〇 3 (Zn〇)ra (but m is an integer of 2 to 20), and the hexagonal crystal layered compound has a maximum crystal grain size of 5 // m or less. The target is formed by sputtering, and the half-turn width of the binding energy peak of the oxygen 1 S orbital measured by X-ray photoelectric molecular spectrometry is 3 e V or less. The transparent conductive oxide film of claim 6 is formed on the substrate or on the coloring layer provided on the substrate. 9 · Transparent conductive oxide film according to claim 7 And forming a transparent conductive oxide film on the substrate or on the coloring layer provided on the substrate. 1) The transparent conductive oxide film according to claim 6 of the patent application, wherein P-V値 determined according to JIS SB0601 The following is a transparent conductive oxide film according to item 7 of the patent application scope, wherein the P-V値 measured according to JIS B0601 is 1 Am or less. (Please read the «Precautions on the back side Fill in this page) tr Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -2 - 1269817 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed System 6, Patent Application Range 1 2 - A method for manufacturing a sputtering target as claimed in claim 1, which contains I Π 2 〇 3 (Zn 〇) m (but m is an integer of 2 to 2 0) a hexagonal layered compound, and A method for producing a sputtering target having a maximum crystal grain size of a hexagonal crystal layered compound of 5 // m or less, which is characterized by comprising the following steps (1) to (3), (1) mixing indium oxide powder with an average particle a step of oxidizing a bell powder having a diameter of 2 // m or less, (2) a step of forming a formed body having an atomic ratio of 0.75 to 0.97 expressed by I η / ( I n + Zn), and (3) at 1 4 0 〇 The step of sintering the shaped body under an oxygen atmosphere or oxygen pressure at a temperature above °C. The method for producing a sputtering target according to the first aspect of the invention, wherein in the step (1), the indium oxide powder is blended with 6 7 to 93% by weight, the tin oxide powder is 5 to 25 wt%, and the oxidation is performed. The zinc powder is 2 to 8% by weight, and in the above step (2), a molded body having an atomic ratio of tin/zinc of 1 or more is formed. A method for producing a sputtering target according to the first aspect of the patent application, which comprises a hexagonal layered compound represented by I n 2 〇 3 (Zn〇) m (but m is an integer of 2 to 20) And a method for producing a sputtering target having a maximum crystal grain size of the hexagonal layered compound of 5 // m or less, which is characterized by comprising the following steps (1) to (5), (1) generating I n2 〇3 (Zn〇)m (but m is an integer of 2 to 20) represents the step of the hexagonal layered compound, and (2) adjusts the maximum crystal grain size of the resulting hexagonal layered compound (please read the back first) Note: Please fill out this page) Order S! This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm)-3 - A8 B8 C8 D8 1269817 夂, the patent application range is 5 / zm or less Step, (3) mixing and adjusting the hexagonal crystal layer compound and the indium oxide powder after the maximum crystal grain size, and (4) forming an atomic ratio represented by I n / (I n + Zn) as 〇·75~0· Step of forming a molded body of 97, (5) Step of sintering the formed body under an oxygen atmosphere or oxygen under a temperature of 14,000 ° C or higher . The method of manufacturing a sputtering apparatus according to any one of claims 1 to 4, wherein the average particle diameter of the indium oxide powder is in the range of 〜 1 to 2 // m. The manufacturing method of the sputtering IE according to any one of the claims 1 to 4, wherein the indium oxide powder and the tin oxide powder are further blended, and the average particle diameter of the tin oxide powder is 〇·〇1 ~1 #m within the range. The method for producing a sputtering target according to any one of claims 1 to 4, wherein, when the formed body is formed, a spinel having a maximum crystal grain size adjusted to 5 # m or less is further blended Structural compound. (Please read the notes on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm).