TW201200616A - Oxide sintered body, oxide mixture, manufacturing methods for same, and targets using same - Google Patents

Abstract

The disclosed oxide sintered body is substantially formed from zinc, titanium, and oxygen, and the atomic ratio (Ti/(Zn+Ti) of the titanium to the sum of the zinc and the titanium is greater than 0.02 but does not exceed 0.1. The disclosed oxide mixture is formed from zinc oxide and titanium oxide, and the atomic ratio (Ti/(Zn+Ti) of the titanium to the sum of the zinc and the titanium is greater than 0.02 but does not exceed 0.1. An electrically conductive transparent zinc oxide film exhibiting excellent conductivity and chemical durability can be formed through using the disclosed oxide sintered body or oxide mixture.

Description

201200616 VI. Description of the Invention: [Technical Field] The present invention relates to an oxide sintered product, an oxide mixture, a method of manufacturing the same, and a target using the same. [Prior Art] In addition to being used as a solar cell, a liquid crystal display element, or an electrode in various other light-receiving elements, the transparent conductive film having both conductivity and light transmittance has also been used for reflection in hotlines of automobile windows or buildings. A wide range of applications such as transparent heat generating bodies for antifogging gas in films, antistatic films, and freezers. In particular, a transparent conductive film having excellent electrical conductivity with low electrical resistance is known to be applicable to liquid crystal display elements such as solar cells, liquid crystals, organic electroluminescence, and inorganic electroluminescence, or touch panels. In the past, as a transparent conductive film, for example, a film of a tin oxide (Sn02) type, a film of a zinc oxide (ZnO) type, and a film of an indium oxide (?n203) type are known. Specifically, a tin oxide-based transparent conductive film is known to contain ruthenium as a dopant or a fluorine-containing dopant (FTO); and a zinc oxide-based transparent conductive film is known to contain aluminum as a dopant A person (() or a person who contains gallium as a dopant (GZO); as for a transparent conductive film of an indium oxide type, a tin-containing dopant (indium tin oxide) is known. Among them, the indium oxide-based transparent conductive film, which is the most commonly used in the industry, is low in electrical resistance and excellent in electrical conductivity. Therefore, it has been widely used in the formation of such transparent conductive films, and it has been widely used in the industry in the past. Plating 201200616 method, ion plating method, pulsed laser deposition method (PLD method), electron beam (EB) vapor deposition method, spray method, melt gel method, and the like. In the film forming method, the target used as a film material is a sintered body or a mixture of a metal, a metal oxide, a metal nitride, a metal carbide, or the like, which is formed of a solid containing a metal element constituting a film to be formed. It is formed as a single crystal depending on the situation. For example, when a film such as an oxide of ITO is formed by sputtering, the target is generally an alloy target formed of a metal element constituting the film (In-Sn alloy when the ITO film is used), or a film containing the constituent film is used. An oxide target obtained by sintering or mixing an oxide of a metal element (the ITO film is a sintered body or a mixture of In-Sn-Ο). However, when an alloy target is used, since the oxygen in the formed film is completely supplied by the oxygen in the atmosphere, the amount of oxygen in the atmosphere is liable to change, and as a result, it is difficult to make the film formation speed or the yield depending on the amount of oxygen in the atmosphere. The characteristics of the film (specific resistance, transmittance) are kept constant. On the other hand, when an oxide target is used, a part of the oxygen supplied to the film is supplied by the target itself, and only a small portion is supplied from the oxygen in the atmosphere, so the amount of oxygen in the atmosphere changes compared to the use of the alloy target. When the suppression is obtained, as a result, a transparent conductive film having a certain film thickness and having certain film characteristics can be easily produced. Therefore, to date, industrial targets have used oxide targets (i.e., oxide sinter or oxide mixtures). However, the indium oxide-based transparent conductive film of the ITO film has a high price and a depletion of resources due to its rare metal, and it is toxic and has the possibility of adversely affecting the environment or the human body. Therefore, in recent years, a transparent conductive film which can be widely used industrially as an ITO film is desired. Among them, the zinc oxide-based transparent conductive material -6 - 201200616 which is industrially produced by the sputtering method is attracting attention, and progress is being made to improve its electrical conductivity. Specifically, attempts have been made to dope various dopants in ZnO capable of improving conductivity, and to report optimum doping amount and minimum resistivity for various dopants (Non-Patent Document 1). According to the report, for example, when doping TiO 2 , the doping amount is most suitable at 2 wt%, and the lowest resistivity at this time is 5.6 χ 1 (Γ4 Ω · cm. Accordingly, the zinc oxide-based transparent conductive film can be improved to obtain no more than The ITO film of the laboratory level has a low electrical resistance. However, the zinc oxide-based transparent conductive film has excellent electrical conductivity, heat resistance, moisture resistance, and chemical resistance (alkali resistance and acid resistance). Further, since the zinc oxide-based transparent conductive film lacks the chemical resistance (acid resistance and alkali resistance) as described above, the zinc oxide-based transparent conductive film is patterned into a desired shape. When necessary (for example, when used for components, etc.), there is a problem that a suitable wet etching solution does not exist, and the pattern cannot be formed well. In detail, zinc oxide has a very high dissolution rate to an acid or a base. Therefore, when the zinc oxide-based transparent conductive film is etched using an acid or a base, the etching rate is extremely large (specifically, the ratio to the ITO film is 100 times or more), and it dissolves on the spot, and a good pattern shape cannot be obtained. In addition, since the tin oxide-based transparent conductive film is excellent in chemical resistance (acid resistance and alkali resistance) and is stable to an acid or a base, it is difficult to dissolve by a usual etching liquid, and conversely means that it cannot be wet-etched. Therefore, the zinc oxide-based transparent conductive film or the tin oxide-based transparent conductive film has been disadvantageous in that it is not used for the purpose of patterning. Therefore, as a means for etching the zinc oxide-based film, proposals have been made. There is a specific acid as an etchant, and by doping the specific element 201200616, the zinc oxide engraving rate of the elemental rose Ti is uncovered. Moreover, its conductivity is also known and is extended in patent Ti02). Crystallization of the crystals of the balance, the etch rate can be suppressed at a low level (Patent Document 1). Specifically, it is shown in ZnO with 6 at% (where "at%" is zinc and the atomic number of the additive element relative to the total number of atoms of 100! The etching example of the zinc oxide thin film and doping 3at% Ti in ZnO An example of the etching of the thin film. However, the zinc oxide-based thin film disclosed in Patent Document 1 has an insufficient etching effect, and it is difficult to reliably control the etching rate, and the film is used instead of the ITO film as a conductive film. In addition, the environmental or chemical fragility of the zinc oxide-based transparent conductive film can be controlled by adding different kinds of metal elements. In particular, the titanium oxide having extremely strong durability is described in In the zinc oxide, the zinc oxide-based transparent conductive film can be improved. However, in Patent Document 2, since the position of the zinc element of the divalent element is replaced by the Ti element of the tetravalent element, the charge solution is increased, and the crystal structure is increased. It is difficult to exhibit sufficient conductivity, and it is difficult to exhibit sufficient conductivity. [Prior Art] [Patent Document 1] [Patent Document 1] JP-A-2008- 1 598 1 4 [Patent Document 2] Japan Special No. 4,295,811 [Patent Document] [Patent Document 1] Monthly Display, September 1999, pio~ 201200616

[Problem to be Solved by the Invention] [Problem to be Solved by the Invention] A first object of the present invention is to provide a preferred oxide for obtaining a zinc oxide-based transparent conductive film having both excellent electrical conductivity and chemical durability. A sintered body and an oxide mixture, a method for producing the same, and a target using the same. A second object of the present invention is to provide a method for forming a zinc oxide conductive film having excellent electrical conductivity and chemical durability, a zinc oxide based transparent conductive film formed by the method, and a transparent conductive substrate having the film. . A third object of the present invention is to provide a pattern of a zinc oxide-based film which has a sufficiently low etching rate at the time of patterning, can easily and surely control an etching rate, and can have a good pattern shape and high conductivity. Method. [Means for Solving the Problems] The present inventors have completed the present invention by repeating the results of the active review in order to solve the above problems, and have found a solution by the following constitution. That is, the oxide sintered body of the present invention is substantially composed of zinc, titanium and oxygen, and the atomic ratio of Ti to (Zn + Ti) of titanium to titanium is more than 0.02 and not more than 0.1. In the method for producing an oxide sintered product of the present invention, after the raw material powder containing the following (A) and/or (B) is molded, the obtained molded product is placed in an inert atmosphere in a vacuum or a reducing atmosphere. A method of sintering at 6001 to 1500 ° C, -9-201200616 (A) a mixed powder of titanium oxide powder and zinc oxide powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder, and (B) a zinc titanate compound powder. The method for producing an oxide sintered product of the present invention is obtained by molding a raw material powder containing the following (A) and/or (B), and then obtaining the obtained molded product in an atmosphere or an oxidizing atmosphere at 600 ° C to 1500 ° C sintering, followed by further annealing in an inert atmosphere, in a vacuum or in a reducing atmosphere (A) a mixed powder of titanium oxide powder and zinc oxide powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder, (B ) Zinc titanate compound powder. The oxide mixture of the present invention is composed of zinc oxide and titanium oxide, and the atomic ratio of Ti to (Zn + Ti ) of titanium to titanium is more than 0.02 and is 0.1 or less. The production method is a method in which a mixed powder containing a titanium oxide powder and a zinc oxide powder, or a raw material powder of a mixed powder of a titanium oxide powder and a zinc hydroxide powder is molded, in an air atmosphere, an inert atmosphere, a vacuum or a reducing atmosphere. A method of annealing the obtained shaped body at 50 ° C or higher and less than 600 ° C. The target of the present invention is a target obtained by processing the above oxide sintered body or the above oxide mixture. The method for forming a zinc oxide-based transparent conductive film of the present invention is a selected one selected from the group consisting of a pulsed laser deposition method (PLD method), a sputtering method, an ionization method, and an electron beam (EB) evaporation method. The method for forming a transparent oxide film of zinc oxide type-10-201200616 is substantially composed of zinc, titanium and oxygen, and the atomic ratio of titanium to total of zinc and titanium is Ti/(Zn + Ti). A method of processing a target obtained by processing an oxide sinter or an oxide mixture of more than 0.02 and less than 0.1. The zinc oxide-based transparent conductive film of the present invention is a film formed by the above-described method for forming a zinc oxide-based transparent conductive film. The transparent conductive substrate of the present invention is a substrate comprising the above-described zinc oxide-based transparent conductive film on a transparent substrate. The zinc oxide-based transparent conductive film forming material of the present invention contains zinc oxide as a main component and contains gallium and aluminum in an atomic ratio of Ti/(Zn + Ti ) of more than 0.02 and 0.1 or less in total of titanium and titanium. At least one of the oxide and the titanium oxide, and the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of metal atoms, and the titanium oxide is of the formula Ti02-x (X = 0.1). ~l) is composed of an oxide mixture of low atomic valence titanium oxide or an oxide sinter. The second target of the present invention is a target obtained by processing a zinc oxide-based transparent conductive film forming material. The second zinc oxide-based transparent conductive film of the present invention is formed by using the second target, by sputtering, ion plating, pulsed laser deposition (PLD) or electron beam (EB) evaporation. A method of forming a zinc oxide-based transparent conductive film. The transparent conductive substrate of the present invention is a substrate comprising a zinc oxide-based transparent conductive film formed on a transparent substrate by a method of forming the transparent conductive film. -11 - 201200616 The patterning method of the present invention is a method for thinning the zinc oxide by acid etching, wherein the zinc oxide-based film is mainly composed of zinc oxide, and the atomic ratio Ti/ is a total of zinc and titanium. (Zn + Ti ) 方法 0.02 and a method of a film of 0.1 or less. [Effect of the Invention] According to the present invention, a conductive conductive and chemically durable zinc-based transparent conductive film can be formed by a sputtering method, an ion plating method, or a PLD ΕΒ vapor deposition method. The transparent conductive film thus formed also has the advantage of having a toxic indium of a rare metal, and is therefore extremely industrially advantageous. Further, according to the present invention, a zinc oxide-based transparent conductive film having a good pattern shape and a high conductivity can be obtained. [Embodiment] (Oxide Sintered Material) The oxide sintered product of the present invention is substantially a sintered body of zinc oxide doped with zinc of titanium, titanium and oxygen. Here, "substantially" 99% or more of all atoms constituting the oxide sintered product are composed of zinc or fishing. The titanium oxide of the present invention has a composite-subnumber ratio Ti/(Zn + Ti) of more than 0.02 and 0.1 or less with respect to zinc and titanium. When the Zn + Ti) is 0.02 or less, an oxide sintered product is used; | the formed film is insufficient in chemical durability such as chemical resistance, and a zinc titanate compound is formed in the sintered body, so that the sintered body is The map of the strength is broad and the titanium is required to exceed the oxygen or the oxygen. Sexuality also means that the composition or oxygen precursor Ti/ (target is in oxygen, and -12-201200616 is difficult to process into a target. On the other hand, when Ti/(Zn + Ti) is more than 0.1, it forms as described later. The oxide sintered body is likely to have a high crystal phase of titanium oxide, and the conductivity or transparency of the film formed with the oxide sintered product as a target tends to decrease. The atomic number is preferably Ti/. (Zn + Ti ) = 0.025-0.09, more preferably Ti / ( Zn + Ti ) = 0.03 ~ 0.09, and more preferably Ti / ( Zn + Ti) = 0.03 ~ 0.08, preferably Ti / ( Zn + Ti) = 0.04 to 0.08 ° The oxide sintered product of the present invention is composed of a zinc oxide phase and a zinc titanate compound phase, and is preferably composed of a zinc titanate compound phase, for example, under excessively severe conditions (high power, etc.). When the film is formed and the zinc oxynitride compound phase is contained in the oxide sinter, the strength of the sinter itself is increased, so that cracking is less likely to occur. As for the zinc titanate compound, for example, in addition to ZnTi03 or Zn2Ti04, the zinc sites are also listed. In the case of solid solution of titanium, or introduction of oxygen deficiency, or Zn/Ti ratio is only by the combination Further, as a non-stoichiometric composition of zinc oxide, for example, in addition to ZnO, those in which titanium is solid-dissolved, those in which oxygen deficiency is introduced, or those in which zinc deficiency is a non-stoichiometric composition are also included. The phase usually has a wurtzite mineral structure. The oxide sintered product of the present invention preferably contains substantially no crystal phase of titanium oxide. When the oxide sintered body contains a crystal phase of titanium oxide, the obtained film may become The specificity of the specific resistance or the like lacks uniformity. The above-mentioned Ti/(Zn + Ti) of the oxide sintered product of the present invention is 〇. 1 or less, so usually titanium oxide is completely reacted in zinc oxide, and is sintered in oxide. The titanium oxide crystal phase is not easily produced in the material. Further, the crystal phase as titanium oxide is also exemplified by, for example, -13-201200616

Other than Ti〇2, Ti203, and TiO, other elements such as Zn in the crystals are exemplified. The oxide sintered product of the present invention preferably further contains at least one element selected from the group consisting of gallium, aluminum lanthanum, cerium, zirconium and hafnium (the term "addition element" is described). By including the additive element, the specific resistance of the film formed by using the oxide sinter as a target can also lower the specific resistance of the oxide sinter itself. For example, the specific resistance of the DC sputtering film formation rate to the oxide sintered body which becomes the sputtering target can improve the film formation property by lowering the specific resistance of the oxide sintered body itself. When the additive element is contained, the total content of the total metal element in the atomic ratio relative to the oxide sintered product is preferably 0.05%, and the content of the additive element is more than 0.05%. The specific resistance of the film increases. The additive element may also be present in the form of an oxide in the oxide or may be replaced (solid solution) in the zinc position of the zinc oxide phase or may be replaced (solid solution) in the titanium position of the zinc titanate compound phase and/or Form exists. The oxide sintered product of the present invention may contain other elements such as indium, bismuth, antimony or bismuth in addition to the essential elements or elements of zinc and titanium. The total content of the elements contained in the impurities is preferably 0 in terms of the atomic ratio of the total amount of all the metal elements constituting the oxide sintered product. The specific resistance of the oxide sintered product of the present invention is preferably 5 kΩ · under. For example, the film formation rate at the time of DC sputtering is related to the fact that it is deposited in the form of sputtering, tin, or the like, and is related to the plating, and is sometimes formed in the following structure, or zinc. The bit addition element is related to the specific resistance of the -14-201200616 oxide sinter of the target relative to .5% in cm, so if the specific resistance of the oxide sinter exceeds 5kD · cm, there will be no DC splashing. The film is formed with stability. In view of the productivity at the time of film formation, the specific resistance of the oxide sintered product of the present invention is preferably as low as possible, and specifically, it is preferably 100 Ω · cm or less. The oxide sintered product of the present invention is preferably obtained by the method for producing an oxide sintered product of the present invention described later, but is not limited to those obtained by such a production method. For example, it may be obtained by combining titanium metal, zinc oxide powder or zinc hydroxide powder, or combining titanium oxide and zinc metal as a raw material. When the oxide sintered product is usually sintered in a reducing atmosphere, the specific resistance of the oxide sintered body can be reduced by introducing an oxygen deficiency, and the specific resistance is increased in the oxidation atmosphere sintering. (Manufacturing Method of Oxide Sintered Material) The method for producing an oxide sintered product of the present invention is obtained by molding a raw material powder containing the following (A) and/or (B), and then obtaining the molded body obtained by sintering to obtain the above-described present invention. (Method of mixing oxide oxides) (A) a mixed powder of titanium oxide powder and zinc oxide powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder, and (B) a zinc titanate compound powder. The raw material powder may be a mixed powder of titanium oxide powder and zinc oxide powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder, or a powder containing zinc titanate compound, or may be titanium oxide powder and zinc oxide powder. A mixed powder of zinc titanate compound powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder and zinc titanate compound powder. Preferably, it is a mixed powder containing a titanium oxide powder and a zinc oxide powder or a mixed powder of a titanium oxide powder and a zinc hydroxide powder -15-201200616. As described above, for example, the oxide sintered product of the present invention can be obtained by combining titanium metal, zinc oxide powder or zinc hydroxide powder, or by combining titanium oxide and zinc metal as a raw material powder. In the oxide sintered body, metal particles of titanium or zinc are easily present. When the film is formed as a target, the metal particles on the surface of the target in the film are finally melted without being released from the target, and the resulting film is The composition is much different from the composition of the target. As the titanium oxide powder, titanium oxide (Ti〇2) composed of tetravalent titanium, titanium oxide (Ti2〇3) composed of trivalent titanium, and titanium oxide (TiO) composed of divalent titanium may be used. A powder of Ti203 was used. The reason is that the crystal structure of Ti2〇3 is trigonal, and the zinc oxide mixed therewith has a hexagonal crystal wurtzite structure, so the crystal structure has the same symmetry, and it is easy to replace solid solution during solid phase sintering. The purity of the titanium oxide powder is preferably 99% by weight or more. The low atomic valence titanium oxide is not only an integer atomic price of TiO ( II) or Ti203 ( III), but also includes Ti305, Ti407, TieOn, Ti5〇9, Ti8015, etc. by the formula Τί02·χ ( Χ = 0·1~1 ) indicates the scope. The low valence titanium oxide represented by the formula Ti02_x ( Χ = 0·1~1 ) may also be a mixture of low atomic valence titanium oxide. Usually, the atmosphere can be reduced by a hydrogen atmosphere or the like, and carbon or the like can be used as a reducing agent to produce titanium oxide (Ti〇2). By adjusting the hydrogen concentration, the amount of carbon as a reducing agent, and the heating temperature, the ratio of the mixture of low-origin titanium oxide can be controlled. The structure of the low-valent titanium oxide can be confirmed by the results of equipment analysis such as X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) -16-201200616. . As the zinc oxide powder, a powder of ZnO or the like of a wurtzite structure is usually used, and it is also possible to use a SiC which has been previously fired in a reducing atmosphere to contain oxygen. The purity of the zinc oxide powder is preferably 99% by weight or more. As the zinc hydroxide powder may be amorphous or crystalline, the zinc barium titanate compound may be a powder such as ZnTiO 3 or Zn 2 Ti 04. In particular, a powder of Zn 2 Ti 04 is preferably used. . The average particle diameter of the compound (powder) used as the raw material powder is preferably 5/zm or less, more preferably lgm or less. Further, the B ET specific surface area of the raw material powder is not particularly limited. When the mixed powder is used as the raw material powder, the mixing ratio of each powder is such that, depending on the type of the compound (powder) used, the ratio of Ti/(Zn + Ti) is determined by the atomic ratio in the finally obtained oxide sintered body. The range is suitable for setting. At this time, it is considered that the zinc phase is more likely to be volatilized than the titanium when sintered at a high vapor pressure, and it is preferable to make the amount of zinc more than the desired composition of the oxide sintered body (the atomic ratio of Ζη to Ti). The way to set the mixing ratio. Specifically, it is difficult to disperse zinc depending on the atmosphere at the time of sintering. For example, when zinc oxide powder is used, the zinc oxide powder itself is not volatilized in the atmosphere or the oxidizing atmosphere, but is sintered in a reducing atmosphere. When the zinc oxide is reduced, it is easy to become a metal zinc which is more likely to be volatilized than zinc oxide. Therefore, the amount of disappearance of zinc is increased (however, as described later, once it is sintered, it is subjected to annealing treatment in a reducing atmosphere, and the annealing treatment is already performed. It becomes a composite oxide, so zinc is not easily volatilized). Therefore, whether or not a certain amount of zinc is added to the target composition in advance can be set in consideration of a sintering atmosphere or the like. For example, if it is sintered in an atmospheric atmosphere or an oxidizing atmosphere, it is 1.0 of the required atomic ratio of -17 to 201200616. It is only about 1.05 times, and it is about 1.1 to 1.3 times of the required atomic ratio when sintering in a reducing atmosphere. The compound (powder) used as the raw material powder may be used alone or in combination of two or more. The method of forming the raw material powder is not particularly limited, and for example, if the raw material powder is mixed, the resulting mixture can be formed. The mixing can be carried out by a conventional mixing method such as a ball mill, a vibrating honing machine, an attritor, a Dino mill, or a dynamic mill. In the case of a wet type, the raw material powder is mixed with an aqueous solvent, and the obtained slurry is sufficiently mixed, and then solid-liquid separation, drying, and granulation are carried out to form the obtained granulated product. The wet mixing is preferably carried out using a wet ball mill or a vibrating honing machine using a hard Zr02 or the like, and the mixing time in the case of using a wet ball mill or a vibrating honing machine is preferably from about 12 hours to about 78 hours. Further, the raw material powder may be directly mixed by dry mixing, but it is preferably wet mixed. Solid-liquid separation, drying and granulation are preferably carried out by a method known per se. When the obtained granules are formed, for example, the granules may be poured into a mold frame, and a cold forming machine such as a cold press or a cold pressure compaction (CIP), a uniaxial press, or the like may be used to apply i ton/cm 2 . Formed by the above pressure. At this time, when a heating plate or the like is used to heat the forming, it is disadvantageous in terms of manufacturing cost, and it is difficult to obtain a large sintered product. Further, when the granulated product as the molded body is obtained, it may be granulated by a known method after drying. In this case, it is preferred to mix the binder together with the raw material powder. The binder is exemplified by a sintered body obtained by, for example, polyvinyl alcohol or vinyl acetate, in an inert atmosphere (nitrogen, argon, helium, -18-201200616 helium, etc.), vacuum, reducing atmosphere (carbon dioxide, hydrogen' In any of the atmospheres such as ammonia, atmospheric atmosphere, and oxidizing atmosphere (the atmosphere having a higher oxygen concentration than the atmosphere), it is carried out at 600 ° C to 1500 ° C. Therefore, when sintering is carried out in an atmospheric atmosphere or in an oxidizing atmosphere, it is preferred to further carry out annealing treatment in an inert atmosphere, a vacuum or a reducing atmosphere. The annealing treatment in an inert atmosphere, a vacuum or a reducing atmosphere applied after sintering in an atmospheric atmosphere or an oxidizing atmosphere is performed to reduce the specific resistance in order to generate an oxygen deficiency in the oxide sintered body. When sintering is carried out in an atmosphere, in a vacuum or in a reducing atmosphere, it is preferred to carry out an annealing treatment after sintering, when it is desired to lower the specific resistance. When sintering in any atmosphere, the sintering temperature is preferably from 600 ° C to 1 700 ° C, more preferably from 600 ° C to 1 500 ° C, more preferably from 1000 ° C to 1 500 ° C, preferably 1 000 ° C ~ 1 300 ° C. When the sintering temperature is less than 600 °C, the sintering cannot be sufficiently performed, so that the dart target density is low. On the other hand, when the temperature exceeds 1,500 °C, the zinc oxide itself decomposes and disappears. When the molded body is heated to the above-mentioned sintering temperature, the temperature increase rate is raised to 1 000 ° C at 5 t / min to 10 ° C / min, and more than 1 000 ° C to 1 500 ° C is 1 ° C / min ~ 4 The temperature rise at ° C/min is preferable on the one hand. The sintering is preferably carried out in a state in which the molded body is embedded in the body of the ΖηΟ powder to prevent decomposition, whereby the density of the obtained sintered body is preferably 80% or more, and more preferably 90%. The target composed of a high-density sintered body is used to reduce the deterioration of the film quality, that is, in the ablation plume which is likely to cause a decrease in crystallinity and surface morphology particularly in the case of the fs-PLD method. Preferably, the sintering time (i.e., the holding time at the sintering temperature) is preferably from 0.5 to 48 hours, more preferably from 3 to 15 hours. The sintering is not particularly limited, and can be carried out using an electric furnace, a gas furnace, a reduction furnace, or the like, and can be carried out by a normal pressure firing method, a hot pressing method, a hot pressure pressing (HIP) method, a discharge plasma sintering (SPS) method, or a cold average. A conventional method such as a compression press (CIP) method. The atmosphere at the time of annealing treatment is exemplified by at least one atmosphere selected from the group consisting of nitrogen, argon, helium, carbon dioxide, and hydrogen, and a vacuum. The annealing treatment can be carried out by, for example, heating at a normal pressure while introducing a non-oxidizing gas such as nitrogen, argon, helium, carbon dioxide or hydrogen, or heating under vacuum (preferably 2 Pa or less). However, in terms of manufacturing cost, the former method of performing at atmospheric pressure is advantageous. The annealing temperature (heating temperature) is preferably from 1000 ° C to 1400 ° C, more preferably from 1 100 ° C to 1 300 ° C. The annealing time (heating time) is preferably from 7 hours to 15 hours, more preferably from 8 hours to 12 hours. When the annealing temperature is less than 1 000 °C, there is a shortage of oxygen deficiency introduced by annealing. On the other hand, when it exceeds 1 400 °C, zinc is easily volatilized, and the composition of the obtained oxide sintered material (the atomic ratio of Zn to Ti) is different from the desired ratio. (Oxide Mixture) The oxide mixture of the present invention is composed of zinc oxide and titanium oxide. That is, the oxide mixture of the present invention is substantially a mixture of zinc, titanium and oxygen. Here, "substantially" means that 99% or more of all atoms constituting the oxide mixture are composed of zinc, titanium or oxygen. -20- 201200616 The ratio of the atomic ratio of titanium to the total of zinc and titanium in the oxide mixture of the present invention exceeds 0.02 and is 0.1 or less. When the enthalpy of Ti/(Zn + Ti ) is 0.02 or less, the chemical durability such as chemical resistance of the film formed using the oxide mixture as a target is insufficient. Preferably, the atomic number is Ti/( Zn + Ti ) =0·025~0·09 ', preferably Ti/( Zn + Ti ) = 0.03 〜0·09, and more preferably Ti/( Zn + Ti ) = 0.03 - 0.08 > Preferably, Ti / ( Zn + Ti ) = 0.04 to 0.08. As the titanium oxide, the above titanium oxide powder can be used. Zinc oxide usually has a wurtzite structure. The oxide mixture of the present invention is obtained by mixing a zinc oxide powder with a titanium oxide powder, and molding it by, for example, molding with a uniaxial pressing machine. In order to increase the mechanical strength of the oxide mixture, the shaped oxide mixture may also be heated up to 600 °C. When the zinc oxide and the titanium oxide are less than 60 (TC, the composite oxide or the like cannot be sintered. The titanium oxide (III) is heated in an atmosphere of oxygen (air atmosphere and oxidizing atmosphere), and is heated to 400 ° C or higher and oxidized. It is converted into titanium oxide (IV). However, in the absence of a reducing atmosphere of oxygen and an inert atmosphere, if the heating temperature is less than 600 ° C, the unsintered mixture may be present. If it is an oxygen atmosphere (oxidizing atmosphere and atmosphere) The atmosphere is preferably heated at less than 400 ° C. By such heating, the mechanical strength of the oxide mixture can be increased. Since the strength of the mixture itself is increased, even in an excessively harsh condition such as being a target (high power) The oxide film of the present invention may also contain the above-mentioned additive element or impurity. The content of the additive element or the impurity is as described above. -21 - 201200616 (Manufacturing method of oxide mixture) The present invention The oxide mixture is produced by mixing a powder of titanium oxide powder and zinc oxide powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder. The method for obtaining the above oxide mixture of the present invention. The raw material powder is preferably a mixed powder of titanium oxide powder and zinc oxide powder, or a mixed powder of oxidized powder and cerium oxide powder, preferably containing titanium oxide powder and zinc oxide. a mixed powder of powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder. The titanium oxide powder, zinc oxide powder or zinc hydroxide powder may be the same as the above oxide sintered product. The mixing ratio of the powder of the zinc powder or the mixed powder of the titanium oxide powder and the zinc hydroxide powder as the raw material powder is preferably based on the type of the compound (powder) used separately, so that the finally obtained oxide mixture is The method of forming the raw material powder is not particularly limited, and the method of forming the raw material powder is not particularly limited, and it can be carried out, for example, in the same manner as the above oxide sintered product. The body is heated and annealed in order to improve the mechanical strength. The annealing is performed by an atmospheric pressure annealing method. It is carried out by a conventional method such as a pressing method, a HIP method, an SPS method, or a CIP method, for example, in an atmosphere such as an atmosphere, an inert atmosphere, a vacuum, or a reducing atmosphere (for example, nitrogen, argon, helium, carbon dioxide, vacuum (preferably In any of the atmospheres of 2 kPa or less, hydrogen, etc., or an oxidizing atmosphere (the atmosphere having a higher oxygen concentration than the atmosphere), it is carried out at 50 ° C or higher and less than 600 ° C. Therefore, when annealing in an oxidizing atmosphere or an atmosphere , should be carried out below 4 〇 0 ° C. Because TiO, Ti203 will eventually oxidize to -22- 201200616

Ti〇2 is the reason. When Ti 2 is used as the titanium oxide, any of the above atmospheres may be used if it is less than 600 °C. Moreover, in terms of manufacturing cost, it is advantageous to anneal at a normal pressure. By annealing, the mechanical strength of the mixed body can be improved. When annealing in any atmosphere, the annealing time (i.e., the holding time at the annealing temperature) is also preferably from 1 hour to 15 hours. When the annealing time is less than 1 hour, the improvement in mechanical strength is insufficient. (Target) The target of the present invention is a target for film formation by, for example, pulsed laser deposition (PLD method), sputtering, ion plating, or electron beam (EB) evaporation. Further, the solid material used in the film formation may be referred to as "tablet", but the present invention includes such a "target". Further, it may be formed by a general film formation method such as a vacuum deposition method, a vacuum deposition method, a chemical vapor phase growth method, a mist CVD method or a melt gel method. The target of the present invention is to process the above-described oxide sinter or oxide mixture of the present invention into a specific shape and a specific size. The processing method is not particularly limited to the use of a suitable conventional method. For example, the oxide sinter or oxide mixture may be subjected to planar dicing, cut to a specific size, and attached to a support table, thereby obtaining the target of the present invention. Further, a plurality of oxide sinter or oxide mixtures may be arranged in a divided shape as needed, and may be used as a large-area target (composite target). (Pulse Laser Stacking Method (PLD Method)) -23-201200616 The method for forming a zinc oxide-based transparent conductive film of the present invention can be carried out by a PLD method. The specific method, conditions, and the like are not particularly limited except for the use of the above-mentioned target (film forming material), and it is preferred to use a conventional method or condition. The following swords · Explain the PLD method, but it is not limited to these. The PLD method collects a pulsed laser beam on a film forming material such as a target, and burns a film forming material (a mixture of titanium oxide and zinc oxide) on the surface of the target by the high energy density of the collected laser pulse. Etching, forming a plasma, which is deposited on the surface of the substrate. At this time, both the target and the substrate are placed in a high vacuum chamber, and the action is controlled by a feedthrough mechanism. The pulse laser source most widely used by the PLD method is a pseudo-electron laser. Excimer lasers have a pulse width of a few nanoseconds (ns) and a wavelength in the UV region. Its typical flux (energy range density) is a few J/cm2 for a typical 10 mm2 spot. However, the nanosecond laser PLD method produces large droplets of several micrometers in size, and is therefore unsuitable for industrial use of nanosecond PLDs. Therefore, as the ablation energy source (pulsed laser source) used in the PLD method, a femtosecond laser or the like ultrashort pulse laser is preferably used. Compared to nanosecond laser pulses, the femtosecond picosecond laser pulse has a very high peak energy due to its ultra-short pulse width, and the nature of the ablation mechanism and nanosecond laser ablator Different on. The basic difference is in the femtosecond pulse width, since abundance of heat conduction is only caused inside the target, ablation occurs substantially in a non-melting condition. Therefore, when the femtosecond PLD method (fs-PLD method) is used, it is preferable to obtain a film without generating droplets. -24- 201200616 When using the femtosecond PLD method to form a film, the pulse width of the laser beam used in the femtosecond pulse laser is usually set to l〇fs~lps, and the pulse energy is usually set to 2 M J to 10OmJ. Initially, the beam was magnified 10 times with a microscope, and then concentrated on the target surface with a collecting lens. By collecting it by shrinking it, the flux (energy density) in the collection spot can be changed to a maximum of 250 J/cm2 in a spot size of 400 μm 2 . Due to the extremely high frontal energy of ultrashort pulses (>5xl06W), the ablation critical enthalpy of the film-forming material (Ti-containing ΖηΟ) using femtosecond laser is lower than that of the nanosecond pulsed laser. Since the ΖηΟ target containing Ti is ablated to form ablated plasma, it is sufficient if the flux is higher than lJ/cm2. However, in order to reduce the number of particles in the plasma soot, it is preferably a high flux of at most 5 J/cm2. Laser deposition on a transparent substrate using a device equipped with a pulsed laser source, a substrate transparent to the wavelength of the pulsed laser, a continuous wave (CW) infrared laser that is irradiated onto the substrate, and a multi-target system A transparent film that can directly stack multiple layers of periodic construction. For example, when a pulsed laser is incident from the back surface of the substrate and is collected on the target through the substrate, the film forming material ablated from the target adheres to the surface of the substrate opposite to the target. Moving the target in parallel can change the distance from the substrate to the target. If the substrate is farther from the target, a large area film can be formed. If the substrate is very close to the target, when the distance between the substrate/target is short, the film can be formed on the substrate to the same size as the laser spot by the narrow angle distribution of the ablation smoke in the base. Subtle patterns. If the substrate moves in the horizontal direction, a pattern structure (for example, periodic lines, grids, dots) can be formed. If the long distance and short distance between the substrate/target are used, and different materials are used, and the two film forming processes are carried out, the multilayer dielectric structure can be formed. The substrate is mounted on a substrate heater that can be heated up to 900 °C. Therefore, the substrate manipulator imparts a lateral direction and a rotating motion to the surface of the substrate, and the substrate robot can adjust the distance between the substrate and the target. Further, the vacuum system was operated by vacuum evacuation with a vortex molecular pump at a base pressure of 1.5 x 10 0.8 Torr. During the growth of the membrane, other gases may be charged into the chamber from the suction port and the exhaust port, for example, an oxygen charging chamber of 0.1 to 20 mTorr. Laser ablation occurs when the laser beam is concentrated on the target surface. During the growth of the film, the laser spot is fixed at one side, and the target of the dish rotates around the vertical axis of the surface, and travels along the surface in the lateral direction to move in parallel. It is equivalent to a laser beam scan over the surface of the target. At this time, the angular velocity of rotation is usually about 1 second. The parallel movement in the horizontal direction is usually about mm3mm/sec, and the flux is usually around 20J/cm_2. The repetition pulse keeps the frequency at 1 kHz. Before the laser beam is collected on the surface of the target, it is preferred to heat the substrate to a maximum of 600 ° C to release the gas, and then treat the substrate with oxygen plasma for about 5 minutes, thereby removing impurities from the substrate by using hydrocarbons. Further, pre-ablative (pre-ablation) of the target surface is preferably performed for about 20 minutes before the laser beam is collected on the surface of the target. The purpose of pre-ablative is to clean the target surface of the contamination during the manufacturing process. The pre-ablation is performed by inserting a baffle between the target and the substrate to protect the surface of the substrate. (Sputtering method) -26-201200616 The method for forming a zinc oxide-based transparent conductive film of the present invention can be carried out by sputtering, and the film forming material is not particularly limited except for the specific method and conditions. The method and conditions of the sputtering method can be used. Film formation by sputtering can be performed by, for example, placing a target in a sputtering apparatus to introduce a sputtering gas into the apparatus, and applying a direct current (dc) or a high frequency (rf) or an electric field of both to perform sputtering. A thin film is formed on the substrate. As for the sputtering gas, an inert gas (e.g., Ar or the like) having a concentration of 99.995 % or more is usually used. Oxidizing gases or reducing gases may also be used as needed. Preferably, however, it is substantially free of oxygen, and the oxygen concentration is preferably, for example, less than 0.05%. The film formation conditions by the sputtering method are not particularly limited, but can be carried out, for example, at a pressure of usually 0.1 to 10 Pa and a substrate temperature of usually 25 to 300 °C. The sputtering method is not particularly limited, and may be based on the specific resistance of the target used, such as, for example, DC sputtering (DC sputtering), RF sputtering (high-frequency sputtering), AC sputtering (AC) Sputtering) or a combination of these methods is suitably employed. For example, the DC sputtering method has a faster film formation speed and superior sputtering efficiency than other methods, and the DC sputtering apparatus has the advantages of being inexpensive, easy to control, and having low power consumption. However, these methods cannot be used when the target is an insulator. In contrast, RF sputtering can also be used when the target is an insulator. (Ion Plating Method) Further, the method for forming a zinc oxide-based transparent conductive film of the present invention can be carried out by ion plating. In the ion plating method, a film forming material (vaporized ammonium material) -27-201200616 is disposed on an earth or the like as an electrode portion disposed in a film forming chamber, and the vapor deposition material is irradiated with, for example, argon plasma for heating. A method of depositing a material and evaporating a film formed by depositing particles of the vapor-deposited material of the plasma on a substrate disposed at a position opposite to the ground. The specific method or condition of the ion plating method is not particularly limited, except for the use of the above-mentioned film forming material, and the method and conditions of the conventional ion plating method may be suitably employed. Hereinafter, an embodiment of the ion plating method will be described with reference to the drawings. Fig. 1 is a view showing an example of a preferred ion plating apparatus for performing ion plating. The ion plating apparatus 10 includes a vacuum vessel 12 having a film forming chamber, a plasma gun (plasma beam generator) 14 that supplies a plasma source of the plasma beam PB in the vacuum vessel 12, and is disposed at the bottom of the vacuum vessel 12. The anode member 16 to which the plasma beam PB is incident and the transport mechanism 18 for appropriately moving the holding member WH of the substrate W for holding the film formation above the anode member 16 are provided. The plasma gun 14 is of a pressure gradient type, and its body portion is provided on the side wall of the vacuum vessel 12. The intensity or distribution state of the plasma bundle PB supplied to the vacuum vessel 12 is controlled by adjusting the power supply to the cathode 14a, the intermediate electrodes 14b, 14c, the electromagnetic coil 14d, and the steering coil Me of the plasma torch 14. . Further, reference numeral 20a denotes an introduction path of a carrier gas composed of an inert gas such as Ar which becomes a plasma beam PB. The anode member 16 is composed of a ground line 16a that is introduced into the main anode of the plasma beam PB and a ring-shaped auxiliary anode 16b disposed around the anode.

The ground line 16a is controlled to a proper positive potential, and the plasma beam PB emitted from the plasma gun 14 is attracted downward. The ground line 16a is formed with a through hole TH at a central portion of the incident plasma beam PB, and the vapor deposition material 22 is mounted in the through hole TH -28-201200616. The vapor deposition material 22 is an ingot formed into a columnar shape or a rod shape, and is heated and sublimated by a current from the plasma beam PB to form a vapor deposition material. The ground wire 16a has a structure in which the vapor deposition material 22 is gradually raised, and the upper end of the vapor deposition material 22 often protrudes only from the through hole TH of the ground wire 16a by a certain amount. The auxiliary anode 16b is constituted by an annular container which is disposed concentrically around the ground line 16a, and the inside of the container houses the permanent magnet 24a and the coil 24b. The permanent magnet 24a and the coil 24b are magnetic field control members, and a cusp-shaped magnetic field is formed directly above the ground line 16a, thereby controlling the direction of the plasma beam PB incident on the ground line 16a and correcting it. The transport mechanism 18 includes a plurality of rollers 18b that support the substrate holding member WH arranged at equal intervals in the horizontal direction in the transport path 18a, and a non-image in which the substrate holding member WH is moved in the horizontal direction at a specific speed by rotating the roller 18b. The drive device shown. Holding the substrate in the substrate holding member WH» In this case, the substrate W may be fixedly disposed above the inside of the vacuum container 12 without providing the transfer mechanism 18 for transporting the substrate W. In the vacuum vessel 12, the oxygen in the oxygen container 19 is supplied by adjusting the flow rate to a specific amount by the mass flow meter 21. Further, reference numeral 2〇b denotes a supply path for supplying an atmosphere gas other than oxygen, and reference numeral 20c denotes a supply path for supplying an inert gas such as Ar to the ground line 16a, and further, reference numeral 20d It is the exhaust system. The ion plating method will be described using the ion plating apparatus 1 of Fig. 1. First, the vapor deposition material 22 is attached to the through hole TH of the ground wire 16a disposed under the vacuum vessel 12. On the other hand, the substrate W is disposed at an opposite position above the ground line 16a. Next, the process gas was introduced into the inside of the vacuum vessel 12 of -29-201200616 according to the film formation conditions. A DC voltage is applied between the cathode 14a of the plasma gun 14 and the ground line 16a. Therefore, a discharge is generated between the cathode 14a of the plasma gun 14 and the ground line 16a, whereby the plasma beam PB is generated. The plasma beam PB is guided to the ground line 16a which is determined by the control coil 14 and the permanent magnet 24a in the auxiliary anode 16b. At this time, since argon gas is supplied around the vapor deposition material 22, the plasma bundle PB can be easily attracted to the ground line. 16 a 〇 The vapor deposition material 22 exposed to the plasma is slowly heated. When the vapor deposition material 22 is sufficiently heated, the vapor deposition material 22 is sublimated, and the vapor deposition material is evaporated (emitted). The vapor deposition material is ionized by the plasma beam PB, adhered (incident) to the substrate W, and formed into a film. Further, by controlling the magnetic field above the ground line 16a by the permanent magnet 24a and the coil 24b, the flying direction of the vapor deposition material can be controlled, so that the plasma activity distribution above the ground line 16a and the reactivity distribution of the substrate W can be matched. By adjusting the film formation rate distribution on the substrate W, it is possible to obtain a film having a uniform film quality over a wide area. The oxygen partial pressure of the vacuum vessel 12 is not particularly limited, but is preferably adjusted to 0.012 Pa or less. Further, a plurality of plasma bundles may be prepared as needed, and film formation may be continuously performed in a plurality of divided vacuum chambers. Method of plating Niy B E /IV beam tpr ✓fv The method for forming a zinc oxide-based transparent conductive film of the present invention may be an electron beam (EB) vapor deposition method. The specific methods and conditions, etc., are not particularly limited except for the use of the above-mentioned film-forming material, and the conventional electron beam (EB) steaming method may be used. Electron beam (EB) vapor deposition method -30-201200616 The electron beam can be evaporated onto a raw material target (ingot) by vacuum evaporation in a vacuum to deposit it on the opposite transparent substrate. A transparent conductive film is formed on the transparent substrate. (Zinc oxide-based transparent conductive film) The zinc oxide-based transparent conductive film of the present invention is a transparent conductive film made of titanium-doped zinc oxide formed by the above-described method for forming a zinc oxide-based transparent conductive film. The atomic ratio of titanium to zinc (Ti/(Zn + Ti )) contained in the zinc oxide-based transparent conductive film of the present invention is as described above. According to this, the excellent doping effect is exhibited by the doping effect of titanium, and the film is excellent in chemical durability. In the zinc oxide-based transparent conductive film, the zinc oxide-based transparent conductive film of the present invention has excellent transparency and has excellent properties as described above. Conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (alkaline resistance, acid resistance), etc.). In particular, the zinc oxide-based transparent conductive film of the present invention improves the past zinc oxide-based transparent conductive film (i.e., does not contain the titanium oxide of a specific amount as in the present invention) without impairing transparency and conductivity. Chemical durability of the biggest disadvantage of zinc-based transparent conductive film). Specifically, the conventional zinc oxide-based transparent conductive film is related to the film thickness, but when the heat resistance is heated in an atmosphere of 200 t for 30 minutes, the specific resistance is rapidly increased, and the moisture resistance is maintained. In a constant temperature and humidity environment (temperature 60 ° C, relative humidity 90%), the specific resistance is increased by about 1 time in 10 hours, and it will eventually become an insulator when it is kept for 1000 hours. Further, the chemical resistance of the conventional zinc oxide-based transparent conductive film is completely lost after, for example, immersion in a 3% aqueous solution of hydrochloric acid at -40 - 201200616 at 40 ° C or a 3% sodium hydroxide solution at 40 ° C for a minute. The film thickness of the zinc oxide-based transparent conductive film of the present invention is not particularly limited as long as it is appropriately set depending on the use, but is preferably from 50 nm to 600 nm, more preferably from 10 nm to 500 nm. When it is less than 50 nm, it is impossible to ensure a sufficient specific impedance. On the other hand, when it exceeds 600 nm, the film may be discolored. (Transparent Conductive Substrate) The transparent conductive substrate of the present invention is those having the above-described zinc oxide-based transparent conductive film on a transparent substrate. The transparent substrate is not particularly limited as long as it can maintain its shape in various film forming methods. For example, an inorganic material such as various glasses, a thermoplastic resin, or a thermosetting resin (for example, epoxy resin, polymethyl methacrylate, polycarbonate, polystyrene, polyethyl sulfide, polyether maple, poly a plate, a sheet, or a film formed of a resin such as an olefin, a polyethylene terephthalate, a polyethylene naphthalate, a triethylene phthalate or a plastic such as a polyimide. The material is preferably a glass plate, a resin film or a resin sheet. The visible light transmittance of the transparent substrate is usually 90% or more, preferably 95% or more. When a resin film or a resin sheet is used as the transparent substrate, in order to uniformize the damage to be absorbed in the film formation, it is preferred to carry out the roll-to-roll film formation method which is industrially performed, while controlling the unwinding speed and the take-up speed. Film formation is performed in a state where tensile stress is applied. Further, the resin film or the resin sheet may be preliminarily formed to form a film, and the resin film or the resin sheet may be cooled during the film formation. In addition, it is effective to shorten the time during which damage is caused in the film formation, and it is also effective to increase the transport speed of the resin film or the resin sheet (for example, 〇m/min or more), in which case, for example, the film-forming resin is shortened. The distance between the film or the resin sheet and the target can also be formed into a film, which is advantageous as an industrial process. The transparent substrate may also be formed of any one of a single layer or a plurality of layers of an insulating layer, a semiconductor layer, a gas barrier layer or a protective layer. The insulating layer is exemplified by a ruthenium oxide film or a tantalum nitride film. The semiconductor layer is exemplified as a thin film transistor (TFT) or the like, and is mainly formed on a glass substrate. The gas barrier layer is exemplified by a ruthenium oxide film, a ruthenium nitride film, a magnesium aluminate film, or the like, and is formed on a resin plate or a resin film as a water vapor barrier film or the like. The protective layer is exemplified by various coating layers such as Si-based, Ti-based, and acryl-based resins in order to protect the surface of the substrate from damage or impact. The specific resistance of the zinc oxide-based transparent conductive substrate of the present invention is usually 2 x 1 (T3 Q*cm or less, preferably 1 x 10 〇 4 Q.cm or less, more preferably 8 x 10 _ 4 Ω · cm or less. (Sheet resistance) varies depending on the application, but is usually 5 to 1 0000 Ω/□, preferably 5 to 300 Ω/Ο, more preferably 10 to 3 Ω Ω/□. Further, the specific resistance and surface resistance can be The transmittance of the zinc oxide-based transparent conductive substrate of the present invention is usually 85% or more, preferably 90% or more in the visible light region. Further, the total light transmittance is good. It is 80% or more, more preferably 85% or more, and the turbidity 値 is preferably 10% or less, more preferably 5% or less. Further, the transmittance can be measured by, for example, a method described later in the examples. The conductive substrate may be laminated with one or two layers, such as a protective film, an anti-reflection film, a filter, or the like, or a resin or inorganic compound layer that functions to adjust the viewing angle of the liquid crystal and anti-fog, as in the case of -33-201200616. The outermost layer. (Zinc oxide-based transparent conductive film forming material) The zinc oxide-based transparent conductive film forming material of the invention is such that the atomic ratio of Ti to (Zn + Ti) exceeds 〇.〇2 and is less than or equal to 1 in the total of titanium to zinc and is based on zinc oxide as a main component. Further, it is composed of an oxide mixture of at least one of gallium and aluminum and an oxide mixture of titanium oxide or an oxide sintered product. When the atomic ratio is 0.02 or less, chemical resistance of a film formed using the material as a target is obtained. On the other hand, when the atomic ratio exceeds 〇·1, titanium cannot be sufficiently replaced by the solid solution in the zinc position, and the film formed using the material as a target has a decrease in conductivity or transparency. The preferred number of atoms is Ti / ( Zn + Ti ) = 0.025-0.09 &gt; more preferably Ti / ( Zn + Ti ) = 0.03 - 0.09 &gt; and more preferably Ti / ( Zn + Ti ) = 0.03 -0.08 , preferably Ti / ( Zn + Ti ) = 0.04 to 0.08 〇 Further, the ratio of the number of atoms of gallium or aluminum is 0.5% or more and 6% or less with respect to the number of atoms of all metals. The number of atoms of gallium or aluminum When the ratio is less than 0.5%, the effect of improving the conductivity becomes insufficient. On the other hand, when it exceeds 6%, Gallium or aluminum cannot be replaced by solid solution in the zinc position', which precipitates at the grain boundary, resulting in a decrease in conductivity and a decrease in transmittance. Also, it is possible to use both A1 and Ga. In this case, the total amount of the above is satisfied as long as the above is satisfied. The conditions of 0.5% or more and 6% or less may be used. The method for producing the oxide mixture or the oxide-34-201200616 is not the raw material powder, except that a mixed powder of further added alumina powder or gallium oxide powder is used. The remainder is the same as the method of manufacturing the oxide mixture or oxide sinter described above. Further, the atomic ratio of gallium or aluminum is 0.5% or more and 6% or less with respect to the total number of atoms of the metal. When the atomic ratio of gallium or aluminum is less than 0.5%, the effect of improving conductivity is insufficient. On the other hand, when it exceeds 6%, gallium or aluminum cannot be substituted and solidified at the zinc site, and precipitates at the crystal grain boundary, resulting in a decrease in conductivity and a decrease in transmittance. Also, it is no problem to use both A1 and Ga. In this case, the total amount of these may be satisfied by satisfying the above conditions of 1% or more and 6% or less. The oxide mixture or the oxide sintered product is a mixed zinc oxide powder, a titanium oxide powder and an alumina powder, or a mixed zinc oxide powder, a titanium oxide powder and a gallium oxide powder, and is subjected to press molding. The titanium oxide powder is preferably trivalent titanium oxide (III) or divalent titanium oxide (II) as described above. Further, the crystal phase of titanium oxide is specifically Ti203 (III) or TiO (II). The zinc oxide-based transparent conductive film forming material of the present invention may contain the above-mentioned additive elements (except for gallium and aluminum) or impurities. The content of the added element or impurity is as described above. In particular, by including an additive element, the specific resistance of the formed transparent conductive film is lowered, whereby conductivity can be improved. When the content of the additive element exceeds 0.05%, the film formed of the obtained zinc oxide-based transparent conductive film forming material may have a higher specific resistance. Further, the additive element may be present in the oxide mixture or the oxide sinter in the form of an oxide, or may be replaced (cured) in the form of a zinc site of the zinc oxide phase, or may be replaced (solidified). The oxide sintered body of the zinc oxide-based transparent conductive film forming material of the present invention preferably has a relative density of 93% or more, more preferably 95% to 100%. Relative density. Here, the relative density is defined as the fact that when the oxide sintered body is divided by the theoretical density and multiplied by 100, the relative density is less than 93%, the film forming speed acceleration characteristic of the sintered product is impaired. The oxide mixture and the oxide sintered body are not particularly limited and can be produced, for example, by the above method. The zinc oxide-based transparent conductive film forming material of the present invention can be processed into a target used for film formation by, for example, a sputtering method, an ion plating method, a pulsed laser deposition method (PLD method), or an electron beam (EB) evaporation method. . Using the processed target, for example, a zinc oxide-based transparent conductive film can be formed, and a transparent conductive substrate can be obtained by forming the conductive film on a transparent substrate. (Drawing method) The patterning method of the present invention is patterned by acid etching a zinc oxide-based film as described above. The etching liquid which can be used in the present invention is not particularly limited as long as it is an acid-containing one. For example, an etching liquid used for patterning a conventional transparent conductive film such as an ITO film can be used. Specific examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrogen halide acid (for example, hydrocyanic acid or hydrocyanic acid), and the like (for example, aqua regia), or oxalic acid or acetic acid. An organic acid such as formic acid, propionic acid, succinic acid, malonic acid, butyric acid or citric acid, which is usually used as a (water) solution dissolved in a suitable solvent, -36-201200616 Can be used directly. Further, various salts such as ammonium sulfate and iron dichloride may be dissolved in the etching solution. The etching liquid may be used singly or in combination of two or more. The concentration of the etching liquid is not particularly limited, and may be a desired etching rate, and may be appropriately set depending on the liquid temperature of the etching liquid or the degree of hardening of the film. The liquid temperature of the etching liquid is preferably from 10 ° C to 150 ° C, more preferably from 20 ° C to 1 〇 (TC. When the liquid temperature of the etching liquid is less than 10 ° C, there may be no etching, another On the other hand, when the temperature exceeds 150 ° C, the solvent such as water is easily volatilized, and the concentration management of the etching liquid becomes difficult. The treatment method for etching using the etching liquid is not particularly limited, and is, for example, on the zinc oxide-based film. Forming a photoresist film having a desired pattern, using an etching solution to remove a portion not covered by the photoresist film, that is, a portion exposed from the photoresist film, and then, by using a suitable solvent (for example, methylcellulose The resin or the like is peeled off and the photoresist film is removed to form a desired pattern. The specific method and conditions for forming or removing the photoresist film and removing the exposed portion by the etching liquid are not particularly limited, and for example, according to IT The method and conditions for the wet etching treatment used in the conventional transparent conductive film such as the film 0 may be appropriately performed. The film patterned by the present invention is highly conductive, for example, by forming the foregoing on the transparent substrate. Zinc oxide film The specific resistance of the transparent conductive substrate obtained by patterning is usually 2x1 0·3 Ω · cm or less, preferably 1 χ 10 _ 3 Ω · cm or less, more preferably 8 χ 10 · 4 Ω · cm or less, and 'the surface resistance (sheet resistance) Depending on the application, it is usually from 5 to 1 0000 Ω/□, preferably from 10 to 30,000 Ω/Ο. -37- 201200616 The patterned film according to the present invention is generally excellent in transparency, for example, The transmittance of the transparent conductive substrate obtained by forming the zinc oxide-based thin film on the transparent substrate in the visible light region is usually 85% or more, preferably 90% or more. Further, the total light transmittance is good. It is 80% or more, more preferably 85% or more, and its turbidity 値 is preferably 10% or less, more preferably 5% or less. It is formed by using the oxide sinter or oxide mixture of the present invention or the target of the present invention. The transparent conductive film is suitable for, for example, a liquid crystal display or a plasma display because it has excellent electrical conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (alkaline resistance, acid resistance), etc.). Inorganic EL (electroluminescence) display, Transparent EL electrodes, transparent electrodes such as electronic paper, window electrodes of photoelectric conversion elements of solar cells, electrodes of input devices such as transparent touch panels, electromagnetic shielding films such as electromagnetic shielding, etc. Further, oxidation using the present invention The transparent conductive film formed of the material sinter or the oxide mixture or the target of the present invention may be used in combination with a transparent electromagnetic wave absorber, an ultraviolet absorber, and further with another metal film or a metal oxide film as a transparent semiconductor device. Since the patterned film according to the present invention can sufficiently control the etching rate, the pattern shape can be accurately formed. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. The limit. -38-201200616 <Specific resistance> The specific resistance was measured using a four-terminal four-probe method using a resistivity meter ("LORESTA-GP ' MCP-T610" manufactured by Mitsubishi Chemical Corporation). In detail, the four needle electrodes are placed on the sample in a straight line, flow through the outer two probes with a certain current, and a certain current flows between the inner two probes, and the potential difference generated between the inner two probes is measured. Find the resistance. <Surface Resistance> The surface resistance (Ω/Cl) was calculated by dividing the specific resistance (Ω · cm ) by the film thickness (cm). <Transmittance> .. The transmittance was measured using an ultraviolet-visible near-infrared spectrophotometer ("V-670" manufactured by 分本分光(股)). <Moisture resistance> The surface of the transparent conductive substrate was measured by maintaining the moisture resistance test for 1 000 hours in an atmosphere of a temperature of 60 ° C and a relative humidity of 90%. When the surface resistance after the moisture resistance test is less than twice the surface resistance before the moisture resistance test, it is said to be excellent in moisture resistance. <Heat resistance> The transparent conductive substrate was kept in the atmosphere at a temperature of 200 ° C for 5 hours. After the heat resistance test, the surface resistance was measured. Surface resistance after heat resistance test -39 - 201200616 When it is 1.5 times or less of the surface resistance before the heat resistance test, it is called heat resistance. <Alkali resistance> The transparent conductive substrate was immersed in a 3% NaOH aqueous solution (40 t) for 1 minute to visually confirm the change in the film quality on the substrate before and after the immersion. (Example 1) <Production of oxide mixture> Zinc oxide powder (ZnO powder; purity 99.9%, average particle diameter 1 / zm or less, manufactured by Wako Pure Chemical Industries Co., Ltd.) and titanium oxide powder (Ti203 powder; purity 99.9%, average particle diameter 1/zm or less, high purity) As a raw material powder, these are added to a resin crucible at a ratio of atomic ratio of Zn:Ti to 94:6, and wet-mixed by a wet ball milling method. The wet mixing system was carried out using a hard Zr02 ball as a ball and a mixing time of 18 hours. Then, the mixed raw material powder slurry was taken out, dried, granulated, and then formed by a cold pressure equalizing press at a pressure of 1 ton/cm 2 to obtain a disk-shaped formed body having a diameter of 10 mm and a thickness of 8 mm. . Next, the obtained molded body was placed in an air atmosphere and kept at 300 ° C for 1 hour to carry out annealing treatment to obtain an oxide mixture (1 ) 〇 an energy dispersive fluorescent X-ray device (Shimadzu Corporation) 40- 201200616 "EDX-700L" manufactured by the analysis of the oxidation mixture (1), the atomic ratio of Zn to Ti is Zn: Ti = 94 : 6 (Ti / ( Zn + Ti ) = 0.06 ). The crystal structure of the oxide mixture (1) was investigated by an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and it was a mixture of a crystal phase of zinc oxide (ZnO) and titanium oxide (Ti203). Next, the obtained oxide mixture (1) was processed into a disk shape of 50 mmcf) to obtain a target for sputtering, and a transparent conductive film was formed by sputtering using the target to prepare a transparent conductive substrate. In other words, the sputtering target and the film formation substrate (quartz glass substrate) are placed in a sputtering apparatus ("E - 200" manufactured by Canon-Anelva Co., Ltd.), and introduced at 12 sc cm. A r gas (purity: 99.9995% or more, Ar pure gas = 5 N) was sputtered under the conditions of a pressure of 0.5 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. For the composition (Zn:Ti) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the measurement was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn: Ti (atomic ratio) = 94: 6. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in.

The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8×41 - 201200616 ΙΟ·4 Ω·cm, and the surface resistance was 1 1.6 Ω/□. Further, the specific resistance distribution on the transparent conductive substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance in the visible light region (380 nm to 78 0 nm) of the quartz glass substrate before film formation was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated. The surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality before and after the immersion was not changed. It was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 2) <Production of oxide mixture> Zinc oxide powder (ZnO powder; purity 99.9%, average particle diameter 1 -42 - 201200616 / zm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide powder ( 1 ^ 203 powder; purity 99.9% 'average particle diameter 1 / zm or less, manufactured by High Purity Chemical Research Institute (stock)) as a raw material powder, so that the atomic ratio of Zn : T i becomes 9 5 : 5 The ratio was added to a resin crucible, and wet mixing was carried out by a wet ball milling mixing method. The wet mixing was carried out using a hard Z r Ο 2 ball as a ball' mixing time of 18 hours. Then, the mixed raw material powder slurry was taken out, dried, granulated, and then subjected to a pressure of Hon/cm 2 by a cold pressure press to form a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. Next, the obtained molded body was placed in an inert gas atmosphere (100% Ar atmosphere) and kept at 500 ° C for 1 hour to carry out annealing treatment to obtain an oxide mixture (2). The oxidation mixture (2) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn: Ti = 95 : 5 ( Ti / ( Zn + Ti ) = 0.05 ). The crystal structure of the oxide mixture (2) was investigated by an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and it was a mixture of a crystal phase of zinc oxide (ZnO) and titanium oxide (Ti203). Next, the obtained oxide mixture (2) was processed into a disk shape of 5 0 ηηηηΦ to obtain a target for sputtering, and the target was used to form a transparent conductive film having a film thickness of 500 nm by sputtering as in Example 1. A film is used to form a transparent conductive substrate. The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed by a fluorescent X-ray method using a calibration curve as in Example 1 - 43 - 201200616, which is Zn : Ti (atomic ratio) = 95 : 5. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and crystal structure of titanium to zinc were investigated, and the single phase of the wurtzite type which is aligned with the C-axis was observed. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.9 x 1 (Γ4 Ω·cm, and the surface resistance was 9.8 Ω/□. Further, the specific resistance distribution on the transparent conductive substrate was in-plane uniform. The transmittance of the conductive substrate is 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation is in the visible light region. The infrared ray region was the same as in Example 1. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality before and after the immersion was evaluated. There is no change, and it is known that the alkali resistance is excellent. Further, the acid resistance of the obtained transparent conductive substrate is evaluated, and the film thickness after thinning is reduced and dissolved, but the film quality before and after the immersion is not From the above, it can be seen that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has transparent electrical conductivity (heat resistance, moisture resistance, alkali resistance, acid resistance). Membrane - 44 - 201200616 (Comparative Example 1) <Production of oxide mixture> Zinc oxide powder (ZnO powder; purity: 99.9%, average particle diameter: 1 /zm or less, manufactured by Wako Pure Chemical Industries, Ltd.) and titanium oxide Powder (1^203 powder; purity 99.9%, average particle diameter 1 from 111 or less, manufactured by High Purity Chemical Research Institute), as a raw material powder, such that the atomic ratio of Zn:Ti becomes 99:1 The ratio was added to a resin crucible, and wet mixing was carried out by a wet ball milling mixing method. The wet mixing was carried out using a hard Zr02 sphere as a ball, and the mixing time was 18 hours. Next, the mixed raw material powder slurry was taken out. After drying, granulation was carried out by a cold pressure press, and a pressure of lton/cm 2 was applied to obtain a disk-shaped formed body having a diameter of 100 mm and a thickness of 8 mm. Next, the obtained shaped body was placed in an inert atmosphere (100%). Ar atmosphere) Annealing treatment was carried out at 500 ° C for 1 hour to obtain an oxide mixture (C 1 ). The resulting oxidation mixture was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). (Cl ) , the atomic ratio of Zn to Ti is Zn : Ti = 99 : 1 ( Ti / ( Zn + Ti ) = 0.01 ) ο Next, the obtained oxide mixture (Cl) is processed into a disk shape of 50 mmcp to obtain As a target for sputtering, a transparent conductive film was formed by sputtering using a target as in Example 1, to produce a transparent conductive substrate. In other words, the sputtering target and the film formation substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-2 00" manufactured by Canon-Anelva Co., Ltd.) at -45-201200616, and introduced at 12 sccm. Ar gas (purity: 99.9995% or more, Ar pure gas = 5N) was sputtered under the conditions of a pressure of 55 Pa, a power of 100 W, and a substrate temperature of 25 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. The composition (Zn : Ti ) in the formed transparent conductive film was quantitatively analyzed by a fluorescent X-ray method using a calibration curve as in Example 1, and was Zn: Ti (atomic ratio) = 99:1. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and crystal structure of titanium to zinc were investigated, and the single phase of the wurtzite type which is aligned with the C-axis was observed. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2×1 (Γ3 Ω·cm, and the surface resistance was 24 Ω/□. Further, the specific resistance distribution on the transparent conductive substrate was in-plane uniform. The transmittance of the substrate is 90% in the visible light region (380 nm to 780 nm) and 70% in the infrared region (780 nm to 2700 nm). » Further, the transmittance of the quartz glass substrate before film formation is in the visible light region. The infrared ray region was the same as in Example 1. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 2.3 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was poor. The heat resistance of the transparent conductive substrate and the surface resistance after the heat resistance test were 2 times and 0 times the surface resistance before the heat resistance test, and it was found that the heat resistance was poor. -46-201200616 The alkali resistance of the obtained transparent conductive substrate was evaluated, and after immersion The film was completely dissolved and disappeared. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared. From the above, the film on the obtained transparent conductive substrate was known. Although it is transparent and has low electrical resistance, it is a transparent conductive film which is inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). (Example 3) <Manufacturing of oxide sintered body> The disc-shaped formed body obtained in general is heated to 1 000 ° C at 5 ° C / min in an atmospheric atmosphere, and is heated to 1 500 ° C at 1 ° C / min over 1000 ° C at a sintering temperature of 1,500 ° C. Sintering was carried out for 5 hours at ° C, and then annealed at 130 ° C for 5 hours in an inert atmosphere (100% Ar atmosphere) to obtain an oxide sintered product (3). Energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation") The oxide sintered product (3) was analyzed, and the atomic ratio of Zn to Ti was Zn: Ti = 93: 7 (Ti/( Zn + Ti ) = 0.07 ) The crystal structure of the oxide sintered product (3) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) as a mixture of crystal phases of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). The titanium oxide is completely absent. Next, the obtained oxide sintered product (3) is processed into a disk shape of 50 ηηηηφ A target for sputtering was obtained, and a transparent conductive film having a film thickness of 50,000 nm was formed by sputtering in the same manner as in Example 1. -47 - 201200616 Composition in a transparent conductive film formed (zn: Ti) was quantitatively analyzed by a fluorescent X-ray method using a calibration curve as in Example 1, and was Zn: Ti (atomic ratio) = 93: 7. Further, the transparent conductive film was as in Example 1. In general, X-ray diffraction is performed, and the doping state of titanium to zinc is investigated, and the single phase of the wurtzite type which is aligned with the C-axis can be understood to be dissolved in zinc by titanium substitution. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 6.2 X 1 (Γ4 Ω·cm, and the surface resistance was 12.4 Ω/□. Further, the specific resistance distribution on the transparent conductive substrate was in-plane uniform. The transmittance of the conductive substrate is 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (78 0 nm to 27 Å Onm). Further, the transmission of the quartz glass substrate before film formation The rate was the same in the visible light region and the infrared region as in Example 1. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. In addition, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. There was no change in the film quality before and after, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness was thinned and dissolved after the immersion, but the film quality before and after the immersion was not The change was found to be excellent in acid resistance. From the above, it was found that the film on the obtained transparent conductive substrate was transparent and low in resistance of -48 to 201200616, and also had chemical durability (heat resistance, moisture resistance, alkali resistance, and acid resistance). (Example 4) <Production of oxide sintered product> The disk-shaped formed body obtained as in Example 2 was heated at 5 ° C / min in an inert atmosphere (100 % Ar atmosphere). To l〇〇〇°C, the temperature is raised to 1 300° C. in l°c/min, and sintering is performed at a sintering temperature of 1300° C. for 5 hours to obtain an oxide sintered product (4). The oxide sintered product (4) was analyzed by a fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn : Ti = 94 : 6 ( Ti / ( Zn + ) Ti) = 〇.〇6). The crystal structure of the oxide sinter (4) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) as zinc oxide (ZnO) and zinc titanate. A mixture of crystalline phases of (Zn2Ti04), titanium oxide is completely absent. Next, the resulting oxidation The sintered product (4) was processed into a disk shape of 50 ηηηηφ to obtain a target for sputtering, and a transparent conductive film having a film thickness of 500 nm was formed by sputtering using the target as in Example 1 to prepare a transparent conductive substrate. The composition (Zn: Ti) in the formed transparent conductive film was quantitatively analyzed by a fluorescent X-ray method using a calibration curve as Zn: Ti (atomic ratio) = 94:6 as in Example 1. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and the crystal structure of the titanium-zinc-49-201200616 were investigated, and the single phase of the Zinc-oriented bauxite type was observed. It can be understood that titanium substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5.8 x 1 (Γ4 Ω·cm, and the surface resistance was 11.6 Ω/□. Further, the specific resistance distribution on the transparent conductive substrate was in-plane uniform. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (78 0 nm to 2 700 nm). Further, the quartz before film formation The transmittance of the glass substrate was the same as that of Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test. In addition, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. Alkaline, there is no change in film quality before and after immersion, and it is known that it is excellent in alkali resistance. Moreover, the acid resistance of the obtained transparent conductive substrate is evaluated, and the film thickness after thinning is dissolved and dissolved, but the film quality before and after immersion It is known that the change in acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). (Comparative Example 2) -50-201200616 <Production of oxide sintered product> The disk-shaped formed body obtained as in Example 1 was placed in an inert atmosphere (100% Ar atmosphere) at 5 ° C / min. The temperature was raised to 1 000 ° C, the temperature was raised to 1 300 ° C at 1 ° C / min over 1 000 ° C, and sintering was carried out at a sintering temperature of 1 300 ° C for 5 hours to obtain an oxide sintered product (C2 ). The oxide sintered product (C2) was analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn: Ti = 98.5: l_5 (Ti/ (Zn + Ti) = 0.015) Next, the obtained oxide sintered product (C2) was processed into a disk shape of 5 〇 ηηηηφ to obtain a target for sputtering, and the target was used, as in Example 1, to be splashed. A transparent conductive film having a film thickness of 500 nm is formed by plating to form a transparent conductive substrate. The composition (Zn : Ti ) in the electric film was quantitatively analyzed by a fluorescent X-ray method using a calibration curve as in Example 1, and was Zn : Ti (atomic ratio) = 98_5 : 1.5. The transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and crystal structure of titanium to zinc were investigated, and the single phase of the wurtzite type of the C-axis alignment was observed. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 8.0×10_4 Ω·cm and a surface resistance of 16 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is uniform in-plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 780 nm) and 70% in the infrared region (201200616 780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation was the same as in Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 2.1 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was poor. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.8 times the surface resistance before the heat resistance test, and it was found that the heat resistance was poor. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared after the immersion. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, but is a transparent conductive film having poor chemical durability (heat resistance, moisture resistance, alkali resistance, and acid resistance). (Example 5) <Production of oxide sintered product (hot press method): Weigh zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.) so that the element ratio of zinc element to titanium element is 97·0: 3.0. Titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute) was poured into a container made of polypropylene, and then poured into a ball of oxidized chrome of 2 ηηηηφ and ethanol as a mixed solvent. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa using a press machine made of graphite, -500 - 201200 After 45 ° and 4 hours of treatment, a disk-shaped oxide sintered product (5) was obtained. The atomic ratio of the oxide sintered product (5) and Ti obtained by analysis of the energy-dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) was Zn: Ti = 97: 3 (Ti/(Zn + Ti) =0. The crystal structure of zinc oxide (ZnO) and zinc titanate (Zn2Ti04) was investigated by X-ray diffraction device (RINT2000 manufactured by Rigaku Electric Co., Ltd.). Then, the obtained oxide sintered product (5) was processed into a 50π1ηιφ disk shape to obtain a sputtering target, and the target film was formed into a film thickness of 500 nm by using the target as in Example 1. A transparent conductive film, a composition (Zn : Ti ) in a transparent conductive film formed by preparing a transparent conductive ruthenium, as in Example 1, is quantified by a fluorescent X-ray method using a calibration curve, and is Zn: Ti (atomic ratio) ) = 97 : 3. Further, as for the transparent guide, as in the first embodiment, X-ray diffraction is performed, and the doping state and the crystal structure of the titanium are investigated, and the fiber-zinc-type of the C-axis is known. The substitution is solid-dissolved in zinc. The specific electrical conductivity of the transparent conductive film on the obtained transparent conductive substrate It is 1 (Τ4 Ω · cm, and the surface resistance is 8.4 Ω/□. Further, the specific resistance distribution on the transparent conductive plate is in-plane uniform. The transmittance of the obtained transparent conductive substrate is 380 nm to 7 8 Onm in the visible light region. The average of 89% in the infrared region of the heat), Ζ η, 03) r, as the circle of the compound is analyzed by the sputtering substrate, the phase of the zinc film, 4·2 基 basic domain (domain - 53 - 201200616 780nm~2700nm) The average value is 60%. The transmittance of the quartz glass substrate before film formation is the same as that of Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate is evaluated. The surface resistance after the wet test was 1.2 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was before the heat resistance test. The surface resistance was 1.2 times, and it was found to be excellent in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after immersion, and it was found that the alkali resistance was excellent. Further, the resistance of the obtained transparent conductive substrate was evaluated. After the immersion, the film thickness is reduced and dissolved, but the film quality is not changed before and after immersion. It is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and has chemical durability (heat resistance). (Transparent conductive film of properties, moisture resistance, alkali resistance, and acid resistance) (Example 6) <Production of oxide sintered product (hot pressing method)> The ratio of elements of zinc element to titanium element was 97.0: 3.0 method of weighing zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), titanium oxide (Ti203 (III), manufactured by High Purity Chemical Research Institute), poured into a container made of polypropylene, and then poured into 2mmcj a ball made of zirconia and ethanol as a mixed solvent. Mixing these with a ball mill to obtain a mixed powder-54-201200616 After mixing, the mixed powder obtained by removing the ball and ethanol is poured into a mold (molre) made of graphite, using a press machine made of graphite, 4 OMP The pressure of a was vacuum-pressed, and heat treatment was performed at 100 ° C for 4 hours to obtain a disk-shaped oxide sintered product (6). The oxide sintered product (6) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 97: 3 (Ti /(Zn + Ti) = 0.03). The crystal structure of the oxide sintered product (6) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Next, the obtained oxide sintered product (6) was processed into a disk shape to obtain a target for sputtering, and a transparent conductive film having a film thickness of 50 Å was formed by sputtering using the target as in Example 1. Preparation of a transparent conductive substrate 组成 a composition (Zn : Ti ) in the formed transparent conductive film, as in Example 1, using a fluorescent X-ray method, quantitative analysis using a calibration curve 'is Zn : Ti (atomic ratio ) = 97 : 3. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and crystal structure of titanium to zinc were investigated, and the single phase of the wurtzite type which is aligned with the C-axis was observed. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 x 10_4 Ω · cm ', and the surface resistance was 8.8 Ω / []. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. -55-201200616 The transmittance of the obtained transparent conductive substrate was 89% on average in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation was the same as in Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 7) <Production of oxide sintered product (normal pressure sintering method of TiO (II))> ZnO powder (ZnO powder; purity 99.9%, average particle diameter 1 or less, and Wako Pure Chemical Industries, Ltd.) And titanium oxide powder (TiO ( II ) powder; purity 99.9%, average particle diameter 1 μ m or less, manufactured by High Purity Chemical Research Institute (stock)) as raw material powder, etc., so that -56- 201200616

The ratio of the atomic ratio of Zn : Ti to 97:3 was added to a resin crucible, and wet mixing was carried out by a wet ball milling mixing method. The wet mixing system uses a hard Zr02 ball as a ball and the mixing time is 18 hours. Then, the mixed raw material powder slurry is taken out, dried, granulated, and then subjected to a cold equalizing press to apply a pressure of lton/cm2. It was molded to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. The resulting disk-shaped formed body is then heated to 1 000 ° C at 5 ° C / min in an inert atmosphere (1 〇〇 % Ar atmosphere), and raised to 1 300 ° C at 1 ° C / min over 1 000 ° C. c, sintering was carried out for 5 hours at a sintering temperature of 130 CTC to obtain an oxide sintered product (7). The oxide sintered product (7) was analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn: Ti = 97: 3 (Ti /( Zn + Ti ) =0.03 ). The crystal structure of the oxide sintered product (7) was investigated by an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Next, the obtained oxide sintered product (7) was processed into a disk shape of 50 π ηηφ to obtain a target for sputtering, and a transparent conductive film having a film thickness of 500 nm was formed by sputtering using the target as in Example 1. Preparation of a transparent conductive substrate 组成 The composition (Zn : Ti ) in the formed transparent conductive film was quantitatively analyzed by a fluorescent X-ray method using a calibration curve as Zn: Ti (atomic ratio) as in Example 1. =97 : 3. Further, this transparent conductive film-57-201200616 was subjected to x-ray diffraction as in Example 1, and the doping state and crystal structure of titanium to zinc were investigated, and the single phase of the wurtzite type of the C-axis was observed. It can be understood that titanium substitution is dissolved in zinc. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 4.2 χ 10_4 Ω · cm and a surface resistance of 8.4 Ω / ΙΙΙ. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (780 nm to 270 nm). » Further, the quartz glass before film formation The transmittance of the substrate was the same as that of Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. -58-201200616 (Comparative Example 3) <Production of oxide sintered product (normal pressure sintering method of TiO (Π))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle diameter 1 &quot; m or less, and Wako Pure Chemical Industries Co., Ltd.) and titanium oxide powder (TiO(II) powder; purity 99.9%, average particle diameter i#m or less, manufactured by High Purity Chemical Research Institute Co., Ltd.) as raw material powder, etc. The ratio of the atomic ratio of Zn:Ti to 88:12 was added to a resin crucible, and wet mixing was carried out by wet ball milling. The wet mixing was carried out using a hard Zr02 ball as a ball and a mixing time of 18 hours. Then, the mixed raw material powder slurry was taken out, dried, granulated, and then subjected to a pressure of lton/cm 2 by a cold pressure press to form a disk-shaped molded body having a diameter of 100 mm and a thickness of 8 mm. The disc-shaped formed body is heated to 100 (TC at 5 ° C / min in an inert atmosphere (100% Ar atmosphere), heated to 1 300 ° C at 1 ° C / min over 1 000 ° C, in sintering Sintering was carried out at a temperature of 1 3 00 ° C for 5 hours to obtain an oxide sintered product (C3). The oxide sintered by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) was analyzed. (C3), the atomic ratio of Zn to Ti is Zn : Ti = 88 : 12 ( Ti / ( Zn + Ti ) = 0.12). X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) The crystal structure of the oxide sintered product (C3) was investigated as a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04) crystal phase, and titanium oxide was completely absent. Next, the obtained oxide sintered product (C3) was processed. 50mm (j) -59- 201200616 disc shape, obtain the target for sputtering, use the target In the same manner as in Example 1, a transparent conductive film having a film thickness of 500 nm was formed by sputtering to prepare a transparent conductive substrate. The composition (Ζιι: Ti) in the formed transparent conductive film was used as in Example 1, using fluorescent X-rays. The method was quantitatively analyzed using a calibration curve, and was Zn: Ti (atomic ratio) = 88: 12. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the titanium to zinc was investigated. The doped state and the crystal structure are single phase of the wurtzite type which is aligned with the C axis, and it is understood that the titanium substitution is dissolved in the zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate is 2.1 X 1 (Γ2 Ω). · cm, the surface resistance is 420.0 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate is 89 in the visible light region (380 nm to 780 nm). % is an average of 66% in the infrared region (78 0 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation is the same as in Example 1 in the visible light region and the infrared region. The obtained transparent conductive substrate was evaluated. Moisture resistance, moisture resistance test The surface resistance was 1.1 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times that of the surface resistance before the heat resistance test. It is known that the heat resistance is excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive-60-201200616 substrate was evaluated and impregnated. The film thickness was thinned and dissolved, but the film quality did not change before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), but is high in resistance. (Example 8) <Production of oxide sintered product (normal pressure sintering method of TiO (II))> Zinc oxide powder (ZnO powder; purity 99.9%, average particle diameter 1 /zm or less, and Wako Pure Chemical Industries Co., Ltd.) (manufacturing) and titanium oxide powder (TiO(II) powder; purity 99.9%, average particle diameter lym or less, manufactured by High Purity Chemical Research Institute), as raw material powder, such that Zn: Ti atoms The ratio of the ratio of 93:7 was added to the resin crucible, and the wet mixing was carried out by a wet ball milling mixing method. The wet mixing system was carried out using a hard Zr02 ball as a ball and a mixing time of 18 hours. Then, the mixed raw material powder slurry was taken out, dried, granulated, and then subjected to a pressure of 1 ton/cm 2 by a cold pressure press to obtain a disk-shaped formed body having a diameter of 1 mm and a thickness of 8 mm. . Next, the obtained disk-shaped formed body was heated to 1 000 ° C at 5 ° C / min in an inert atmosphere (10 ° C atmosphere) over 1 Torr. (3) The temperature was increased to 1300 ° C and held at a sintering temperature of 130 ° C for 5 hours to obtain an oxide sintered product (8). The energy-dispersive fluorescent X-ray device (Shimadzu) The oxide sinter (8) obtained by "EDX-700L" manufactured by the company (stock), the atomic ratio of Zn -61 - 201200616 to Ti is Zn: Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). The crystal structure of the oxide sintered product (8) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) as a crystal phase of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). The mixture was completely absent from titanium oxide. Next, the obtained oxide sintered product (8) was processed into a disk shape of 5 Ommcj) to obtain a target for sputtering, and the target was used as in Example 1 to be sputtered. A transparent conductive film having a film thickness of 500 nm was formed, and a composition (Zn : Ti ) in the transparent conductive film formed in the transparent conductive substrate was prepared, and the calibration curve was used for quantification by a fluorescent X-ray method as in Example 1. Analysis 'is Zn: Ti (atomic ratio) = 93: 7. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and crystal structure of titanium to zinc were investigated, and the single phase of the wurtzite type which is aligned with the C-axis was observed. It is dissolved in zinc. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 5.9 x 10_4 Ω · cm and a surface resistance of 1 1 · 8 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation was the same as in Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance of the surface after the moisture resistance test was -1.2 to 201200616, which was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The evaluation of the alkali resistance of the obtained transparent conductive substrate, and the film quality before and after the immersion. There is no change, and it is known that it is excellent in alkali resistance. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 9) <Production of oxide sintered product (normal pressure sintering method of TiO (II))> Manufactured by zinc oxide powder (ZnO powder; purity 99.9%, average particle diameter 1 or less) and Wako Pure Chemical Industries, Ltd. And titanium oxide powder (TiO ( II) powder; purity 99.9%, average particle diameter m or less, manufactured by High Purity Chemical Research Institute), as the raw material powder, so that the atomic ratio of Zn: Ti becomes The ratio of 91:9 was added to a resin crucible, and wet mixing was carried out by a wet ball milling mixing method. The wet mixing was carried out using a hard Z r Ο 2 ball as a ball for a mixing time of 18 hours. Next, the mixed raw material powder slurry was taken out, dried, granulated, and then formed by a cold pressure-pressure press using a pressure of lton/cm 2 to obtain a disk-shaped formed body having a diameter of 1 mm and a thickness of 8 mm. -63- 201200616 Next, the obtained disk-shaped formed body was heated to 1 000 ° C at 5 ° C / min in an inert atmosphere (1 〇〇 % Ar atmosphere), and exceeded 1 ° C at 1 ° C The temperature was raised to 1 3 00 ° C in /min, and sintering was carried out at a sintering temperature of 1,300 ° C for 5 hours to obtain an oxide sintered product (9). The oxide sintered product (9) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 91: 9 (Ti /(Zn + Ti) =0·09) . The crystal structure of the oxide sintered product (9) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ΖηΟ) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Then, the obtained oxide sintered product (9) was processed into a disk shape of 50 mm 4 > to obtain a target for sputtering, and a transparent conductive film having a film thickness of 500 nm was formed by sputtering using the target as in Example 1. Preparation of a transparent conductive substrate 组成 a composition (Zn : Ti ) in the formed transparent conductive film, as in Example 1, using a fluorescent X-ray method, quantitative analysis using a calibration curve, which is Zn : Ti (atomic ratio ) = 91 : 9. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 1, and the doping state and the crystal structure of titanium to zinc were investigated, and the single phase of the C-aligned fiber bismuth type was observed. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.2 x 10 · 3 Ω · cm, and the surface resistance was 44.0 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. -64-201200616 The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 780 nm) and 65% in the infrared region (780 nm to 27 Å Onm). Further, the transmittance of the quartz glass substrate before film formation was the same as in Example 1 in the visible light region and the infrared region. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 1 〇) As a raw material, zinc oxide powder (manufactured by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti2〇3; manufactured by High Purity Chemical Research Institute, purity: 99.99%) The powder was mixed in such a ratio that the atomic ratio of Zn:Ti was 96:4 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and formed into a pressure of 500 kg/cm 2 at a pressure of -65 to 201200616 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was annealed at 40 ° C for 3 hours under an argon atmosphere at a normal pressure (10 〇 1.325 kPa) to obtain an oxide mixture (10 ) 0 as an energy dispersive fluorescent X-ray device (Shimadzu Corporation) The "oxidation mixture (10) obtained by "EDX-700L") was analyzed, and the atomic ratio of Zn to Ti was Zn: Ti = 96: 4 (Ti / ( Zn + Ti ) = 0.04 ). The crystal structure of the oxide mixture (10) was investigated by an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ZnO) and titanium oxide (Ti203). Next, the obtained oxide mixture (1 Å) was processed into a disk shape of 50 ηηηηφ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sCCm (purity of 99.9995% or more). Ar pure gas = 5 N), sputtering was performed under the conditions of a pressure of 0.5 Pa, an electric power of 75 W, and a substrate temperature of 25 (TC), and a transparent conductive film having a thickness of 500 nm was formed on the substrate. The composition in the formed transparent conductive film (Zn) : Ti ), using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), using a fluorescent X-ray method, using a calibration curve for quantitative analysis, Zn : Ti (atoms) In the case of the transparent conductive film, an X-ray diffraction device ("RINT2 0 00" manufactured by Rigaku Electric Co., Ltd.) is used, and a film is used. Determination -66- 201200616 The χ-ray diffraction was carried out with the accessory, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and then an electric field emission electron microscope (FE-SEM) was used. Investigate the crystal structure, which is a C-axis oriented wurtzite type It can be understood that the titanium substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate is 5.1 χ 10_4 Ω · cm, and the surface resistance is 10.2 Ω / □. Further, on the transparent substrate The specific resistance distribution is in-plane uniformity. The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). The transmittance of the quartz glass substrate in front of the film in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 27 Å Onm) was 94% on average. The obtained transparent conductive substrate was evaluated. Moisture resistance and surface resistance after the moisture resistance test were 1.2 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was In the case of the surface resistance of the heat-resistance test, it is known that the heat resistance is excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. The transparent conductive substrate is resistant to acid, and the thickness of the transparent conductive substrate is reduced and dissolved. However, the film quality is not changed after the immersion, and it is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance. A transparent conductive film having chemical durability (heat resistance, moisture resistance, alkali resistance, -67-201200616 acid resistance) (Example 11) Processed by the oxide mixture (1 〇) obtained in Example 1 The wafer was formed into a disk shape of 50 ηηπιψ, and a target was produced, and a transparent conductive film was formed by sputtering using the target to prepare a transparent conductive substrate. In other words, the target and the transparent substrate (acrylic transparent resin sheet) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.9995%). As described above, Ar pure gas = 5 N) was sputtered under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C to form a transparent conductive film having a thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the calibration was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn : Ti (atomic ratio) = 96 : 4 ( Ti / ( Ti + Zn) = 0.04). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalysis was used. The instrument (TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the fiber-zinc-type alignment of the C-axis. In zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.2 x 1 〇·4 n.cm, and the surface resistance was 14.4 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. • 68 - 201200616 The transmittance of the obtained transparent conductive substrate is 88% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance in the visible light region (380 nm to 780 nm) of the acrylic transparent resin sheet before film formation was 93% on average, and the transmittance in the infrared region (780 nm to 27 Å Onm) was 93% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.4 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 1 2) As a raw material powder, zinc oxide powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%) were used. These were mixed in such a ratio that the atomic ratio of Zn:Ti was 96:4 to obtain a mixture of raw material powders -69-201200616. Then, the obtained mixture was poured into a mold, and molded at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was annealed at 500 ° C for 3 hours under an atmospheric pressure of normal pressure (101.325 kPa) to obtain an oxide mixture (11) » Energy dispersive fluorescent X-ray device (manufactured by Shimadzu Corporation) The "EDX-700L" analysis of the obtained oxidation mixture (1 1 ), the atomic ratio of Zn to Ti is Zn: Ti = 96: 4 (Ti / (Zn + Ti) = 0_04). The crystal structure of the oxide mixture (11) was investigated by an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ΖηΟ) and a crystal phase of titanium oxide. Next, the obtained oxide mixture (11) was processed into a disk shape of 50 mm cj) to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 SCCm (purity of 99.9995 % or more, Ar). Pure gas = 5 N), sputtering was carried out under the conditions of a pressure of 0_5 Pa, a power of 100 W, and a substrate temperature of 130 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the calibration was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn : Ti (atomic ratio) = 96 : 4 ( Ti / ( Zn + Ti ) = 0.04). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and an accessory for film measurement was used, and an energy dispersive type X was used. The ray microanalyzer (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the C-axis aligned wurtzite type. The substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 8. Ox 10_4 Ω · cm, and the surface resistance was 16 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is uniform in-plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 780 nm) and 62% in the infrared region (78 nm to 2700 μm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.4 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it was found that the film on the obtained transparent conductive substrate was transparent and had a low electrical resistance of -71 - 201200616 and a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 1 3) As a raw material powder, zinc oxide powder (made by ZnO: Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%), These were mixed in such a ratio that the atomic ratio of Zn:Ti was 97:3 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. This molded body was sintered at 800 ° C for 4 hours under an argon atmosphere under normal pressure (1.0 1 3 25 x 102 kPa) to obtain an oxide sintered product (12). The oxide sintered product (12) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03 ). The crystal structure of the oxide mixture (12) was investigated by an X-ray diffraction device ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.) as a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Then, the obtained oxide sintered product (12) was processed into a disk shape of 50 mmφ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were respectively placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva (-72-201200616)), and Ar gas was introduced at 12 sccm (purity). 99.9995 % or more, Ar pure gas = 5 N), sputtering was carried out under the conditions of a pressure of 55 Pa, a power of 75 W, and a substrate temperature of 250 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1700WS" manufactured by Shimadzu Corporation) is used, and a calibration curve is used by a fluorescent X-ray method. For quantitative analysis, it was Zn : Ti (atomic ratio) = 97 : 3 ( Ti / ( Zn + Ti) = 0.03). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer was used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the C-axis aligned wurtzite type. In zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4·4 χ 1 (Γ4 Ω·cm, and the surface resistance was 8.8 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform). The transmittance of the conductive substrate is 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the quartz glass substrate before film formation is The transmittance in the visible light region (3 80 nm to 78 0 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the moisture resistance test was performed. Table-73-201200616 The surface resistance is 1.2 times the surface resistance before the moisture resistance test, and it is known that the moisture resistance is excellent. The heat resistance of the obtained transparent conductive substrate is evaluated, and the surface resistance after the heat resistance test is before the heat resistance test. When the surface resistance was 1.2 times, it was found to be excellent in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after immersion, and it was found that the alkali resistance was excellent. Further, the obtained transparent conductive substrate was evaluated. It is acid-resistant, and the film thickness is thinned and dissolved after immersion. However, it is known that the film quality is excellent when the film quality is not changed before and after immersion. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance and chemical durability ( Transparent conductive film of heat resistance, moisture resistance, alkali resistance, and acid resistance. (Comparative Example 4) Zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; high) Purity Chemical Research Institute (purity: 99.99%) was used as a raw material powder, and these were mixed at a ratio of the atomic ratio of Zn:Ti to 99:1 to obtain a mixture of raw material powders. Then, the obtained mixture was poured. The mold was molded into a mold at a molding pressure of 500 kg/cm 2 to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was subjected to 400 ° under an argon atmosphere at a normal pressure (101.325 kPa). C was annealed for 3 hours to obtain an oxide mixture (C4). The oxidation mixture (C4), Zn-74-, was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of 201200616 to Ti is Zn: Ti = 99: l(Ti/(Zn + Ti) = 0.01) ο Next, the obtained oxide mixture (C4) is processed into a disk shape to prepare a target, and the target is used. The target is formed by sputtering a transparent conductive film to obtain a transparent conductive substrate, that is, the target and the transparent substrate (quartz glass substrate) are respectively disposed on a sputtering apparatus ("Eon" by Canon-Anelva In -200"), Ar gas (purity: 99.9995 % or more, Ar pure gas = 5 N) was introduced at 12 sccm, and sputtering was performed under the conditions of a pressure of 0.5 Pa, a power of 100 W, and a substrate temperature of 130 ° C to form a film thickness on the substrate. 200 nm transparent conductive film. For the composition (Zn:Ti) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the measurement was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn: Ti (atomic ratio) = 99: 1 (Ti/(Zn + Ti) = 0.01). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer was used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 2.5 x 10 -3 Ω · cm and a surface resistance of 125 Ω / □. Further, the specific resistance distribution on the transparent substrate is uniform in-plane. The transmittance of the obtained transparent conductive substrate was 90% on average in the visible light region (-75-201200616 380 nm to 7 8 Onm) and 7 Ο% in the infrared 780 nm to 2700 nm. Further, the film-forming glass substrate is 94% in the visible light region (380 nm to 780 nm) and 94% in the infrared region (78 nm to 2700 nm). The moisture resistance of the obtained transparent conductive substrate was evaluated, and the wet resistance was 2.6 times that of the surface resistance before the moisture resistance test, which may be undesirable. Further, the surface resistance after the test of the obtained transparent conductive substrate was evaluated as the surface resistance before the heat resistance test, and it was found that the heat resistance was poor. The obtained transparent conductive substrate was evaluated for alkali resistance, immersed, dissolved, and disappeared. Further, the obtained transparent conductive substrate was completely dissolved and disappeared. From the above, it is understood that the film obtained on the transparent conductive substrate is high in electrical resistance and has poor chemical durability (heat resistance, moisture resistance, alkali resistance). (Comparative Example 5) 2.3 parts by weight of an alumina powder having an average particle diameter of 1/zm of 97.7 by weight and a particle diameter of 0.2 m was poured into a polymerization mixture, and mixed by a dry ball mill for 72 hours to obtain a compound. The resulting mixture was poured into a mold and pressed at a pressure of a forming pressure to obtain a shaped body. After the densification treatment was applied to the formed body by CIP at 3 ton/cm 2 , the following line region was used (the average quartz glass lapse rate was the average after the transmittance test, and the heat resistance was 2.0 times, and the heat resistance was 2.0 times. The film is completely resistant to acidity, and the film is transparent, but it is acidic and acid-resistant. It is mixed with the average ethylene-made baking powder at a pressure of 300 kg/cm2, and the alloy is sintered at -76-201200616 to obtain oxidation of doped aluminum. Zinc oxide sinter (C5) Sintering temperature: 1 5 0 0 °c Heating rate: 5 〇 ° C / hour Holding time: 5 hours Sintering atmosphere: The oxide sinter (C5 ) obtained in the atmosphere is X-rayed The shot analysis is a mixed structure of ZnO and ΖηΑ12〇4. Next, the obtained oxide sinter (C5) is processed into a shape of 4 inches φ, 6 mmt, and fixed on an oxygen-free copper support plate using indium solder ( On the backing plate, a target was produced. Then, using the target, a film was formed by sputtering under the following conditions, and a transparent conductive film having a film thickness of 300 nm was formed on a transparent substrate (quartz glass substrate) to obtain transparent conductivity. Substrate The content of A1 in the film is 2.3% by weight. Device: dc magnetron sputtering device Magnetic field strength \ : 1000 Gauss (directly above the target, horizontal component) Substrate temperature: 200.

Reaching vacuum: 5xl (TP

Sputtering gas: A r Sputtering gas pressure: 0.5 Pa DC power: 3 00 W The specific conductive resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.6 -77 - 201200616 l (r4n.cm, surface resistance was 25.3 Ω / 0. The transmittance of the obtained transparent conductive substrate was 88% in the visible light region (380 nm to 7 8 Onm) and 55% in the infrared region (780 nm to 2700 nm). The moisture resistance of the obtained transparent conductive substrate was evaluated. The surface resistance after the moisture resistance test was 3.2 times that of the surface resistance before the moisture resistance test, and it was found to be poor in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was before the heat resistance test. When the surface resistance was 7.0 times, it was found that the heat resistance was poor. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared after the immersion. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared. As described above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, but is a transparent conductive film having poor chemical durability (heat resistance, moisture resistance, alkali resistance, and acid resistance). Example 1 4) As a raw material, zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): High Purity Chemical Research Institute, 99.99% purity) The powder was mixed in such a ratio that the atomic ratio of zn: Ti was 97:3 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold and formed at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine. A disk-shaped molded body having a diameter of 30 mm and a thickness of 5 mm was obtained, and the molded body was sintered at 1 Torr (rc for 4 hours) under an argon atmosphere at a normal pressure (-78-201200616 102 kPa) to obtain an oxide sintered product. (1 3 ) The oxide sintered product (13 ) was analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03 ). The crystal structure of the oxide sintered product (13) was investigated by an X-ray diffraction device ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.) as zinc oxide. a mixture of (ZnO) and a crystalline phase of zinc titanate (Zn2Ti04), oxidized Titanium is completely absent. Next, the obtained oxide sintered product (13) is processed into a disk shape of 50 mmc|) to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.9995 % or more). 1* pure gas = 5 〇, sputtering was performed under the conditions of a pressure of 0.5 Å, a power of 75 W, and a substrate temperature of 250 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device (^XRF-1700WS manufactured by Shimadzu Corporation) is used, and a calibration curve is used by a fluorescent X-ray method. Quantitative analysis was performed for Zn: Ti (atomic ratio) = 97:3 (Ti/(Zn + Ti) = 0.03). In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was carried out using an accessory for film measurement" while using energy dispersive X-ray-79-201200616 Microanalyzer (TEM-EDX) was used to investigate the doping state of titanium on zinc, and then the electric field radiation electron microscope (FE-SEM) was used to investigate the crystal structure, which is a single phase of the C-axis aligned wurtzite type. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 χ 1 (Γ4 Ω·cm, and the surface resistance was 8.4 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the substrate is 89% in the visible light region (3 80 nm to 7 8 Onm) and 60% in the infrared region (780 nm to 2700 nm). Further, the quartz glass substrate before the film formation is in the visible light region (3) The transmittance in the range of 80 nm to 780 nm is 94% on average, and the transmittance in the infrared region (780 nm to 27 Å Onm) is 94% on average. The moisture resistance of the obtained transparent conductive substrate and the surface resistance after the moisture resistance test were evaluated. The surface resistance before the moisture resistance test was 1.2 times, and it was found to be excellent in moisture resistance. The heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test. It is excellent in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated. The film thickness was reduced and dissolved, but the film quality was not changed before and after immersion. It was found that the film was excellent in acid resistance. From the above, it was found that the film on the obtained transparent conductive substrate was transparent and low in electrical resistance, and also had chemical durability (heat resistance and resistance). Transparent conductive film of wetness, alkali resistance, and acid resistance. -80-201200616 (Example 1 5) A mixture of raw material powders was obtained as in Example 14. After the mixing operation, the mixed powder obtained by removing the balls and ethanol was obtained. Pour into a mold made of graphite (mould), and use a press machine made of graphite, vacuum-pressurize at a pressure of 40 MPa, and heat treatment at 1 〇〇 0 ° C for 4 hours to obtain a disk-shaped oxide. Sintered material (I4) (hot pressing method) The oxide sintered product (14), the atomic number of Zn and Ti were analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) The ratio is Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03 ). The oxide sintered product (14 ) was investigated by an X-ray diffraction device ("RINT2 0 00" manufactured by Rigaku Electric Co., Ltd.). Crystal structure, which is zinc oxide (ZnO And a mixture of the crystal phase of zinc titanate (Zn2Ti〇4), titanium oxide is completely absent. Next, the obtained oxide sintered product (I4) is processed into a disk shape of 5〇πηηφ to prepare a target, and the target is used. The target is formed into a transparent conductive film by sputtering to obtain a transparent conductive substrate. That is, the target and the transparent substrate (quartz glass substrate) are respectively disposed on a sputtering apparatus ("E-" manufactured by Caiion-AneWa Co., Ltd. In 200"), Ar gas was introduced at 12 sccm (purity: 99.9995 % or more, Ar pure gas = 5 N), and sputtering was performed under the conditions of a pressure of 55 Pa, a power of 75 W, and a substrate temperature of 250 ° C. 500 nm transparent conductive film. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("81 - 201200616 XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used. Quantitative analysis using a calibration curve is Zn : Ti (atomic ratio) = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the zinc-type aligned with the C-axis. It can be understood that titanium is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2×1 (T4Q.cm, and the surface resistance was 8.4 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane.) The obtained transparent conductive substrate The transmittance is 8.9 % in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (78 〇 nm to 2700 nm). Furthermore, the quartz glass substrate before film formation is visible. The transmittance in the region (3 80 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface after the moisture resistance test was evaluated. The electric resistance was 1.2 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance. The heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times that of the surface resistance before the heat resistance test. It is known that the heat resistance is excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive-82-201200616 substrate was evaluated. After the immersion, the film thickness is reduced and dissolved, but the film quality is not changed before and after immersion. It is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and has chemical durability (heat resistance). Transparent conductive film of properties, moisture resistance, alkali resistance, and acid resistance. (Example 1 6 ) Zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203 (III) ): a high-purity chemical research institute (purity: 99.99%), as a raw material powder, which is mixed in a ratio of atomic ratio of Zn:Ti to 97:3 to obtain a mixture of raw material powders. Pour the mixed powder obtained by removing the ball and ethanol into a mold (mould) made of graphite, and pressurize with a pressure of 40 MP a using a press machine made of graphite to carry out 1 ° C, 4 hours. Heat treatment to obtain a disk-shaped oxide sintered product (15) (hot pressing method) ° Oxidation of the oxide obtained by analysis of an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) Object (15) The atomic ratio of Zn to Ti is Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03 ). The oxide is investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.). The crystal structure of the sinter (15) is a mixture of zinc oxide (ZnO) and zinc silicate (Zn2Ti04) crystal phase, and the oxidization is completely absent. Next, the obtained oxide sinter (15) is processed into 50 mmcj) -83-201200616 A disk shape was used to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a plating apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 Sccm (purity of 99.9995 % or more). Ar pure gas = 5 N), sputtering was carried out under the conditions of a pressure of 55 Pa, an electric power of 7 SW, and a substrate temperature of 250 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the calibration was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn : Ti (atomic ratio) = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4 x 10_4 Q.cm, and the surface resistance was 8.8 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 27 Å Onm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was -84 - 201200616 94%, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the transparent conductive substrate and the surface resistance after the moisture resistance test were 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Comparative Example 6) As a raw material powder, zinc oxide powder (manufactured by ZnO and Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203 (III): manufactured by High Purity Chemical Research Institute, purity: 99.99%) These were mixed in such a ratio that the atomic ratio of Zn:Ti was 8 8 : 12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite to carry out l〇〇 (TC, 4). After the heat treatment of the hour, a disk-shaped oxide sinter (C6) was obtained. -85-201200616 The oxide sintered by the energy dispersive fluorescent ray-ray device ("EDX-700L" manufactured by Shimadzu Corporation) (C6), the atomic ratio of Zn to Ti is Zn : Ti = 88 : 1 2 ( Ti / ( Zn + Ti ) = 0.12 ). X-ray diffraction device (r RINT2000 manufactured by Rigaku Motor Co., Ltd.) The crystal structure of the oxide sintered product (C6) is investigated as a mixture of zinc oxide (ΖηΟ) and a crystal phase of zinc titanate (Zn2Ti04), and titanium oxide is completely absent. Next, the obtained oxide sintered product (C6) The film is processed into a disk shape to prepare a target, and a transparent conductive film is formed by sputtering using the target to obtain a transparent conductive substrate. That is, the target and the transparent substrate (quartz glass substrate) are separately disposed. Plating device (Canon-Anelva) In the "E-200"), Ar gas was introduced at 12 sccm (purity: 99.9995 % or more, Ar pure gas = 5 N), and sputtering was performed under the conditions of a pressure of 55 Pa, a power of 75 W, and a substrate temperature of 250 ° C. A transparent conductive film having a thickness of 500 nm is formed thereon. A wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used for the composition (Zn : Ti ) in the formed transparent conductive film. Quantitative analysis using a calibration curve using a fluorescent X-ray method is Zn: Ti (atomic ratio) = 88 : 12 (Ti / ( Zn + Ti ) = 0.12). Further, using X for the transparent conductive film The ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) uses X-ray diffraction using an accessory for film measurement, and uses an energy dispersive X-ray microanalyzer (TEM-EDX) to investigate the doping of titanium to zinc. In the heterogeneous state, the electric field radiation electron microscope (FE-SEM) was used to investigate the crystal structure, which is a single phase of the w-zinc type of the C-axis alignment of -86-201200616. It can be understood that the titanium substitution is dissolved in zinc, but the crystallinity is lowered. The transparent conductive film on the obtained transparent conductive substrate The resistance is 2.2 x 10 Ω · cm, and the surface resistance is 440 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate is average in the visible light region (380 nm to 780 nm). It is 89% and averages 66% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 78 Å) was 94% on average, and the transmittance in the infrared region (78 Å to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.1 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film, but is high in resistance. -87-201200616 (Comparative Example 7) Manufactured by zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): High Purity Chemical Research Institute, purity 99.99) %) As a raw material powder, these were mixed at a ratio of the atomic ratio of Zn:Ti to 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite, and 1000 ° C for 4 hours. Heat treatment 'obtained a disk type oxide sinter (C7). The oxide sintered product (C7) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-7 00L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 88: 12 ( Ti/(Zn + Ti) = 0.12). The crystal structure of the oxide sintered product (C7) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Next, the obtained oxide sintered product (C7) was processed into a disk shape of 5 to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 Sccm (purity of 99.9995% or more). Ar pure gas = 5 N), sputtering was performed under the conditions of a pressure of 0.5 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. -88 - 201200616 The composition (Zn: Ti) in the transparent conductive film formed by using the wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), using the fluorescent X-ray method Quantitative analysis using a calibration curve is Zn : Ti (atomic ratio) = 88 : 12 ( Ti / ( Zn + Ti ) = 0.12). In addition, the X-ray diffraction apparatus ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc, the crystallinity decreases. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 2.1 X 10 2 Q·cm and a surface resistance of 420 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is an in-plane uniform sentence. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 7 8 Onm) and 66% in the infrared region (780 nm to 27 Å Onm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.1 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times that of the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent in the range of -89 to 201200616. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance), but is high in resistance. (Example 1 7) It is made of zinc oxide powder (made by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203 (III): High Purity Chemical Research Institute (purity), purity 99.99%) The raw material powders were mixed in such a ratio that the atomic ratio of Zn:Ti was 93:7 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite to carry out l〇〇〇°C, 4 hours of heat treatment to obtain a disk-shaped oxide sinter (16) (hot pressing method) ° oxidized by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) The material sinter (16), the atomic ratio of Zn to Ti is Zn. Ti = 93: 7 (Ti / (Zn + Ti) = 0.07). The crystal structure of the oxide sintered product (16) was investigated by an X-ray diffraction device ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.), and -90-201200616 was zinc oxide (ZnO) and zinc titanate (Zn2Ti04). A mixture of crystalline phases, titanium oxide is completely absent. Next, the obtained oxide sintered product (16) was processed into a disk shape of 5 Οιηιηφ to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive plug. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.9995 % or more). Human 1* pure gas = 5 〇, sputtering was performed under the conditions of a pressure of 0.5 Å, a power of 75 W, and a substrate temperature of 25 (TC) to form a transparent conductive film having a film thickness of 500 nm on the substrate. The composition (Zn : Ti ) of the medium is quantitatively analyzed by a fluorescence X-ray method using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation). Zn : Ti (atomic ratio) = 93 : 7 ( Ti / ( Zn + Ti ) = 0.07). Further, an X-ray diffraction device ("RINTMOO" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film. X-ray diffraction was carried out using an accessory for film measurement, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and then investigated by electric field emission electron microscopy (FE-SEM). Crystalline structure, single phase of wurtzite type aligned with C axis It can be understood that the titanium substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate is 6.2X 1 (Γ4 Ω·cm, and the surface resistance is 1 2.4 Ω/□. Further, on the transparent substrate The specific resistance distribution is in-plane uniformity. The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (-91 - 201200616 3 80 nm to 78 0 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The obtained transparent conductive substrate was evaluated. Moisture resistance and surface resistance after the moisture resistance test were 1.2 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was The surface resistance before the heat resistance test was 1.1 times, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. The obtained transparent conductive substrate has an acid resistance, and the film thickness after the immersion is thinned and dissolved. However, the film quality is not changed after the immersion, and it is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance. A transparent conductive film having chemical durability (heat resistance, moisture resistance, alkali resistance, and acid resistance). (Example 18) A zinc oxide powder (ZnO: Wako Pure Chemical Industries, Ltd., special grade) and Titanium oxide powder (TiO (II): manufactured by High Purity Chemical Research Institute, purity: 99.99%) is used as a raw material powder, and these are mixed at a ratio of atomic ratio of zn:Ti to 93:7 to obtain a raw material. a mixture of powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and pressed at a pressure of 40 MPa by a press machine made of graphite to carry out 1000 ° C. After heat treatment for 4 hours, a disk-shaped oxide sinter (17) (hot pressing method) was obtained, and an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) was analyzed. The oxide sintered product (17), the atomic ratio of Zn to Ti is Zn : Ti = 93 : 7 ( Ti / ( Zn + Ti ) = 0.07). The crystal structure of the oxide sintered product (17) was investigated by an X-ray diffraction device ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.) as a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Next, the obtained oxide sintered product (17) was processed into a disk shape of 5 Ommcj) to prepare a target, and a transparent conductive film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the upper target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.9995 % or more). , Ar pure gas = 5 N), sputtering was carried out under the conditions of a pressure of 55 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a transparent conductive film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the calibration was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn : Ti (atomic ratio) = 93 : 7 ( Ti / ( Zn + Ti ) = 0.07). Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction accessory using a X-ray diffraction apparatus ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive type X was used. Ray microanalyzer (TEM-EDX) investigates the doping state of titanium to zinc 'reuse electric field emission electron microscope (FE-SEM) to investigate the crystal structure, which is a single phase of the C-axis aligned wurtzite type. The substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 5·9 χ 4·4 Ω·cm, and the surface resistance was 1 1.8 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 89% on average in the visible light region (380 nm to 780 nm), and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 27 Å Onm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it was found that the film on the obtained transparent conductive substrate was transparent and had a low electrical resistance of -94 to 201200616, and also had a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 1 9) As a raw material powder, zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%) were used as raw material powders. These were mixed in such a ratio that the atomic ratio of Zn:Ti was 96:4 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a forming pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The molded body was heated at 500 ° C for 1 hour under an argon atmosphere under normal pressure (1.0 1 3 25 x 1 02 kPa) to obtain an oxide mixture (18) °. Energy dispersive fluorescent X-ray device (Shimadzu Corporation) (EDM) "EDX-700L" manufactured by analysis of the obtained oxidation mixture (18), the atomic ratio of Zn to Ti is Zn: Ti = 96: 4 (Ti / (Zn + Ti) = 0.04). The crystal structure of the oxide mixture (18) was investigated by an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and it was a mixture of zinc oxide (ZnO) and a crystal phase of titanium oxide (Ti2?3). Next, the obtained oxide mixture (18) was processed into a disk shape of 20 mm cj) to prepare a target, and a transparent conductive film was formed by a PLD method using the target to obtain a transparent conductive substrate. In other words, the target and the quartz glass substrate facing the target are placed in a pulsed laser vapor deposition device ("PS-2000" manufactured by Seonnam Kogyo Co., Ltd.), and laser light is used. Device-95-201200616 ("Comex 205 type" manufactured by Lambda Physik Co., Ltd.) was formed into a transparent conductive film having a thickness of 300 nm under the film formation conditions described below under a film formation time of 120 minutes. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm)

Laser energy: 1 8 mJ Repeat frequency: 5 Hz Target to substrate distance: 40 nm Substrate: Corning #1737 Substrate temperature (°C): 250 〇C Base pressure: 7.2x1 0_4Pa Gas pressure (oxygen): 0.25 Pa gas flow rate: 8.6 sccm film thickness: 300 nm The composition (Zn : Ti ) in the formed transparent conductive film is a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation). Quantitative analysis using a calibration curve using a camp X-ray method is Zn: Ti (atomic ratio) = 96:4. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy-96-201200616 (FE-SEM), which is a single phase of the C-axis aligned wurtzite type. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.4×10 −4 Q·cm, and the surface resistance was 14.7 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 90% on average in the visible light region (380 nm to 780 nm) and 65% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. -97-201200616 (Example 20) A transparent plate film was processed into an example to obtain a target of 120% of the oxide mixture (1 8 ) 2〇πιηιφ obtained in Example 19 to prepare a target, and the target was used.耙, and the transparent substrate (quartz glass substrate) of 19 is replaced with an acrylic grease sheet (80 mm X 80 mm x 2 mmt flat plate), and the member (substrate temperature) is replaced by the following, and the rest is as in the case of Example 19. The film formation time was minute, and a film having a film thickness of 300 nm was formed by the PLD method. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm)

Laser energy: 1 8 mJ Repetition frequency: 5 Hz Target to substrate distance: 40 nm Substrate: Corning #l 737 Substrate temperature (°C): 1 3 0 °C Base pressure: 7.2x1 (T4Pa gas pressure ( Oxygen): 〇.25Pa Gas flow rate: 8.6 sccm Film thickness: 30,000 nm The composition of the transparent conductive film formed by the wave-made line (Zn: Ti), long-dispersion fluorescent X-ray device (Shimadzu Corporation) (XRF-1 700WS"), which is quantitatively analyzed by the fluorescent X-ray method using a quantity of -98 to 201200616, and is Zn: Ti (atomic ratio) = 96: 4. Further, for the transparent conductive film, X-ray diffraction was carried out as in Example 19, and the doping state and crystal structure of titanium to zinc were investigated, and it was found that the C-axis was a single phase of the wurtzite type, and the titanium substitution was dissolved in zinc. The specific resistance of the transparent conductive film on the conductive substrate is 6·3 χ·4 Ω·cm, and the surface resistance is 21 Ω/□. Further, the specific resistance distribution on the transparent substrate is in-plane uniform. The obtained transparent conductive substrate The transmittance is 89% in the visible region (380 nm to 780 nm), in red The average area of the line region (780 nm to 2700 nm) is 65%. Furthermore, the transmittance of the resin sheet before film formation in the visible light region (380 nm to 780 nm) is 94% on average, and in the infrared region (780 nm to 2700 nm). The average transmittance was 94, and the moisture resistance of the obtained transparent conductive substrate was evaluated. The surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the obtained transparent conductivity was evaluated. The heat resistance of the substrate and the surface resistance after the heat resistance test were 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found to be alkali resistant. In addition, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after immersion was thinned and dissolved. However, the film quality was not changed before and after immersion, and it was found that the acid resistance was excellent. From the above, the film on the obtained transparent conductive substrate was known. A transparent conductive film that is transparent and has low electrical resistance and also has chemical durability (heat resistance, moisture resistance, alkali resistance -99 - 201200616, acid resistance). 1) As a raw material powder, zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%) The atomic ratio of Zn: Ti was mixed in a ratio of 96: 4 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and formed at a forming pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a diameter of 30 mm and a thickness. 5 mm disc shaped body. This molded body was sintered at 800 ° C for 4 hours under an argon atmosphere under a normal pressure (1.01325 x 1 02 kPa) to obtain an oxide sintered product (19). The oxidized sintered product (19) was analyzed by an energy dispersive fluorescent X-ray apparatus (EDX-700L J manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 96: 4 (Ti/ (Zn + Ti) = 0.04). The crystal structure of the oxide sintered product (19) was investigated by an X-ray diffraction device ("RINT2 0 00" manufactured by Rigaku Electric Co., Ltd.), which was zinc oxide (ZnO) and titanium. A mixture of crystalline phases of zinc acid (Zn2Ti04), which is completely absent. Then, the obtained oxide sintered product (19) was processed into a disk shape of 20 ηηηηφ to prepare a target, and a transparent conductive film was formed by a PLD method using the target to obtain a transparent conductive substrate. In other words, the target and the quartz glass substrate facing the target are placed in a pulsed laser vapor deposition device ("PS-2000" manufactured by Seonnam Kogyo Co., Ltd.), and laser light is used. Device-100-201200616 ("Comex 205 type" manufactured by Lambda Physik Co., Ltd.) was formed into a transparent conductive film having a thickness of 300 nm under the film formation conditions described below under a film formation time of 120 minutes. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm)

Laser energy: 18mJ Repeat frequency: 5Hz Target to substrate distance: 40nm Substrate: Corning #1737 Substrate temperature (°C): 2 5 0 °C Base pressure: 7.2x1 (T4Pa gas pressure (oxygen): 0.25 Pa gas flow rate: 8.6 sccm Film thickness: 300 nm The composition (Zn : Ti ) in the formed transparent conductive film, using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) Quantitative analysis using a calibration curve using a fluorescent X-ray method, Zn: Ti (atomic ratio) = 96 ·· 4 » Further, using an X-ray diffraction device for the transparent conductive film (Like ) "RINT2000" manufactured by X-ray diffraction using an accessory for film measurement, and an energy dispersive X-ray microanalyzer (TEM-EDX) to investigate the doping state of titanium to zinc, and then using electric field radiation type electrons. Microscope-101 - 201200616 (FE-SEM) investigated the crystal structure, which is a single phase of a wurtzite type aligned with C-axis, and can understand the specific resistance of a transparent conductive film on a transparent conductive substrate obtained by dissolving titanium in solid solution in zinc. 4.4x 1 (Γ4 Ω · cm, surface electricity The ratio of the specific resistance on the transparent substrate is uniform in the plane. The transmittance of the obtained transparent conductive substrate is 90% in the visible light region (3 80 nm to 780 nm) in the infrared region. (average of 65% in (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) is 94% on average, and is transmitted in the infrared region (780 nm to 2700 nm). The average rate was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. The heat resistance of the substrate, the surface resistance after the heat resistance test was 1.2 times that of the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality did not change before and after the immersion, and it was found that the film resistance was resistant. Further, the acidity of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved, but the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. As described above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. -102 - 201200616 (Comparative Example 8) Using zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%) as raw material powder, etc. A mixture of raw material powders was obtained by mixing the atomic ratio of Zn: Ti to a ratio of 99:1. Then, the obtained mixture was poured into a mold, and molded at a forming pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The molded body was heated at 400 ° C for 3 hours under an argon atmosphere of a normal pressure (1.01325 x 10 kPa) to obtain an oxide mixture (C8 ) °. Energy dispersive fluorescent X-ray device (manufactured by Shimadzu Corporation) "EDX-700L") analysis of the obtained oxidation mixture (C8), the atomic ratio of Zn to Ti is Zn: Ti = 99: l (Ti / (Zn + Ti) = 0.001) ο Next, the obtained oxide mixture (C8) It was processed into a disk shape of 20πιπι, and a target was produced. Using this target, a transparent conductive film having a thickness of 3 20 nm was formed by a PLD method in a film formation time of 120 minutes as in Example 19. For the composition (Zn : Ti) in the transparent conductive film to be formed, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the amount of measurement is measured by a fluorescent X-ray method. The line was quantitatively analyzed as Zn: Ti (atomic ratio) = 99:1. Further, the transparent conductive film was subjected to X-ray diffraction as in Example 19, and the doping state and crystal structure of titanium to zinc were investigated, and the Zinc-oriented wurtzite-type -103-201200616 single phase was And understand that titanium replacement is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 2.3 4 x 1 (r3Q.Cm, and the surface resistance was 73.2 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The obtained transparent conductive substrate The transmittance was 90% on average in the visible light region (380 nm to 780 nm). Further, the transmittance of the quartz glass substrate before the film formation in the visible light region was the same as in Example 19. Evaluation of the resistance of the obtained transparent conductive substrate The surface resistance after the moisture resistance test was 2.4 times that of the surface resistance before the moisture resistance test, and it was found to be poor in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was a heat resistance test. The surface resistance of the former was 2.2 times, which was found to be poor in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film after immersion was completely dissolved and disappeared. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved. From the above, it can be seen that although the film on the obtained transparent conductive substrate is transparent, the electric resistance is large and the conductivity is poor, and the chemical durability (heat resistance, moisture resistance, A transparent conductive film which is also poor in alkali resistance and acid resistance. (Example 22) A zinc oxide powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; High Purity Chemical Research Institute) (manufactured by a product, purity: 99.99%) as a raw material powder, which is mixed in a ratio of atomic ratio of Zn:Ti to 97:3 to obtain a mixture of raw material powders -104 to 201200616. Next, the resulting mixture is poured. In the mold, a single-axis press was used to form a forming pressure of 500 kg/cm 2 to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was subjected to an argon atmosphere at a normal pressure (1.0 1 325 xl 02 kPa). Sintering at 8 00 °C for 4 hours to obtain an oxide sinter (20). The oxidized sinter (20) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti is Zn: Ti = 97: 3 (Ti/(Zn + Ti) = 〇.〇3). X-ray diffraction device ("RINT2〇00" manufactured by Rigaku Motor Co., Ltd.) Investigate the crystal structure of the oxide sinter (2〇), which is zinc oxide (ZnO) and A mixture of crystal phases of zinc zirconium (ZnaTiCU) is completely absent. Next, the obtained oxide sintered product (20) is processed into a disk shape of 2 〇ηηπιφ to prepare a target, and the target is formed by PLD method. A transparent conductive film is obtained to obtain a transparent conductive substrate. That is, the target and the quartz glass substrate facing the target are placed in the "PS-2000" manufactured by the pulsed laser vapor deposition device industry. In the laser light-emitting device ("Comex 205" manufactured by Lambda Physik Co., Ltd.), a transparent conductive film having a film thickness of 3 〇〇 nm was formed under the film formation conditions described below for a film formation time of 120 minutes. &lt;film formation conditions&gt;

Laser: ArF excimer laser (wavelength = 193 nm) Laser energy: 1 8 m J -105- 201200616

Repeat frequency: 5Hz Target to substrate distance: 40nm Substrate: Corning #1737 Substrate temperature (°C): 200V Base pressure: 7.2xlO — 4Pa Gas pressure (oxygen): 〇.25Pa Gas flow rate: 8.6sccm Membrane Thickness: 3 OOnm Composition of the transparent conductive film formed (Zn:Ti) 'Using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), using the fluorescent X-ray method Quantitative analysis using a calibration curve is Zn: Ti (atomic ratio) = 97:3. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2 x 1 (Γ4 Ω·cm, and the surface resistance was 1 4.0 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the substrate is 90% in the visible light region (380 nm to 780 nm) and 65% in the infrared region (-106-201200616 780 nm to 2700 nm). Further, the glass substrate before film formation is visible light. The transmittance in the region (380 nm to 780 nm) was 94%, and the transmittance in the infrared region (780 nm to 2700 nm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the moisture resistance test surface resistance was before the moisture resistance test. The surface resistance of the obtained transparent conductive substrate after the heat resistance test was evaluated as 1.3 of the surface resistance before the heat resistance test, and the heat resistance was excellent. The obtained transparent conductive substrate was evaluated. Alkali resistance, change before and after immersion, it is known that it is excellent in alkali resistance. Moreover, the acid resistance of the obtained transparent substrate was evaluated, and the film thickness after immersion was thinned and dissolved, but the acid resistance was not changed before immersion. From the above, it is understood that the film on the obtained transparent conductive substrate is a transparent conductive film which has both chemical resistance (heat resistance, moisture resistance, and acid resistance) and is also oxidized. Zinc powder (ΖηΟ; Wako Pure Chemical Industries Co., Ltd. grade) and titanium oxide powder (TiO; High Purity Chemical Research Institute (stock, purity 99.99%) as raw material powder, so that Zn: sub-ratio becomes The ratio of 97:3 was mixed, and the raw material powder was mixed. The obtained mixture was poured into a mold and formed by a uniaxial press at a pressure of 500 kg/cm2 to obtain a diameter of 30 mm and a thickness of 5 mm. Properties, heat-resistant times, film quality, non-conductivity, film quality and low alkali resistance, special production of Ti. The shaped disk -107-201200616 shaped body. The shaped body is at normal pressure ( 1.01325x102kPa) was sintered at 800 °C for 4 hours under an argon atmosphere to obtain an oxide sintered product (21). The energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation) was analyzed. Oxidized burning The atomic ratio of the precipitate (21) and Zn to Ti is Zn: Ti = 97: 3 (Ti/(Zn + Ti) = 0.03). The x-ray diffraction device ("RINT2000" manufactured by Rigaku Motor Co., Ltd.) The crystal structure of the oxide sintered product (21) was investigated as a mixture of a crystal phase of zinc oxide (ZnO) and zinc titanate (Zn2Ti04), and the oxidation was completely absent. Next, the obtained oxide sintered product (21) The disk was processed into a disk shape of 2 Ommcj), and a target was produced, and a transparent conductive film was formed by a PLD method using the target to obtain a transparent conductive substrate. In other words, the target and the quartz glass substrate facing the target are placed in a pulsed laser vapor deposition device ("PS-2 0 00" manufactured by Seonnam Industrial Co., Ltd.), and a thunder is used. A light-emitting device ("Comex 205 type" manufactured by Lambda Physik Co., Ltd.) was used to form a transparent conductive film having a film thickness of 300 nm under the film formation conditions described below under a film formation time of 120 minutes. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm) Laser energy: 1 8 mJ Repetition frequency: 5 Hz Target to substrate distance: 40 nm -108 - 201200616

Substrate: Corning#〗 737 Substrate temperature (°C): 2 0 0 °C Base pressure: 7.2x1 (T4Pa gas pressure (oxygen): 〇.25Pa Gas flow rate: 8.6sccm Film thickness: 3 OOnm Transparent formation In the conductive film, (Zn : Ti ) ', a long-spreading type fluorescent X-ray device (XRF-1 700WS manufactured by Shimadzu Corporation) was quantitatively analyzed by a fluorescent X-ray method using a calibration curve to obtain Zn. : Ti (atomic ratio) = 97 : 3. In addition, the X-ray diffraction device ("RINT2000" from Rigaku Electric Co., Ltd.) is used for X-ray diffraction, and the X-ray diffraction is used for the attachment of the film. The energy dispersive X-ray microanalyzer (ΤΕΜ· ) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission type electron display (FE-SEM), which is a single phase of the fiber-zinc ore aligned with the C axis. The titanium substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate is 1〇-40. (111, the surface resistance is 13.30/匚|. Further, the transparent substrate has a specific resistance in the surface. Uniform. The transmittance of the obtained transparent conductive substrate is 380 nm in the visible light region. 78 0nm) an average of 90% 'in) in the infrared region 7 80nm ~ 2700nm average of 65%. Furthermore, the transmittance of the stone substrate before the film formation in the visible light region (380 nm to 780 nm) is the domain on the 4.Ox of the ray-emitting EDX micromirror type (domain (both of which is - 109-201200616 94%, the transmittance in the infrared region (780nm to 2700nm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the moisture resistance test surface resistance was 1.7 times that of the surface resistance before the moisture resistance test. In addition, the surface resistance after the heat resistance test of the obtained transparent conductive substrate was 1.3 as the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated before and after the immersion. In addition, the acid resistance of the obtained transparent substrate was evaluated, and the thickness of the obtained transparent substrate was evaluated to be thin and dissolved. However, it was found that the acid resistance was excellent without change before immersion. From the above, it was found that the obtained transparent conductive substrate was obtained. The upper film is a transparent conductive film which has both chemical resistance (heat resistance, moisture resistance, and acid resistance). (Example 24) Zinc oxide powder (ZnO; and light) Pure pharmaceutical industry (stock) grade) and titanium oxide powder (Ti203 (III); high purity chemical ruthenium), purity 99.99%) as raw material powder, the atomic ratio of j:Ti is 97:3 The mixture is mixed in proportion to obtain the original mixture. After the mixing operation, the ball and the ethanol are removed and poured into a mold (mold) made of graphite, and vacuum-pressurized by a pressure of 40 MPa by a graphite structure press. 〇0 (TC, 4 heat treatment, obtain a disk type oxide sinter (22) (the heat rate is average after the table moisture resistance, heat resistance, the film quality is not conductive, the film quality is clear and low alkali resistance, The research institute (analyzed Zn powder powder and powdered into a small amount of pressed-fired -110-201200616). The energy dispersive fluorescent ray-ray device ("EDX-700L" manufactured by Shimadzu Corporation) The oxide sintered product (22), the atomic ratio of Zn to Ti is Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03 ). The X-ray diffraction device (made by Rigaku Motor Co., Ltd.) RINT2000") investigated the crystal structure of the oxide sintered product (22), which is oxygen A mixture of zinc (ZnO) and a zinc crystal of zinc titanate (Zn2Ti04) is completely absent. Next, the obtained oxide sintered product (22) is processed into a disk shape of 20 ηηηηφ to prepare a target, and the target is used. A transparent conductive film is formed by a PLD method to obtain a transparent conductive substrate, that is, the target and the quartz glass substrate facing the target are placed on a pulsed laser vapor deposition device (manufactured by Chengnan Industrial Co., Ltd.) In the "PS-2000", a laser light-emitting device ("Comex 205" manufactured by Lambda Physik Co., Ltd.) was used, and a film thickness of 300 nm was formed under the film formation conditions described below for 120 minutes. Conductive film. &lt;film formation conditions&gt; Laser: ArF excimer laser (wavelength = l93 nm)

Laser energy: 18mJ Repeat frequency: 5Hz Target to substrate distance: 40nm Substrate: Corning#l 737

Substrate temperature (°C) : 2 0 0 °C Base pressure: 7.2xlO_4Pa -111 - 201200616 Gas pressure (oxygen): 〇.25Pa Gas flow rate: 8.6sccm Film thickness: 300nm The composition of the transparent conductive film formed ( Zn : Ti ), using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), using a fluorescent X-ray method, quantitative analysis using a calibration curve, and Zn: Ti ( Atomic ratio) = 97 : 3. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4.2×1 (Γ4 Ω·cm, and the surface resistance was 14.0 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the substrate is 90% in the visible light region (3 80 nm to 7 8 Onm) and 65% in the infrared region (780 nm to 2700 nm). Further, the quartz glass substrate before film formation is in the visible light region (380 nm). The transmittance in ~780 nm) is 94% on average, and the transmittance in the infrared region (780 nm to 27 〇 Onm) is 94% on average. The moisture resistance of the obtained transparent conductive substrate is evaluated, and the moisture resistance test is shown in Table-112. - 201200616 The surface resistance is 1.7 times the surface resistance before the moisture resistance test, and it is known that it is excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was the surface resistance before the heat resistance test. 1.3 times, it is known that the heat resistance is excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated. After the immersion, the film thickness is reduced and dissolved, but the film quality is not changed before and after the immersion, and it is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and also has chemical durability ( Transparent conductive film of heat resistance, moisture resistance, durability, and acid resistance. (Example 25) Zinc oxide powder (ΖηΟ; manufactured by Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II) ): a high-purity chemical research institute (purity: 99.99%), as a raw material powder, which is mixed in a ratio of atomic ratio of Zn:Ti to 97:3 to obtain a mixture of raw material powders. Pour the mixed powder obtained by removing the ball and ethanol into a mold (mould) made of graphite, and pressurize with a pressure of 40 MP a using a press machine made of graphite to carry out 100 ° C for 4 hours. The heat treatment was carried out to obtain a disk-shaped oxide sintered product (23) (hot press sintering), and the obtained oxide sintered product was analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). (twenty three), The atomic ratio of Zn to Ti is Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) -113 - 201200616 = 0-03 ). The oxidation is investigated by a xenon ray diffraction device (Riichi Electric Co., Ltd.) The material sinter (23) is a combination of zinc oxide (ZnO) and zinc titanate (Zn2Ti04), and titanium oxide is completely absent. Next, the obtained oxide sinter (23) is processed into a disk shape to prepare a target. Using this target, a film was formed by a PLD method to obtain a transparent conductive substrate. That is, the target, the opposite quartz glass substrate is placed in the "PS-2000" manufactured by the pulsed laser evaporation industry (shares), and the "Comex" is manufactured by Lambda Physik (share). 205 A transparent conductive film formed at a film formation time of 1 to 20 minutes under the following film formation conditions. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm)

Laser energy: 1 8 mJ Repeat rate: 5 Hz Target to substrate distance: 40 nm Substrate: Corning #l 737

Substrate temperature (°C): 200°C Base pressure: 7.2xl (T4Pa gas pressure (oxygen): 〇.25Pa gas flow rate: 8.6sccm Film thickness: 300nm) Manufactured “crystal structure, crystal phase mixture 2 Οηιιηφ The film is transparently conductive and is placed in the transparent conductive film formed by the film thickness of 10000 nm -114-201200616 (Zn:Ti) using a wavelength-dispersive type of fluorescent light. The X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was quantitatively analyzed by a fluorescent X-ray method using a calibration curve, and was Zxi ·· Ti (atomic ratio) = 97 ··3. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 4·0 χ 10·4 Ω·cm, and the surface resistance was 13.3 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 90% on average in the visible light region (380 nm to 780 nm) and 65% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.7 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.3 times that of the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent in the range of -115 to 201200616. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Example 26) As a raw material, zinc oxide powder (manufactured by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): manufactured by High Purity Chemical Research Institute, purity: 99.99%) The powder was mixed in such a ratio that the atomic ratio of Zn:Ti was 93:7 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and pressurized by a pressure of 40 MP a using a press machine made of graphite to carry out 1 000 ° C, 4 After an hour of heat treatment, a disk-shaped oxide sinter (24) (hot press sintering) was obtained. The oxide sintered product (24) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn : Ti = 93 : 7 ( Ti / ( Zn + Ti ) = 0-07). The crystal structure of the oxide sintered product (24) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and was a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Next, the obtained oxide sintered product (24) is processed into a disk shape of 20 ηηηηφ to prepare a standard, and a transparent conductive film β is obtained by a PLD method using the target to obtain a transparent conductive substrate β, that is, the target, and The quartz glass substrate which is aligned with the target -116-201200616 is placed in a pulsed laser evaporation apparatus ("PS-2000" manufactured by Seonnam I Co., Ltd.), and a laser illuminating device (Lambda Physik) is used. "Comex 205 type" manufactured by "Company" was formed into a transparent conductive film having a thickness of 3 〇〇 nm under the film formation conditions described below under a film formation time of 120 minutes. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm)

Laser energy _ 18mJ Repeat frequency: 5Hz Target to substrate distance: 40ηιη Substrate: Corning#l737 Substrate temperature (°C): 200°C Base pressure: 7.2xlO_4Pa Gas pressure (oxygen): 〇.25Pa Gas Flow rate: 8.6 sccm Film thickness: 30,000 nm The composition (Zn: Ti) in the transparent conductive film to be formed is used by a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation). The fluorescent X-ray method was quantitatively analyzed using a calibration curve, and was Zn: Ti (atomic ratio) = 93:7. In addition, X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray-117-201200616 diffraction was performed using an accessory for film measurement, and energy-dispersive X-rays were used. The microanalyzer (ΤΕΜ) investigates the doping state of titanium to zinc, and then uses electric field emission type electron display (FE-SEM) to investigate the crystal structure, which is a C-axis oriented fiber zincite single phase, and it can be understood that titanium replacement is dissolved in zinc. in. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 10 - 4 O.cm and a surface resistance of 30.0 Ω / □. Further, the transparent substrate has a uniform in-plane specific resistance distribution. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region (380 nm to 780 nm) and 67% in the infrared region 780 nm to 2700 nm. Further, the transmittance of the glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94%, and the transmittance in the infrared region (780 nm to 27 Å Onm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.4 times the surface resistance before the moisture resistance test, and it was found that the surface resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. (Comparative Example 9) As a raw material powder, zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (TiO (II); high purity chemical research institute), purity 99.99% These are mixed so that the atomic ratio of Ti is 88:12, and the domain of the raw material powder-EDX micromirror type on the 9.Ox is obtained (the field (the average glass is wet and heat resistant, can, special ( Stock Zn: the mixture of -118- 201200616. After the mixing operation, the ball and ethanol are removed and put into a mold (mold) made of graphite, and vacuum-pressurized by a graphite machine at a pressure of 40 MPa for 1 000. °C, heat treatment, to obtain a disk-shaped oxide sinter (C9) ( ). The oxides of the sintered Zn and Ti were analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). The ratio is Zn : Ti = 88 : 12 ( Ti / 0.12 ). The oxide sinter (C9) is investigated as zinc oxide (ZnO) and zinc titanate by an X-ray diffraction device (Rcimeter RINT2000). The precipitate of (Zn2Ti04), titanium oxide is completely absent. Next, the obtained oxygen The sintered product (C9) is processed into a disk shape to prepare a target, and a target is formed by a PLD method using the target to obtain a transparent conductive substrate. That is, the target is placed in a pair of quartz glass substrates in a pulsed mine. In the "PS-2 000" manufactured by the Jet Vapor Coating Co., Ltd., and formed by Lambda Physik ("Comex 205" under the film forming conditions below, the film formation time is 1 20 minutes. Transparent conductive film. &lt;Film formation conditions&gt; Laser: ArF excimer laser (wavelength = 193 nm) Laser energy: 18 mJ Repeat frequency: 5 Hz Mixed powder is formed by pressing for 4 hours of heating and pressing sintering. (C9), (Zn+Ti) = ) "Crystal structure, crystal phase mixing 20mm &lt;j&gt; film transparent conductive and the target (Shengnan industrial light-emitting device type)), in film thickness 300nm -119- 201200616

Target to substrate distance: 40 nm Substrate: Corning #l 737 Substrate temperature (°C): 200°C Base pressure: 7.2xlO_4Pa Gas pressure (oxygen): 〇.25Pa Gas flow rate: 8.6sccm Film thickness: 300nm For the composition (Zn : Ti ) in the transparent conductive film to be formed, a wavelength-dispersive fluorescent X-ray device ("XRF-l7〇OWS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used for inspection. Quantitative analysis of the measuring line is Zn: Ti (atomic ratio) = 88:12. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then uses electric field radiation type electron microscopy (FE-SEM) to investigate the crystal structure, which is a single phase of the C-axis aligned wurtzite type. In zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 X 1 (Γ2 Ω · cm, and the surface resistance was 3 67.0 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the transparent conductive substrate is 90% in the visible light region (380 nm to 780 nm) and is % in the infrared region (780 nm to 2700 nm). Further, the quartz glass-120-201200616 glass substrate before film formation The transmittance in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (78 〇 nm to 27 〇 Onm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated and resistant. The surface resistance after the wet test was 1.1 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was the surface before the heat resistance test. When the electric resistance is 1.1 times, it is known that the heat resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). through Conductive film, but high resistance. (Comparative Example 1 〇) Zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203 (III): High Purity Chemical Research Institute ( (manufactured by the company), purity 99.99%) as a raw material powder, which is mixed in a ratio of atomic ratio of Zn:Ti to 8 8 : 1 2 to obtain a mixture of raw material powders. After the mixing operation, the ball and ethanol are removed. The mixed powder is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite, and heat-treated at 1 000 ° C for 4 hours to obtain a disk-shaped oxidation. Sintered material (C10) (hot press sintering). The obtained oxide sintered product (C10), Zn and Ti atoms were analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). The ratio is Zn: Ti = 88: 12 (Ti/(Zn + Ti -121 - 201200616 ) = 0.1 2 ). The oxide sintering is investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.). Crystal structure of the substance (C10), which is zinc oxide (ZnO) and titanium A mixture of crystal phases of zinc (Zn2Ti04), titanium oxide is completely absent. Next, the obtained oxide sintered product (C10) is processed into a disk shape of 20 mm (J) to prepare a target, and the target is formed by PLD method. A transparent conductive film is obtained to obtain a transparent conductive substrate, that is, the target and the quartz glass substrate facing the target are disposed on a pulsed laser vapor deposition device ("PS-" manufactured by Seonnam Industrial Co., Ltd. In 2000), a transparent conductive film having a thickness of 300 nm was formed by a laser light-emitting device ("Comex 205 type j" manufactured by Lambda Physik Co., Ltd.) under the film formation conditions described below for a film formation time of 120 minutes. &lt;film formation conditions&gt; Laser: ArF excimer laser (wavelength = l93 nm)

Laser energy: 18mJ Repeat frequency: 5Hz Target to substrate distance: 40nm Substrate: Corning#1737

Substrate temperature (°C) · 200°C Base pressure: 7.2xlO_4Pa Gas pressure (oxygen): 0_25Pa Gas flow rate: 8.6sccm Film thickness: 300nm • 122- 201200616 Composition in the formed transparent conductive film (Zn: Ti) Quantitative analysis using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) using a calibration curve to measure Zn: Ti (atomic ratio) =88 : 12. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. The transparent conductive film on the transparent conductive substrate obtained has a specific resistance of 2.4 x 10 _2 Ω·cm and a surface resistance of 800.0 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the transparent conductive substrate is 90% in the visible light region (380 nm to 780 nm), and averaged in the infrared region (780 nm to 2700 nm). 75%. Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (78 nm to 27 Å Onm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.1 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times that of the surface resistance before the heat resistance test, and it was found that -123-201200616 was excellent in heat resistance. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent, and at the same time, it has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film, but is high in resistance. (Example 27) As a raw material powder, zinc oxide powder (made by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%) These were mixed in such a ratio that the atomic ratio of Zn:Ti was 96:4 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a forming pressure of 50 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was annealed at 500 ° C for 3 hours under an argon atmosphere under a normal pressure (100 Pa) to obtain an oxide mixture (25). The oxidation mixture (25) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 96: 4 (Ti/( Zn + Ti) = 0.04) Then, the obtained oxide mixture (25) was processed into a disk shape of 2 Οιηιηφ to prepare a target. A transparent conductive film was formed by ion plating using the target to obtain a transparent conductive substrate. In other words, ion plating was performed using an ion plating apparatus ("SUPLaDUO" manufactured by Sino-foreign Furnace Co., Ltd.) under the following conditions, and a film thickness of 200 nm was formed on a transparent substrate (thickness-free 7 mm thin glass substrate). 124- 201200616 Transparent conductive film. : 2 5 0. . : 0.3Pa : argon gas = 160sccm, oxygen: 100A: 200 seconds before the film formation, pre-heating temperature of the film formation, film formation, atmospheric gas condition at the time of film formation = 2 s ccm, discharge current, film formation time, film formation The composition (Zn : Ti ) in the transparent conductive film is measured by a fluorescent X-ray method using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) Quantitative analysis is Zn: Ti (atomic ratio) = 96: 4. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 7.3 X 10 4 Ω · cm, and the surface resistance was 36.5 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region (380 nm to 780 nm) and 65% in the infrared region (780 nm to 2700 nm). Further, the glass substrate-125-201200616 before the film formation had an average transmittance of 94% in the visible light region (380 nm to 780 nm) and an average transmittance of 94% in the infrared region (780 nm to 2700 nm). The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.3 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. (Comparative Example 11) As a raw material powder, zinc oxide powder (manufactured by ZnO: Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity: 99.99%) These were mixed in such a ratio that the atomic ratio of Zn:Ti was 99:1 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a forming pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was annealed at 400 ° C for 3 hours under an argon atmosphere of normal pressure (100 Pa) at 1200 - 201200616 to obtain an oxide mixture (Cl 1 ). The obtained oxidation mixture (C11) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 99: 1 (Ti/( Zn + Ti) =0_01) Next, the obtained oxide mixture (C11) is processed into a disk shape of 20 mm φ to prepare a target, and a transparent conductive film is formed by ion plating using the target to obtain a transparent conductive substrate. . In other words, ion plating was performed using an ion plating apparatus ("SUPLaDUO" manufactured by Sino-foreign Furnace Co., Ltd.) under the following conditions, and a film thickness of 150 nm was formed on a transparent substrate (an alkali-free glass substrate having a thickness of 77 mm). Transparent conductive film. Pre-filming temperature before film formation Film pressure at film formation Gas atmosphere condition at film formation = 2 sccm Discharge current film formation time at film formation Time-dependent transparent conductive film medium-length dispersion type fluorescent X-ray device (XRF-1) 700WS"), using Quantitative Analysis of Camp Light, for Zn:Ti (Atomic Conductive Film, X-ray Diffraction: 25 0〇C: 0.3Pa: Xenon = 160sccm, Oxygen: 100A: 150 seconds) (Zn: Ti), using the X-ray method manufactured by the Shimadzu Manufacturing Co., Ltd., using the calibration line to calculate the number ratio = 99: 1. In addition, the translucent device (RIT2000, manufactured by Rigaku Motor Co., Ltd. -127-201200616) ") X-ray diffraction was carried out using an accessory for film measurement, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM), and then electric field emission type electron emission (FE-SEM) was used to investigate crystallization. The structure is a single phase of the wurtzite aligned with the C axis, and it can be understood that the titanium substitution is dissolved in the zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 10·3 Ω·cm, and the surface resistance was 467 Ω/□. Further, the transparent substrate has a uniform in-plane specific resistance distribution. The transmittance of the obtained transparent conductive substrate was 91% in the visible light region of 380 nm to 780 nm, and 70% in the infrared region of 780 nm to 2700 nm. Further, the transmittance of the glass plate before film formation in the visible light region (380 nm to 780 nm) was on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 3.1 times that of the surface resistance before the moisture resistance test, and it was found to be resistant. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the test was 3.0 times the surface resistance before the heat resistance test, and it was found that the heat resistance was poor. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was completed and disappeared after the immersion. Further, the acid resistance of the obtained transparent conductive substrate was evaluated and all dissolved and disappeared. From the above, it can be seen that the film on the obtained transparent conductive substrate is transparent but has high electrical resistance and chemical durability (heat resistance, moisture resistance, and alkali-resistant EDX micromirror type on the field of 7. Ox (field) The base I 94 is a transparent conductive film which is wet heat-resistant, fully melt-soluble, and resistant to -128 to 201200616 acid. (Example 28) An oxide mixture obtained as in Example 27 (25) processing into a disk shape of 20 mmcj), producing a target, and forming a transparent conductive film by ion plating using the target to obtain a transparent conductive substrate. That is, using an ion plating apparatus (manufactured by Sino-foreign furnace industry) "SUPLaDUO") was subjected to ion plating under the following conditions to form a 50 nm-th transparent conductive film on a transparent substrate (an alkali-free glass substrate having a thickness of 0.7 mm): 25 0 〇C: 0.3 Pa: argon = 160 sccm 'Oxygen: 1 00A: 50 seconds before film formation, pre-heating temperature at film formation, film formation pressure, ambient gas condition, 2 sc cm, discharge current, film formation time

For the composition (Zn:Ti) in the formed transparent conductive film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) was used, and the amount of the measurement was measured by the fluorescent X-ray method. The line was quantitatively analyzed as Zn: Ti (atomic ratio) = 96:4. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX -129- 201200616 )Investigate the doping state of titanium to zinc 'Re-use electric field emission type electron-display (FE-SEM) to investigate the crystal structure, which is a C-axis oriented fiber zinc-zinc single phase, which can be understood to be titanium-substituted solid solution. In zinc. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 10 _ 4 Ω · cm and a surface resistance of 160 Ω / □. Further, the transparent substrate has a uniform in-plane specific resistance distribution. The transmittance of the obtained transparent conductive substrate was 91% in the visible light region of 3 80 nm to 7 8 Onm ) and 70% in the infrared region of 78 0 nm to 2700 nm. Further, the transmittance of the glass plate before film formation in the visible light region (380 nm to 780 nm) was averaging 5%, and the transmittance in the infrared region (78 0 nm to 27 Å Onm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.8 times the surface resistance before the moisture resistance test, and it was found that the surface resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the test was 1.5 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent guide substrate was evaluated, and the film thickness was thinned and dissolved after the impregnation, but it was found that the acid resistance was excellent without change before and after the immersion. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and has a chemical resistance (heat resistance, moisture resistance, alkali resistance, acid resistance) and a transparent conductive film. The domain of the mirror type 8.0 X (domain (the glass base I 94 is wet heat resistant, the quality of the electrolyte film is not long - 130-201200616 (Example 29)) as obtained by Example 27. The oxide mixture (25) is processed into a disk shape of 20 mm &lt; p, and a target is produced, and a transparent conductive film is formed by ion plating using the target to obtain a transparent conductive substrate. That is, an ion plating apparatus (Chinese and foreign furnaces) is used. "SUPLaDUOj" manufactured by the Industrial Co., Ltd. is subjected to ion plating under the following conditions, and a transparent conductive film having a thickness of 200 nm is formed on a transparent substrate (a heat-resistant transparent resin film having a heat resistance of 3.3 mm or more). Membrane : 2 00 ° C : 0.3 Pa : gas = 160 sccm, oxygen: 1 00 A : 2 00 seconds Substrate pre-heating temperature before film formation Pressure at film formation Gas atmosphere condition = 2 sc cm Film formation Discharge current In the film formation time, the composition (Zn : Ti ) in the transparent conductive film to be formed is a wavelength-dispersive fluorescent X-ray device ("XRF- 1 7 00WS" manufactured by Shimadzu Corporation), and the fluorescent X-ray method is used. Quantitative analysis using a calibration curve is Zn: Ti (atomic ratio) = 96: 4. Further, an X-ray diffraction device ("RINT20Q0" manufactured by Rigaku Electric Co., Ltd.) is used for the transparent conductive film. X-ray diffraction was carried out using an accessory for film measurement, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and then an electric field emission type electron microscope was used -131 - 201200616 (FE- SEM) investigated the crystal structure, which is a single phase of the C-axis alignment, and it can be understood that the titanium substitution is dissolved in zinc. The ratio of the transparent conductive film on the obtained transparent conductive substrate is 10_4 Ω·cm, and the surface resistance is 42.5 Ω/□. Furthermore, the specific resistance distribution is in-plane uniform. The transmittance of the obtained transparent conductive substrate is 85 % in the range of j 3 80 nm to 780 nm, and 65 in the red 780 nm to 2700 nm. %. Further, the film-forming resin film is visible light. 90% in the domain (380 nm to 780 nm) and 90% in the infrared region (780 nm to 2700 nm). The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance before moisture resistance test was 1.8. In addition, it is known that the surface resistance after the test of the obtained transparent conductive substrate is the surface resistance before the heat resistance test, and it is excellent in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the immersion was changed, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the immersion was not changed, and it was found that the acid resistance was excellent. From the above, it is understood that the film heat-resistant film obtained on the transparent conductive substrate is also transparent and low-resistance, and also has a transparent wurtzite type resistance (heat resistance, moisture resistance, alkali resistance, acid resistance). It is the I-light area (the line area on the 8.5 X bright substrate). The surface after the transmittance test of the heat-resistant transmittance is known as moisture-resistant heat, heat-resistant 1.5 times, and there is no transparent conductive stain on the front and back film. For example, the substrate is a chemically durable conductive film. -132- 201200616 (Example 3 0 ) Zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and Oxide powder (Ti2〇3; high purity) The Chemical Research Institute (product) produced 'purity of 99.99%' as a raw material powder, and the mixture was mixed in a ratio of the atomic ratio of zn: Ti to 9 ό 4 to obtain a mixture of raw material powders. Then, the obtained mixture was poured. The mold was molded at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was subjected to a helium atmosphere at a normal pressure (1.0 1 325 x 1 〇 2 kPa). At 800 °C The resulting oxide sinter (26) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation). The ratio is Zn: Ti = 96: 4 (Ti/(Zn + Ti) = 0.04). The oxide sintered product (26) is investigated by an x-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.). The crystal structure is a mixture of a crystal phase of zinc oxide (ZnO) and zinc titanate (Zn2Ti04), and the titanium oxide is completely absent. Next, the obtained oxide sintered product (26) is processed into a disk shape of 20ηιπιφ, and is produced. In the target, a transparent conductive film is formed by ion plating using the target to obtain a transparent conductive substrate. That is, ion plating is performed under the following conditions using an ion plating apparatus ("SUPLaDUO" manufactured by Sino-foreign Furnace Co., Ltd.). A transparent conductive film having a film thickness of 200 nm was formed on a transparent substrate (an alkali-free glass substrate having a thickness of 0.7 mm). -133- 201200616 Pre-heating temperature of the substrate before film formation: 2 5 0 〇C Pressure at film formation: 0.3 Pa atmosphere when filming Body conditions: argon: cm Discharge current at film formation: 1 00A Film formation time: 200 sec. Composition of oxygen-related transparent conductive film (Zn : Ti ) 'Long-spread fluorescent X-ray device (Shimadzu Manufactured by the manufacturer (sold) XRF-1 700WS), quantitative analysis using a calibration curve using a fluorescent X-ray method, Zn: Ti (atomic ratio) = 96:4. In addition, an X-ray diffraction device ("RINT2000" of Rigaku Electric Co., Ltd.) was used for the bright conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer (TEM·) was used. The doping state of titanium to zinc was investigated, and the crystal structure was investigated by electric field emission type electron emission (FE-SEM), which was a single phase of the fiber-zinc ore aligned with the C-axis. It can be understood that the titanium substitution is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1 CT4 Ω·cm, and the surface resistance was 39.0 Ω/□. Further, the transparent substrate has a uniform in-plane specific resistance distribution. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region of 380 nm to 78 nm, and was 65% in the infrared region of 780 nm to 2700 nm. Furthermore, the transmittance of the glass plate before film formation in the visible light region (3 80 nm to 780 nm) is averaged; | the wave is used to perform the transmission on the ray of the EDX micromirror type on the 7.8x domain (domain ( Glass base I 94 -134 - 201200616 %, 94% in the infrared region (780 nm to 2700 nm). The moisture resistance of the obtained transparent conductive substrate was evaluated, and the sheet resistance was 1.5 times that of the surface resistance before the moisture resistance test. In addition, the surface resistance after the test of the obtained transparent conductive substrate was evaluated as the surface resistance before the heat resistance test, and the heat resistance was excellent. The evaluation of the alkali resistance and the change in the immersion of the obtained transparent conductive substrate was considered to be alkaline resistance. In addition, the acid resistance of the substrate was evaluated, and the film thickness after thinning was reduced and dissolved. However, it was found that the acid resistance was excellent without change. From the above, it was found that the resistance on the obtained transparent conductive substrate was also chemically durable. Transparent conductive film (heat resistance, resistance, acid resistance). (Example 3 1 ) Zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd.) and titanium oxide powder (Ti203; high purity chemical structure, pure 99.99%) As a raw material powder, the atomic ratio is mixed at a ratio of 96:4 to obtain a raw dog. After the mixing operation, the mold (mold) composed of the mixed ink obtained by removing the ball and ethanol is used. A pressure vacuum pressure of 40 MPa was formed from graphite, and 1000 ° C, 4 /J. was obtained to obtain a disk-shaped oxide sintered product (27). The average transmittance after the wet test is known as moisture resistance and heat resistance. , 1.3 times of heat resistance, can be made before and after the film is not transparent, conductive film is transparent and low-humidity, alkali-resistant stock before and after the impregnation, the U-made Zn: Ti powder mixture powder Pour into the stone punching machine and heat it at the same time -135- 201200616 The atomic ratio of the oxide Zn to Ti obtained by the energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimajima) is Zn: Ti = 96 : 4 = 0.04) «Investigate the oxide sinter with X-ray diffraction device (RIT2000) (27 is zinc oxide (ZnO) and zinc titanate (Zn2Ti04), and titanium oxide does not exist at all. Next, the obtained oxide sintered product (27) Adding a disk shape to prepare a target, and using the target to obtain a transparent conductive substrate by using an ion-electric film, that is, using "SUPLaDUO" manufactured by an outer furnace industry (stock), ion plating, on a transparent substrate ( On a thickness of 〇7 mm), a transparent conductive film having a film thickness of 200 nm was formed.

Pre-heating temperature of substrate before film formation: 250 °C Pressure at film formation: 0.3 Pa Ambient gas condition at film formation: Argon = 2

Discharge current at the time of film formation: 100 A Film formation time: 200 seconds. Composition in a transparent conductive film formed (Zn long-dispersion fluorescent X-ray device (Shimadzu Corporation XRF-1 700WS)), using a fluorescent X-ray method, Quantitative analysis: Zn: Ti (atomic ratio) = 96: crystallization plant (27), crystal structure of "Ti/ ( Zn + Ti ) (stock), "crystal phase" A method of forming a transparent transparent electrode electroplating device by a method of mixing into a film of 20 π ι η φ (in the case of "no glass substrate 1 60 sccm, oxygen: Ti under the following conditions", using a wave (stock)" The X-ray diffraction device ("RINT2〇00" of Rigaku Electric Co., Ltd.) is used for the conductive film of 136-201200616, and X-ray diffraction is performed using an accessory for film measurement, and energy-dispersive X-ray is used. The microanalyzer (TEM) was used to investigate the doping state of titanium on zinc, and then the electric field radiation-type electron display (FE-SEM) was used to investigate the crystal structure. The C-axis is aligned with the wurtzite single phase, and the titanium substitution is dissolved in zinc. The transparent guide on the obtained transparent conductive substrate The specific resistance of the film is 10_4n.cm, and the surface resistance is 36.5Ω/□. Furthermore, the specific resistance of the transparent substrate is in-plane. The transmittance of the obtained transparent conductive substrate is in the visible light region of 380 nm to 7 8 Onm. The average is 90%, and the average is 65% in the infrared region of 780 nm to 2700 nm. Further, the transmittance of the glass plate before film formation in the visible light region (380 nm to 780 nm) was 1% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found to be excellent in resistance. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the test was 1.3 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent guide substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, it was found that the acid resistance was excellent without change before and after the immersion. The field on the 7.3x of the ray EDX micromirror type is produced (the field (the glass base | 94 is a wet heat-resistant, temperament-free film-137-201200616. From the above, it is known that the film on the obtained transparent conductive substrate is A transparent conductive film which is transparent and has low electrical resistance and also has chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). (Example 32) Zinc oxide powder (ZnO; Wako Pure Chemical Industries Co., Ltd. Manufactured, special grade) and titanium oxide powder (TiO; manufactured by High Purity Chemical Research Institute, purity: 99.99%) as a raw material powder, which are mixed in such a ratio that the atomic ratio of Zn: Ti is 97:3. A mixture of raw material powders is obtained. After the mixing operation, the mixed powder obtained by removing the balls and the ethanol is poured into a mold (mould) made of graphite, and pressed by a press machine made of graphite at a pressure of 40 MPa. The heat treatment at 1000 ° C for 4 hours was carried out to obtain a disk-shaped sintered product, and then the sintered product was sintered at 80 °C for 4 hours under an argon atmosphere to obtain an oxide sintered product (28). Fluorescent X-ray The oxide sinter (28) was analyzed by the line device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti is Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03). The crystal structure of the oxide sintered product (28) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), which is a crystal phase of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Then, the obtained oxide sinter (28) is processed into a disk shape of 20 ηηηηφ to prepare a target, and a transparent conductive film is formed by ion plating using the target to obtain a transparent conductive substrate. -138-201200616 That is, an ion plating apparatus ("SUPLaDUOj" manufactured by Sino-foreign Furnace Industry Co., Ltd.) was used for ion plating under the following conditions to form a film on a transparent substrate (an alkali-free glass substrate having a thickness of 0.7 mm). Transparent conductive film with a thickness of 200 nm. : 25 0 〇C : 〇.3Pa : Μ gas = 160 sccm, oxygen: 100 A: 200 sec. Pre-heating temperature of the substrate before film formation. Pressure at film formation. 2sccm discharge during film formation The composition (Zn : Ti ) in the transparent conductive film formed by the current film formation time is a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), and the fluorescent X-ray method is used. Quantitative analysis using a calibration curve is Zn: Ti (atomic ratio) = 97: 3. Further, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) is used for the transparent conductive film. X-ray diffraction was carried out using an accessory for film measurement, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and then an electric field emission electron microscope (FE-SEM) was used to investigate crystallization. The structure is a single phase of the wurtzite type aligned with the C axis, and it can be understood that the titanium substitution is dissolved in the zinc. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 6.0 × 10 -4 Ω · cm and a surface resistance of 30.0 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. -139-201200616 The transmittance of the obtained transparent conductive substrate was 90% on average in the visible light region (3 8 〇 11111 to 78 〇 11111) and 65% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.3 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, testability, and acid resistance) transparent conductive film. (Example 33) As a raw material powder, zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and Oxygen powder (TiO; Bureau of Purity Chemical Research Institute (purity: 99.99%) were used as raw material powders. These were mixed so that the original 'sub-number ratio of Zn: Ti became 97:3' to obtain a mixture of raw material powders. -140-201200616 Next, the obtained mixture was poured into a mold, and molded at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The molded body was sintered at 1000 ° C for 4 hours under an argon atmosphere at a normal pressure (1.0 1 3 25 x 1 02 kPa) to obtain an oxide sintered product (29) and an energy dispersive fluorescent X-ray device (Shimadzu Corporation) (EDM) Manufactured "EDX-700L") The oxidized sintered product (29) was analyzed, and the atomic ratio of Zn to Ti was Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti) = 0.03 ). The X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used to investigate the crystal structure of the oxide sintered product (29), which is a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). And the titanium oxide is completely absent. Next, the obtained oxide sintered product (29) was processed into a disk shape of 20 ηηηιφ to prepare a target, and a transparent conductive film was formed by ion plating using the target to obtain a transparent conductive substrate. In other words, ion plating was performed using an ion plating apparatus ("SUPLaDUO" manufactured by Sino-foreign Furnace Co., Ltd.) under the following conditions, and a film thickness of 200 nm was formed on a transparent substrate (an alkali-free glass substrate having a thickness of 77 mm). Transparent conductive film. Pre-heating temperature of substrate before film formation: 250t Pressure at film formation: 0.3Pa Ambient gas condition at film formation: Argon gas = 160 sccm' Oxygen = 2 sccm

Discharge current at the time of film formation: 100A - 141 - 201200616 Film formation time: 2 0 〇 Second, the composition (Zn : Ti ) in the formed transparent conductive film, and the long-dispersion type fluorescent X-ray device (Shimadzu Corporation) Manufacture of XRF-1 700WS") by fluorescence X-ray method using a calibration line quantitative analysis, Zn: Ti (atomic ratio) = 95:5. In addition, the X-ray diffraction device ("RINT2000" of Rigaku Electric Co., Ltd.) is used for the bright conductive film, and X-ray diffraction is performed using an accessory for film measurement, and an energy-dispersive X-ray microanalyzer (TEM.) is used. Investigate the doping state of titanium on zinc, and then use electric field emission type electron display (FE-SEM) to investigate the crystal structure, which is a single phase of the fiber-zinc ore aligned with C-axis, and can understand the transparent conductivity of titanium in solid solution in zinc. The specific conductive resistance of the transparent conductive film on the substrate was 10_4 Ω · cm, and the surface resistance was 30.0 Ω / □. Further, the transparent substrate has a uniform in-plane specific resistance distribution. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region of 380 nm to 780 nm, and 65% in the infrared region of 780 nm to 270 Å. Further, the transmittance of the glass plate before film formation in the visible light region (380 nm to 780 nm) was f%, and the transmittance in the infrared region (780 nm to 2700 nm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.6 times the surface resistance before the moisture resistance test, and it was found to be excellent in resistance. In addition, the heat resistance of the obtained transparent conductive substrate was evaluated, and the wave was used to perform the field of 6.0 X on the ray-transmission EDX micromirror type (m (glass base | 94 is a table of wet heat resistance - 142 - 201200616 test) The surface resistance of the surface resistance was 1.3 times that of the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. The obtained transparent conductive substrate has an acid resistance, and the film thickness after the immersion is thinned and dissolved. However, the film quality is not changed after the immersion, and it is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance. A transparent conductive film which has chemical durability (heat resistance, moisture resistance, alkali resistance, and acid resistance). (Comparative Example 1 2 ) Manufactured by zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) And titanium oxide powder (TiO; manufactured by High Purity Chemical Research Institute, purity: 99.99%) as a raw material powder, such that the atomic ratio of Zn: Ti is 98.5:1.5. The mixture was mixed to obtain a mixture of the raw material powders. Then, the obtained mixture was poured into a mold, and formed at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. Under an argon atmosphere of pressure (1.0 1 3 25 XI 02 kPa), it was sintered at 1 ° C for 4 hours to obtain an oxide sintered product (C12). Energy dispersive fluorescent X-ray device (Shimadzu Corporation) The "EDX-700L" manufactured by the analysis of the obtained oxidized sintered product (C12), the atomic ratio of Zn to Ti is Zn : Ti = 98.5 : 1.5 ( Ti / ( Zn + Ti ) = 0.015 ). Using X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.). The crystal structure of the oxide sintered product (C12) was investigated, and it was found that the crystal structure of zinc oxide (ZnO) and zinc titanate (Zn2Ti04) was a mixture. Next, the obtained oxide sintered product (C12) is processed into a disk shape of 20πηηφ to prepare a target, and a transparent conductive film is formed by ion plating using the target to obtain a transparent conductive substrate. Using ions The plating apparatus ("SUPLaDUO" manufactured by Sino-foreign Furnace Industry Co., Ltd.) was subjected to ion plating under the following conditions, and a transparent conductive film having a thickness of 200 nm was formed on a transparent substrate (an alkali-free glass substrate having a thickness of 77 mm). 2 5 0〇C : 0.3Pa : Hydrogen = 160sccm, Oxygen: 1 00A : 2 00 seconds Substrate pre-heating temperature before film formation Pressure at film formation Gas atmosphere condition 2 s ccm Discharge current at film formation In the film formation time, the composition (Zn:Ti) in the transparent conductive film to be formed is a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), and the X-ray method is used. Quantitative analysis using a calibration curve is Zn: Ti (atomic ratio) = 98.5: 1.5. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM- -144- 201200616 EDX ) Investigate the doping state of titanium to zinc, and then investigate the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-oriented bauxite type. It is dissolved in zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.2×10 −3 Ω·cm, and the surface resistance was 60.0 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region (380 nm to 780 nm) and 70% in the infrared region (78 0 nm to 2700 nm). Further, the transmittance of the glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (78 0 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 2.6 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was poor. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 2.0 times the surface resistance before the heat resistance test, and it was found that the heat resistance was poor. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared after the immersion. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared. From the above, it is understood that the film on the obtained transparent conductive substrate is a transparent conductive film which is transparent and has low electrical resistance but is inferior in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). 145-201200616 (Comparative Example 1 3 ) Manufactured by zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO; manufactured by High Purity Chemical Research Institute, purity 99.99%) As the raw material powder, these were mixed at a ratio of the atomic ratio of Zii : Ti to 8 8 : 1 2 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a forming pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was sintered at 1000 ° C for 4 hours under an argon atmosphere under a normal pressure (1.0 1 3 25 x 12 2 kPa) to obtain an oxide sintered product (C13). The oxidized sintered product (C13) was analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn: Ti = 88: 12 (Ti/ (Zn + Ti) =0·12 ). The crystal structure of the oxide sintered product (C13) was investigated by an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and it was found that the crystal phase of zinc oxide (ZnO) and zinc titanate (Zn2Ti04) was a mixture. And the titanium oxide is completely absent. Next, the obtained oxide sintered product (C13) was processed into a disk shape of 20 π ιηφ to prepare a target, and a transparent conductive film was formed by ion plating using the target to obtain a transparent conductive substrate. In other words, ion plating was performed using an ion plating apparatus (manufactured by Sino-foreign Furnace Co., Ltd.) under the following conditions to form a transparent film having a thickness of 200 nm on a transparent substrate (an alkali-free glass substrate having a thickness of 0.7 mm). Conductive film. -146- ·· 2 50〇C : 0.3Pa : argon = 160sccm, :1 00A : 200 seconds oxygen 201200616 Pre-heating temperature of the substrate before film formation Temperature at film formation Gas atmosphere condition at film formation = 2sccm Film formation In the case of the discharge current, the film formation time is related to the composition (Zn : Ti ) in the transparent conductive film formed, and the long-spreading type fluorescent X-ray device (XRF-1 700WS manufactured by Shimadzu Corporation) is used for fluorescent X-rays. The method is quantitatively analyzed using a calibration curve, and is Zn: Ti (atomic ratio) = 88:12. In addition, the X-ray diffraction device ("RINT2000" of Rigaku Electric Co., Ltd.) was used for X-ray diffraction using an accessory for film measurement, and an energy dispersive X-ray microanalyzer (TEM) was used for investigation. The doping state of titanium to zinc, and then the electric field radiation type electron display (FE-SEM) is used to investigate the crystal structure, which is a single phase of the fiber-zinc ore aligned with the C axis. It can be understood that the titanium substitution is dissolved in zinc, but the crystallinity is low. By. The transparent conductive film on the obtained transparent conductive substrate had a specific resistance of 10 Å Q.cm and a surface resistance of 1200.0 Ω / □. Further, the specific resistance distribution of the transparent group is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region (80 nm to 780 nm) and 73% in the infrared region 780 nm to 2700 nm. Furthermore, the transmittance of the glass plate before film formation in the visible light region (380 nm to 780 nm) is the same as that of the wave plate of the EDX micromirror type (field) (field I 94 -147-201200616%, the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was the surface resistance before the moisture resistance test. In addition, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the conductive substrate was not changed before and after immersion, and it was found to be excellent in alkali resistance. The acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness was thinned and dissolved after the immersion, but the film quality did not change before and after immersion. It is understood that the film is excellent in acid resistance. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent, and also has chemical durability (heat resistance, moisture resistance, alkali resistance, Transparent conductive film of acidity, but high resistance. (Example 34) It is made of zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (T i 2 Ο 3 ( 111 ): A high-purity chemical research institute (purity: 99.99%) is used as a raw material powder, and these are mixed in a ratio of atomic ratio of Zn:Ti to 93:7 to obtain a mixture of raw material powders. The mixed powder obtained by removing the ball and the ethanol was poured into a mold (molre) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite, and subjected to heat treatment at 丨000 ° C for 4 hours. Disc-type oxide sinter (30) (hot press) -148-201200616 The oxide sinter obtained by the energy dispersive fluorescent ray-ray device ("EDX-700L" manufactured by Shimadzu Corporation) The atomic ratio of Zn to Ti is Zn : Ti = 93 : 7 ( Ti / ( Zn + Ti ) = 0.07 ). The oxidation is investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.). Crystal structure of the material sinter (30), which is an oxidation word A mixture of ZnO) and a crystal phase of zinc titanate (Zn2Ti04), titanium oxide is completely absent. Next, the obtained oxide sintered product (30) is processed into a disk shape of 20 mmct> to prepare a target, and the target is used. A transparent conductive film is formed by ion plating to obtain a transparent conductive substrate, that is, an ion plating apparatus ("SUPLaDUO" manufactured by Sino-foreign Furnace Co., Ltd.) is used for ion plating under the following conditions, in a transparent substrate (thickness 〇. A transparent conductive film having a film thickness of 200 nm was formed on a 7 mm alkali-free glass substrate. :25 0〇C :0.3Pa : Xenon =160sccm, Oxygen: 1 00 A : 20 0 seconds Pre-heating temperature of the substrate before film formation Temperature at film formation Gas atmosphere condition when film formation = 2 seem When film formation In the discharge current forming time, the composition (Zn : Ti ) in the transparent conductive film to be formed, using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), using fluorescent X-rays The method was performed using a calibration curve for -149-201200616 quantitative analysis, which was Zn: Ti (atomic ratio) = 93: 7. In addition, the X-ray diffraction apparatus ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 1.1 × 1 (Γ3 Ω · cm, and the surface resistance was 5 5 · 0 Ω / □. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the obtained transparent conductive substrate was 90% in the visible light region (380 nm to 78 nm) and 67% in the infrared region (780 nm to 2700 nm). Further, the glass substrate before film formation was in the visible light region. The transmittance in the (3 80 nm to 780 nm) is 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) is 94% on average. The moisture resistance of the obtained transparent conductive substrate and the surface resistance after the moisture resistance test were evaluated. The surface resistance before the moisture resistance test was 1.4 times, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test. In the case of being excellent in heat resistance, the alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion. It is known that the alkali resistance is excellent. Further, the acid resistance of the obtained transparent conductive substrate is evaluated, and the film after immersion is evaluated. It is thinned and dissolved, but it is known that the film quality is excellent when the film quality is not changed before and after immersion. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and also has chemical durability (heat resistance). Transparent conductive film of moisture resistance, alkali resistance, and acid resistance. (Example 3 5 ) Zinc oxide powder (ZnO: Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO ( II ) : manufactured by a high-purity chemical research institute (purity: 99.99%) as a raw material powder, which is mixed in a ratio of atomic ratio of Zn:Ti to 93:7 to obtain a mixture of raw material powders. The mixed powder obtained by removing the ball and the ethanol is poured into a mold (mould) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite to perform i〇〇〇°c and heating for 4 hours. After the treatment, a disk-shaped oxide sinter (31) (hot press) was obtained. The obtained oxide sinter was analyzed by an energy dispersive fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). ), Zn The atomic ratio of Ti is Zn : Ti = 93 : 7 ( Ti / ( Zn + Ti ) =0_07). The oxide sintered product is investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) 31) The crystal structure is a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti〇4), and the titanium oxide is completely absent. Next, the obtained oxide sintered product (3 1 ) is processed into 20 mm. A disk-shaped 'production target' of φ was used to form a transparent conductive film by ion plating using the target to obtain a transparent conductive substrate. In other words, ion plating was performed using an ion plating apparatus ("SUPLaDUO" manufactured by Futeng Furnace Co., Ltd.) to form an ion plating on a transparent substrate (an alkali-free glass substrate having a thickness of 0.7 mm). A transparent conductive film having a film thickness of 200 nm. Pre-heating temperature of substrate before film formation: 2 50 〇C Pressure at film formation: 0.3Pa Ambient gas condition at film formation: Argon gas = =1 60sccm, oxygen = 2sccm Discharge current at film formation: 1 00A Film time: 200 seconds for the composition (Zn : Ti ) in the formed transparent conductive film, using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), using fluorescent X-rays The method was quantitatively analyzed using a calibration curve, and Zn: Ti (atomic ratio) = 93:7. Further, the transparent conductive film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The specific resistance of the transparent conductive film on the obtained transparent conductive substrate was 9.4 x 1 (Γ4 Ω·(: ηη, surface resistance was 47.0 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the substrate is 90% in the visible light region (-152-201200616 3 80 nm to 780 nm) and 67% in the infrared region (780 nm to 2700 nm). Further, the glass substrate before film formation is in the visible light region. The transmittance in (3 80 nm to 780 nm) is 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) is 94% on average. 耐 Evaluation of moisture resistance of the obtained transparent conductive substrate, surface resistance after moisture resistance test The surface resistance before the moisture resistance test was 1.4 times, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test. The heat resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated. After the immersion, the film thickness is reduced and dissolved, but the film quality is not changed before and after the immersion, and it is known that the acid resistance is excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and also has chemical durability ( Transparent conductive film of heat resistance, moisture resistance, alkali resistance, and acid resistance. (Example 36) Zinc oxide was weighed so that the element ratio of zinc element to gallium element and titanium element was 93.0: 2.0: 5.0 ( ZnO, manufactured by Kishida Chemical Co., Ltd., gallium oxide (Ga2〇3, manufactured by Sumitomo Chemical Co., Ltd.), and yttrium oxide (Ti203, manufactured by High Purity Chemical Research Institute), and poured into a container made of polypropylene Then, 2mmcj) of chrome oxide ball and ethanol as a mixed solvent of 153-201200616 are poured in. The ball is mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol is poured. The mold was pressed at a pressure of 40 MP a to obtain a disk-shaped molded body, which was placed in an electric furnace and heat-treated at 1,300 ° C in an Ar atmosphere to obtain a sintered product. The sintering was calculated from the size of the sintered product. Object The relative density was 95.3%. Further, the relative density was obtained by the following formula: The obtained sintered product was subjected to boring and surface honing to obtain a sintered body of 50.8 mm cj) and a thickness of 3 mm. Relative density = l〇〇x [(density of sintered product) / (theoretical density)] where, theoretical density = (monomer density of zinc oxide X mixed weight ratio + monomer density of gallium oxide X mixed weight ratio + titanium oxide The monomer density X mixed weight ratio) Using a copper plate as a support plate, the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions are as follows, and a film having a thickness of about 500 nm is obtained.

Target size: 5 0.8 mmcj> : Sputtering device: Canon Anelv Sputtering method: DC magnetic sputtering to reach vacuum: 2.0x1 0'4Pa Ar pressure: 0.5Pa Substrate temperature: 2 5 0〇C Sputtering power: 30W M-thickness -154- 201200616 Substrate: Sodium bell glass (5 0 · 8mm X 5 0.8mm X 0.5 mm The obtained film was dissolved in twice diluted hydrochloric acid by ICP-AES (Thermo-6500, manufactured by Thermo Scientific) The film composition is measured to obtain a film having a composition that is almost equal to the composition of the target. The X-ray diffraction device ("RINT2〇00" manufactured by Rigaku Electric Co., Ltd.) is used for the transparent conductive film. The X-ray diffraction was carried out at the same time, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and the crystal structure was investigated by electric field emission electron microscopy (FE-SEM). A single phase of the fiber-zinc-type alignment of the axis, it can be understood that the titanium substitution is dissolved in zinc. The sheet resistance of the obtained film is four-probe method (Mitsubishi Chemical Co., Ltd., surface resistance meter), which is manufactured by Tencor Corporation. Alp The film thickness was measured by ha-Step IQ, and the specific resistance was calculated to be 4.7×10 −4 Qcm. The surface resistance was 9.4 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform, and the transmittance of the transparent conductive substrate was in the visible light region. (3 8〇11111~78〇11111) has an average of 89% and an average of 60% in the infrared region (780nm to 2700nm). Furthermore, the quartz glass substrate before film formation is in the visible region (380 nm to 780 nm). The average transmittance is 94%, and the transmittance in the infrared region (780 nm to 27 〇 Onm) is 94% on average. The moisture resistance of the obtained transparent conductive substrate is evaluated, and the surface resistance after the moisture resistance test is -155-201200616 The surface resistance before the heat resistance test of the obtained transparent conductive substrate was 1.2 as the surface resistance before the heat resistance test, and it was considered that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was changed before and after immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent substrate was evaluated, and the film thickness after immersion was thinned and dissolved, but there was no change before immersion. In view of the above, it is understood that the film on the obtained transparent conductive substrate is a transparent conductive film having chemical resistance (heat resistance, moisture resistance, and acid resistance) and a transparent conductive film. It is alkaline and acid-resistant, so it is presumed that it has an appropriate etching rate when patterning (Example 3 7). Zinc oxide (ZnO) is weighed so that the element ratio of zinc element to gallium element and titanium element is 2.0:4.0. Kishida Chemical (manufactured), gallium oxide (Ga203, manufactured by Sumitomo Chemical Co., Ltd.), and (Ti2〇3, manufactured by High Purity Chemical Research Institute), and then poured into the container of 2% ηηηηφ The ball made of the ball and the solvent of the ethanol. The mixture was mixed in a ball mill to obtain a mixed powder mixing operation, and the mixed powder obtained by removing the ball and the ethanol was pressurized at a pressure of 40 Torr to obtain a disk-shaped formed body in an electric furnace. The oxide mixture was heat treated at 00 °C. Moisture resistance, heat resistance, film quality, no conductivity, good film quality, and low alkali resistance. 94.0: Titanium oxide is made into polypropylene as a mixed mash. It was obtained from -156 to 201200616 using a copper plate as a support plate, and the obtained oxide mixture was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 50.8mmφ 3mm Thick sputtering device: “E-200S” manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 〇'4Pa Ar pressure: 0.5Pa substrate temperature: 2 5 0〇 C Sputtering power: 30W Substrate: Sodium glass (5 0·8mmx5 0 · 8mmxO · 5mm) The obtained film was dissolved in twice diluted hydrochloric acid by ICP-AES (Therm〇-65, manufactured by Thermo Scientific) 00") The film composition was measured to obtain a film having a composition almost equal to the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigated the doping state of titanium on zinc, and then investigated the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of c-axis aligned bauxite type. It can be understood that titanium substitution is dissolved in zinc. The sheet resistance of the obtained film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd. 'surface resistance meter), and the film thickness was measured by "Alpha-Step-157-201200616 IQj" manufactured by Tencor Corporation, and the specific resistance was calculated to be 4 ·6χ1 (Γ4Ω·resistance is 9.2 Ω/□. Moreover, the transmittance of the transparent conductive substrate obtained on the transparent substrate on the transparent substrate is 89% in the visible: 380nm~ 780nm), and 780nm~2700nm in the infrared strip. The average of the film is 57%. In addition, the glass substrate before the film formation is 94% in the visible light region (380 nm to 780 nm) and 94% in the infrared region (780 nm to 2700 nm). Moisture resistance of the substrate The moisture resistance test surface resistance was 1.2 times that of the surface resistance before the moisture resistance test, and it was found to be excellent. The surface resistance after the heat resistance test of the obtained transparent conductive substrate was evaluated as the surface resistance before the heat resistance test. The evaluation of the alkali resistance of the obtained transparent conductive substrate was carried out before the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained substrate was evaluated, and the film thickness after the immersion was thinned and dissolved, but the immersion did not change. In the above, it is understood that the film on the obtained transparent conductive substrate is a transparent conductive film having electrical resistance (heat resistance, moisture resistance, and acid resistance), and also has alkali resistance. Sexuality and difference, it is presumed that there is an appropriate etching rate when patterning. (Comparative Example 1 4) cm. The surface is the in-plane averaged area (spring area (the quartz glass average is the average of the over-rates after the test). Moisture resistance, heat resistance. 2 times, the film quality is clear and low, and the alkali resistance and acid resistance are good before and after the film quality is 158-201200616. The zinc oxide powder with an average particle size of l^m is 97.7 weight. '2.3 parts by weight of alumina powder having an average particle diameter of 0.2/zm was poured into a crucible made of polyethylene, and mixed for 72 hours using a dry ball mill to obtain a mixture of raw material powders. The resulting mixture was poured into a mold to a molding pressure of 300 kg/ The pressure of cm2 was pressed to obtain a molded body. The compact was subjected to densification treatment at a pressure of 3 t〇n/cm 2 by CIP, and then sintered under the following conditions to obtain a sintered body of aluminum-doped zinc oxide. Temperature: 1 500 ° C Heating rate: 50 ° C / hour Holding time: 5 hours Sintering atmosphere: The obtained sinter in the atmosphere is analyzed by X-ray diffraction, which is a mixed structure of ZnO and ΖηΑ1204 two phases. Next, the obtained oxide sintered body was processed into a shape of 4 inches φ and 6 mm thick, and fixed on an oxygen-free copper support plate using indium solder to prepare a target. Then, using this target, a film was formed by a sputtering method under the following conditions, and a transparent conductive film having a thickness of 500 nm was formed on a transparent substrate (quartz glass substrate) to obtain a transparent conductive substrate. The A1 content in the formed film was 2.3% by weight. Ore-service device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering Magnetic field strength: 10 00 Gauss (directly above the target, horizontal component)

Substrate temperature: 250 ° C -159- 201200616

Vacuum reached: 5xl (T5Pa Sputtering gas: Ar Sputtering gas pressure: 〇.5Pa DC Power: 300W The specific conductive resistance of the transparent conductive film on the obtained transparent conductive substrate is 4.2X l (T4Q.cm, surface resistance is 8.4Ω) /ΙΙ] The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (380 nm to 78 0 nm) and 50% in the infrared region (780 nm to 2700 nm). Evaluation of the resistance of the obtained transparent conductive substrate The surface resistance after the moisture resistance test was 2.1 times that of the surface resistance before the moisture resistance test, and it was found to be poor in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was a heat resistance test. The surface resistance of the former was 2.0 times, which was found to be poor in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared after immersion. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film was completely dissolved and disappeared. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, but is transparent in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance). (Example 3 8 ) Weigh zinc oxide (Zn〇, manufactured by Kishida Chemical Co., Ltd.) so that the ratio of elemental ratio of zinc element to gallium element and titanium element is 96.5: -160-201200616 0.5: 3.0 Gallium oxide (GazO3, manufactured by Sumitomo Chemical Co., Ltd.) and titanium oxide (manufactured by ThCh 'High Purity Chemical Research Institute), and poured into a container made of polypropylene, then poured into a 2mmcj) oxidized pin. The ball and the ethanol as a mixed solvent were mixed in a ball mill to obtain a mixed powder. After the mixing operation, 'the mixed powder obtained by removing the ball and the ethanol was poured into a mold' was pressurized at a pressure of 40 MPa to obtain a disk-shaped formed body. This was placed in an electric furnace and heat-treated in an Ar atmosphere at 1; 3 ° C to obtain a sintered product. The relative density of the sintered product was calculated to be 96.8 % from the size of the sintered product. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50.8 mm cj) and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 50.8πηηφ 31 nra thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 2 5 0 〇C Sputtering power: 30W Substrate: Soda-lime glass (50.8mmx50.8mmx0.5mm -161 - 201200616 The obtained film is dissolved in twice diluted hydrochloric acid, manufactured by ICP-AES (Thermo S ci en ti fi c company) "Thermο -65 00") The film composition was measured to obtain a film having almost the same composition as the target composition. In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film. X-ray diffraction was carried out using an accessory for film measurement, and the doping state of titanium to zinc was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and then an electric field emission electron microscope (FE-SEM) was used to investigate crystallization. The structure is a single phase of the wurtzite type aligned with the C-axis, and it can be understood that the titanium substitution is solid-dissolved in the zinc. The sheet resistance of the obtained film is four-probe method (Mitsubishi Chemical Co., Ltd., surface resistance meter), using Tenc The film thickness was measured by "Alpha-Step IQ" manufactured by Or Company, and the specific resistance was calculated to be 4.1 χ 1 (Γ4 Ω·cm. The surface resistance was 8.2 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the transparent conductive substrate is 89% in the visible light region (380 nm to 780 nm) and 59% in the infrared region (780 nm to 27 Å Onm). Further, the quartz glass substrate before film formation is The transmittance in the visible light region (3 80 nm to 78 0 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the moisture resistance test was performed. The surface resistance was 1.2 times that of the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance -162 to 201200616. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was before the heat resistance test. When the surface resistance was 1.2 times, it was found to be excellent in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after immersion, and it was found that the alkali resistance was excellent. Further, the obtained transparent conductive group was evaluated. The acid resistance is improved, and the film thickness is reduced and dissolved after immersion. However, it is known that the film quality is excellent when the film quality is not changed before and after immersion. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and also has chemical durability. A transparent conductive film (heat resistance, moisture resistance, alkali resistance, acid resistance). Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. (Example 3 9 ) Weigh zinc oxide (ZnO, Kishida Chemical Co., Ltd.), gallium oxide (Ga203, etc.) so that the element ratio of the zinc element to the gallium element and the titanium element is 9 4.5 : 〇 _5 : 5.0 Sumitomo Chemical Co., Ltd. and titanium oxide (Ti203, manufactured by High Purity Chemical Research Institute), and poured into a container made of polypropylene, then poured into a 2mmcj zirconia ball and used as a mixed solvent. Ethanol. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold, and pressurized at a pressure of 40 MPa to obtain a disk-shaped formed body. This was placed in an electric furnace and heat-treated at 1 300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated from the size of the sintered product to be 94.6%. Further, the relative density was determined as in Example 36. The obtained sintered product -163-201200616 was subjected to boring and surface honing to obtain a sintered body of 5 〇·8ιηιηφ and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Standard size: 50·8ηιιηηφ 3mm thick Splashing device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering The degree of vacuum reached: 2.0xl0_4Pa Ar Pressure: 0.5Pa

Substrate temperature: 250 ° C

Sputtering power: 30 W Using a substrate: sodium korea glass (50.8 mm x 50 _ 8 mm x 0.5 mm) The obtained film was dissolved in twice diluted hydrochloric acid, and the film composition was measured by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). A film consisting almost identically to the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. -164-201200616 The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the resistivity was calculated to be 4.6 χ10. · 4 Ω · cm. The surface resistance was 9.2 Ω/□. Moreover, the specific resistance distribution on the transparent substrate is the in-plane uniformity of 0. The transmittance of the transparent conductive substrate is 89% in the visible light region (3 8〇11111~7 8〇11111), and is in the infrared region (780 nm). The average of 2700 nm) is 59%. Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 78 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. -165-201200616 (Example 40) A cerium oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.) and gallium oxide (Ga2) were measured in such a manner that the element ratio of the zinc element to the gallium element and the titanium element was 92.5:0.5:7.0. 〇3, manufactured by Sumitomo Chemical Co., Ltd.) and titanium oxide (Ti2〇3, manufactured by High Purity Chemical Research Institute), and poured into a container made of polypropylene, and then poured into a ball of zirconia of 2ιηιηφ With ethanol as a mixed solvent. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold, and pressurized at a pressure of 40 Torr to obtain a disk-shaped formed body. This was placed in an electric furnace and heat-treated at 1 300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated from the size of the sintered product to be 93.9 %. Further, the relative density was determined as in Example 36. The obtained sintered product was subjected to boring and surface honing to obtain a sintered body having a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Standard Bag Size: 50.8mmcj) 3mm Thick Beach Equipment: "E-200S" by Canon Anelva Sputtering Method: DC Magnetic Sputtering Reaching Vacuum: 2.0x1 0_4Pa

Ar pressure: 0.5Pa -166- 201200616

Substrate temperature: 250 ° C

Sputtering power: 30 W Substrate: Sodium #5 Glass (50.8 mm x 50.8 mm x 0.5 mm) The obtained film was dissolved in twice diluted hydrochloric acid, and the film was measured by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). In the composition, a film having a composition almost equal to the composition of the target is obtained. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) is used for the transparent conductive film, and X-ray winding is performed using an accessory for film measurement. At the same time, the energy-dispersive X-ray microanalyzer (TEM-EDX) was used to investigate the doping state of titanium to zinc, and then the electric field radiation electron microscope (FE-SEM) was used to investigate the crystal structure, which was a C-axis oriented wurtzite. The single phase of the type can be understood that titanium substitution is dissolved in zinc. The sheet resistance of the obtained film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., surface resistance meter), and the film thickness was measured by "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 5.5 x 1 0_4 Ω·cm. The surface resistance is U.0 Ω/□. Further, the specific resistance distribution on the transparent substrate is uniform in plane. The transmittance of the obtained transparent conductive substrate was 89% on average in the visible light region (3 8 〇 11111 to 78 〇 11111), and 59% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 78 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. -167-201200616 The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. (Example 4 1 ) Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.) and gallium oxide (Ga203, Sumitomo Chemical Co., Ltd.) were weighed so that the element ratio of the zinc element to the gallium element and the titanium element was 96.5:0.5:3.0. (manufactured by the company) and titanium oxide (manufactured by TiO(II) 'High Purity Chemical Research Institute), and poured into a container made of polypropylene, then poured into a ball made of oxidized pin of 2 ηηπιφ and used as a mixed solvent. Ethanol. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold, and pressurized at a pressure of 40 Torr to obtain a disk-shaped formed body. This was placed in an electric furnace, and heat-treated at 13 ° C in an Ar atmosphere to obtain a sintered product of -168 - 201200616. The relative density of the sintered product was calculated from the size of the sintered product to be 96.7 %. Further, the relative density was determined as in Example 36. The obtained sintered product was subjected to boring, surface honing 'to obtain 50.8 mm cj), and a sintered body having a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 5 0.8 mm φ 3 mm thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering to reach vacuum: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 25 0〇C Sputtering power: 30W Substrate: Sodium consuming glass (50.8mmx50.8mmx0.5mm) Dissolve the obtained film in twice diluted hydrochloric acid by ICP-AES (Thermo-.6500, manufactured by Thermo Scientific) The film composition was measured to obtain a film having a composition almost equal to the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigated the doping state of titanium on zinc, and then investigated the crystal structure by electric field-electron microscopy (FE-SEM) using a -169-201200616 field, which is a single phase of the C-axis aligned wurtzite type. The substitution is dissolved in zinc. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 3.9 χ1 (Γ4 Ω·cm). The surface resistance is 7.8 Ω / □. Moreover, the specific resistance distribution on the transparent substrate is the in-plane uniformity. The transmittance of the transparent conductive substrate is 89% in the visible light region (380 nm to 7 8 Onm). In the infrared region (780 nm to 2700 nm), the average is 59%. Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) is 94% on average, and in the infrared region (780 nm to 2 700 nm). The average transmittance was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. The heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated before the immersion. The film quality was not changed, and it was found to be excellent in alkali resistance. The acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after immersion was thinned and dissolved. However, the film quality was not changed before and after immersion, and it was found that the acid resistance was excellent. It is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance - 170-201200616, acid resistance) transparent conductive film. Since it is excellent in alkali and acid resistance, it is presumed that it has an appropriate uranium engraving rate when patterning. (Example 42) Weighing and oxidizing the element ratio of zinc element to gallium element and titanium element to 94.5:0.5:5.0 Zinc (made by ZnO, Kishida Chemical Co., Ltd.), gallium oxide (Ga203, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute), and poured into poly In a container made of propylene, a ball made of chrome oxide of 2πιηηφ and ethanol as a mixed solvent are poured, and the mixture is mixed by a ball mill to obtain a mixed powder. After the mixing operation, the ball and the ethanol are removed. The powder was poured into a mold and pressurized at a pressure of 40 MPa to obtain a disk-shaped formed body, which was placed in an electric furnace and heat-treated at 1,300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated to be 94.5 %. Further, the relative density was determined as in Example 3. The obtained sintered product was subjected to boring and surface honing to obtain a sintered body of 5 〇.8 η ιηηφ and a thickness of 3 mm. Using a copper plate as a support plate, the resulting sintered product was fixed using indium solder to obtain a sputtering target. Using the resulting sputtered target, film formation was performed by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Standard IG size: 50.8mmcj) 3mm thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering -171 - 201200616 Reaching vacuum: 2.0x 1 0*4pa Ar pressure: 0.5Pa substrate Temperature: 25 0 〇 C Sputtering power: 30 W Substrate: Sodium silicate glass (50.8 mm x 50.8 mm x 0.5 mm) The obtained film was dissolved in twice diluted hydrochloric acid by ICP-AES (Thermo- company "Thermo- 6500") The film composition was measured to obtain a film having a composition almost equal to the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 4.4 χ1 (Γ4 Ω·cm). The surface resistance is 8 · 8 Ω / □. Moreover, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (380 nm to 78 Onm), in the infrared region. The average value of (780nm to 2700nm) is 59%. Furthermore, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) is -172-201200616 94%, in the infrared region (7 80 nm~ The transmittance in the 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. The heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated. The film quality was not changed, and it was found to be excellent in alkali resistance. The acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after thinning was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. As described above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Since it is excellent in acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning. (Example 43) Zinc oxide (ZnO) was weighed so that the element ratio of the zinc element to the gallium element and the titanium element was 92.5:0.5:7.0. , manufactured by Kishida Chemical Co., Ltd., gallium oxide (Ga203, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute), and poured into a container made of polypropylene. Then, 2 mm (t) of zirconia balls and ethanol as a mixed solvent are poured in. The mixture is mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is obtained. In the mold-173-201200616, a disk-shaped molded body was obtained by pressurizing at a pressure of 40 MP a, placed in an electric furnace, and heat-treated at 1300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated to be 94.0%, and the relative density was determined as in Example 3. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50.8 ηηηφφ and a thickness of 3 mm. The copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions are as follows to obtain a film having a thickness of about 500 nm. Target size: 50.8 mmcj) 3 mm thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches a vacuum degree: 2.0 x 1 0'4 Pa Ar pressure: 0.5Pa Substrate temperature: 2 5 0〇C Sputter power: 30W Substrate: Sodium glass (50.8mmx50.8mmx0.5mm) Dissolve the obtained film in twice diluted hydrochloric acid to ICP-AES (Thermo The film composition of "Therm〇-6 5 00 j" manufactured by Scien tifi c company was measured to obtain a film having almost the same composition as the target composition. In addition, an X-ray diffraction device was used for the transparent conductive film (Like) "RINT2000" manufactured by the method, using the film measurement with the attachment of -174-201200616 for χ-ray diffraction, and using the energy dispersive X-ray microanalyzer (TEM-EDX) to investigate the doping state of titanium to zinc, and then using the electric field. The radioactive electron microscope (FE-SEM) investigated the crystal structure and was a single phase of the wurtzite type aligned with the C-axis. It can be understood that the titanium substitution is dissolved in zinc. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 5.3 χΙΟ·4 Ω. Cm. The surface resistance was 10.6 Ω/□. Further, the specific resistance distribution on the transparent substrate is uniform in plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 7 8 On m) and 59% in the infrared region (78 0 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. In the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. In addition, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning (Example 44) so that the element ratio of the zinc element to the gallium element and the titanium element is 96.5 : 0.5 : 3.0 Method for weighing zinc oxide (made by ZnO, Kishida Chemical Co., Ltd.), gallium oxide (Ga203, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute) a mixture of powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized by a pressure of 4 Torr MPa using a press machine made of graphite. Heat treatment at ° C for 4 hours to obtain a disk-shaped sintered body. (Hot press sintering) The relative density of the sintered body was calculated from the size of the sintered product to be 96.3%. Further, the relative density was determined as in Example 36. The obtained sintered product was subjected to boring and surface honing to obtain a sintered body of 5 Å. 8 ηηηιφ and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Standard IE size: 50.8mmcj) 3mm thick Sputtering device: "E-200S" manufactured by CanonAnelva Sputtering method: DC magnetic sputtering -176- 201200616 Reaching vacuum Ar pressure Substrate temperature Sputtering power Using substrate

:2.0xlO*4Pa :0.5Pa :2 5 0〇C :30W • Nano-glass (5 0.8 mm X 5 0.8 mm X 0.5 mm) Dissolve the obtained film in twice diluted hydrochloric acid by ICP-AES (Thermo The "Thermo-6500" manufactured by Scientific Corporation measures the composition of the film to obtain a film having a composition almost equal to that of the target. In addition, the X-ray diffraction device ("RINT2〇00" manufactured by Rigaku Electric Co., Ltd.) is used for the transparent conductive film, and X-ray diffraction is performed using an accessory for film measurement, and energy dispersive X-ray microanalysis is used. The instrument (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 3·9 χ 10_4 Ω · cm » The surface resistance was 7.8 Ω/□. Moreover, the transmittance of the transparent conductive substrate obtained by the specific resistance distribution on the transparent substrate is 90% in the visible light region (380 nm to 78 nm), and is in the infrared region (780 nm to 27 〇 Onm). The average is 59%. Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was -177 - 201200616 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate and the surface resistance after the moisture resistance test were 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. (Example 45) Weigh zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.) and gallium oxide (Ga203, Sumitomo Chemical Co., Ltd.) in such a manner that the element ratio of the zinc element to the gallium element and the titanium element is 94.5 : 〇·5: 5_0. (manufactured by the company) and titanium oxide (Ti〇 (II), manufactured by the High Purity Chemical Research Institute) to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite to carry out l〇〇〇°c, 4 - 178 - 201200616 hours of heat treatment to obtain a disc-shaped sinter. (Hot press sintering) The relative density of the sintered product was calculated from the size of the sintered product to be 95.6%. Further, the relative density was determined as in Example 36. The obtained sintered product was subjected to boring and surface honing to obtain a sintered body of 5 〇 8 mm (j) and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 50.8mmcj) 3mm thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 2 5 0 〇C Sputtering power: 30W Substrate: Sodium consuming glass (50.8 mm x 50.8 mm x 0.5 mm) The obtained film was dissolved in twice diluted hydrochloric acid and determined by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). The film is composed of a film having a composition almost equal to that of the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure using the electric-179-201200616 field emission electron microscope (FE-S EM), which is a single phase of the C-axis aligned bauxite type. Titanium replacement is dissolved in zinc. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 4.4 x 1 (Γ4 Ω · cm). The surface resistance is 8.8 Ω/□. Moreover, the specific resistance distribution on the transparent substrate is in-plane. The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (380 nm to 7 8 Onm). In the infrared region (780nm~270〇nm), the average is 59%. Furthermore, the transmittance of the quartz glass substrate before film formation in the visible light region (380nm~780nm) is 94% on average, in the infrared region (780nm~ The average transmittance in the case of 2 700 nm) was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. In addition, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance and the impregnation of the obtained transparent conductive substrate were evaluated. The film quality was not changed, and it was found to be excellent in alkali resistance. The acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after immersion was thinned and dissolved. However, the film quality was not changed before and after immersion, and it was found that the acid resistance was excellent. It is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance - 180 - 201200616, acid resistance) transparent conductive film. Since it is excellent in alkali and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning. (Example 46) Weigh zinc oxide so that the element ratio of zinc element and aluminum element and titanium element becomes 96.5 : 0.5: 3.0. (ZnO, manufactured by Kishida Chemical Co., Ltd.), alumina (ai2o3, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (Ti203, manufactured by High Purity Chemical Research Institute), and poured into a container made of polypropylene. Then, the zirconia ball and the ethanol as a mixed solvent are poured in. The mixture is mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured. In the mold, a disk-shaped molded body was obtained by pressurizing at a pressure of 40 MPa, and this was placed in an electric furnace, and heat-treated at 1,300 ° C in an Ar atmosphere to obtain a sintered product. The sintered product was calculated from the size of the sintered product. The relative density is 96.9%. Further, the relative density is obtained by the following formula: The obtained sintered product is boring and surface honed to obtain a sintered body of 5 〇·8ιηηιφ and a thickness of 3 mm. Relative density = l〇〇x [ (density of sintered product) / (theoretical density)] wherein, theoretical density = (monomer density of zinc oxide X mixed weight ratio + monomer density of alumina X mixed weight ratio + monomer density of titanium oxide X mixed weight ratio Using a copper plate as a support plate, the obtained sintered body was fixed using indium solder to obtain a sputtering target. -181 - 201200616 Using the resulting sputtering target, film formation was performed by sputtering. The sputtering conditions were as follows to obtain a film having a thickness of about 500 nm. Target size: 50.8mmc|&gt; 3mm thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 2 5 0〇C Sputtering power: 30W Substrate used: Sodium bismuth glass (50.8mmx50.8mmx0_5mm) Dissolve the obtained film in twice diluted hydrochloric acid to ICP-AES ("Thermo-6500" by Thermo Scientific) The film composition was measured to obtain a film having a composition almost equal to that of the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigated the doping state of titanium on zinc, and then investigated the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of c-axis aligned bauxite type. It can be understood that titanium substitution is dissolved in zinc. The sheet resistance of the film obtained by the middle layer was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using "Alpha-Step IQj film thickness" manufactured by Tencor Corporation and the specific resistance was calculated to be 4.1 χ 10·4 Ω. Cm. The surface resistance is 8·2 Ω /□. And the specific resistance distribution on the transparent substrate is in-plane average -182-201200616. The transmittance of the obtained transparent conductive substrate is average in the visible light region (3 80 nm to 7 80 nm). 89%, in the infrared region (780nm~27〇0nm), the average is 59%. Furthermore, the transmittance of the quartz glass substrate before film formation in the visible light region (380nm~780nm) is 94% on average, in the infrared region. (780nm~ The transmittance in the 2700 nm was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. The heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality before and after the immersion was not obtained. In addition, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after immersion was thinned and dissolved. However, the film quality was not changed before and after immersion, and it was found that the acid resistance was excellent. The film on the conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. In addition, it is excellent in alkali resistance and acid resistance. Therefore, it is presumed that there is an appropriate etching rate at the time of patterning. (Example 47) The ratio of the elements of zinc element to aluminum element and titanium element is 9 4.5 : 0.5: 5.0 Weighing zinc oxide (made by ZnO, Kis Hi Da Chemical Co., Ltd. - 183-201200616), alumina (made by Aldo 3's Sumitomo Chemical Co., Ltd.), and Oxidation Chin (Ti2〇3, High Purity Chemical Research Institute) (manufactured by the company), and poured into a container made of polypropylene 'then poured into a cerium oxide ball and ethanol as a mixed solvent. These are mixed in a ball mill to obtain a mixed powder. After the mixing operation, the ball is removed. The mixed powder obtained by ethanol was poured into a mold, and pressurized at a pressure of 40 MPa to obtain a disk-shaped formed body, which was placed in an electric furnace and heat-treated at 1300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated from the size of the sintered product to be 9 4.8%. Further, the relative density was determined as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered body having a thickness of 50.8 mm cj) and a thickness of 3 mm. 铜 A copper plate was used as a support plate, and the obtained sintered product was fixed with indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 ηπ was obtained. Target size: 50.8ιηιηφ 3mm Thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 250〇C splash Plating power: 30W Substrate: Sodium #5 Glass (50.8mmx50.8mmx0_5mm) -184 - 201200616 The obtained film was dissolved in twice diluted hydrochloric acid and determined by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). The film is composed of a film having a composition almost equal to that of the target composition. In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc. The sheet resistance of the obtained film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd. 'surface resistance meter), and the film thickness was measured by "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 4.6 x 1 0 · 4 Ω. Cm. The surface resistance was 9.2 Ω/□. Further, the specific resistance distribution on the transparent substrate is the in-plane uniformity. The transmittance of the transparent conductive substrate is 89% in the visible light region (380 nm to 780 nm), and is in the infrared region (78 〇 nm to 27 〇 Onm). The average is 59%. Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average » Evaluation of the obtained transparent conductive substrate The moisture resistance and the surface resistance after the moisture resistance test were 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times that of the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent in the range of -185 to 201200616. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. (Example 48) Weigh zinc oxide (ZnO, Kishida Chemical Co., Ltd.), alumina (ai2o3, Sumitomo Chemical Co., Ltd.) so that the element ratio of zinc element to aluminum element and titanium element is 92.5 : 0.5 : 7.0 (manufactured) and titanium oxide (Ti203, manufactured by High Purity Chemical Research Institute), poured into a container made of polypropylene, and then poured into a ball of chrome oxide of 2πιηηφ and ethanol as a mixed solvent. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold, and pressurized at a pressure of 40 Torr to obtain a disk-shaped formed body. This was placed in an electric furnace, and heat-treated at 1,300 Torr in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated from the size of the sintered product to be 94.2%. Further, the relative density was determined as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50.8 mm cj) and a thickness of 3 mm. -186-201200616 A copper plate was used as a support plate, and the obtained sintered product was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 5 0.8mm&lt;j) 3 r ϊΐ m thick sputtering device: manufactured by Canon Anelva Sputtering method: DC magnetic sputtering to reach vacuum: 2.0x1 0 4Pa Ar pressure: 0.5Pa substrate temperature: 250〇 C Sputtering power: 30W Substrate used: Sodium consuming glass (50_8mmx50) The obtained film was dissolved in twice diluted hydrochloric acid, and the film composition was determined by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) is used for the transparent conductive film, and X-ray diffraction is performed using an accessory for film measurement, and energy is used at the same time. A dispersive X-ray microanalyzer (TEM-EDX) was used to investigate the doping state of titanium on zinc, and then the electric field radiation electron microscope (FE-SEM) was used to investigate the crystal structure, which was a single phase of the C-axis aligned wurtzite type. It can be understood that the titanium substitution is dissolved in zinc. The sheet resistance of the obtained film is four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter), and "Alpha-Step-187-" manufactured by Tencor Corporation. 201200616 IQ", the film thickness was measured, and the specific resistance was calculated to be 5.5 x 1 〇 -4 Ω · cm. The surface resistance was 1 1 · 〇 Ω / □. Moreover, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the substrate is 89% in the visible light region (380 nm to 780 nm) and 59% in the infrared region (780 nm to 2700 nm). Further, the quartz glass substrate before film formation is in the visible light region (3 80 nm). The transmittance in the range of ~780 nm was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was moisture resistance. The surface resistance before the test was 1.2 times, and it was found to be excellent in moisture resistance. Moreover, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found to be heat resistance. The evaluation of the alkali resistance of the obtained transparent conductive substrate was carried out, and the film quality was not changed before and after immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film after immersion was evaluated. It is known that it is thin and soluble, but it is known that the film quality is not changed before and after immersion. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and low in electrical resistance, and also has chemical durability (heat resistance and moisture resistance). A transparent conductive film which is resistant to alkali and acid. Moreover, since it is excellent in alkali resistance and acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning. (Example 49) -188-201200616 The ratio of the elemental ratio of the zinc element to the aluminum element and the titanium element is 96.5: 0.5. 3.0. The amount of zinc oxide (zn〇, manufactured by Kishida Chemical Co., Ltd.) Ah〇3 'manufactured by Sumitomo Chemical Co., Ltd.) and titanium oxide (manufactured by TiO(II) 'High Purity Chemical Research Institute), poured into a container made of polypropylene, and then poured into zirconia The ball and the ethanol as a mixed solvent. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold to pressurize at a pressure of 40 MP a to obtain a disk-shaped formed body. This was placed in an electric furnace and heat-treated at 1,300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered body was calculated from the size of the sintered product to be 96.8%. Further, the relative density was determined as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered body having a thickness of 3 mm _8 τηιηφ and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered product was fixed with indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained.

Target size: 50.8mmcf) 3] Splashing device: Canon Anelva Sputtering method: DC magnetic sputtering to reach vacuum: 2.0x1 0'4Pa Ar pressure: 0.5Pa Substrate temperature: 2 5 0〇C Sputtering power: 30W Thickness -189- 201200616 Substrate used: sodium-depleting glass (50.8 mm x 50.8 mm x 0.5 mm) The obtained film was dissolved in twice diluted hydrochloric acid and determined by IC P-AES ("Thermo-6500" manufactured by Thermo Scientific). The film is composed of a film having a composition almost equal to that of the target composition. In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 3.9 x 1 0 · 4 Ω. Cm. The surface resistance is 7.8 Ω/□. Further, the specific resistance distribution on the transparent substrate is uniform in plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 7 8 Onm) and 59% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent from -190 to 201200616. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. (Example 5 0) Zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.) and alumina (ai2o3, Sumitomo Chemical Co., Ltd.) were weighed so that the element ratio of the zinc element to the aluminum element and the titanium element was 9 4.5 : 0.5: 5.0. (manufactured by the company) and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute), and poured into a container made of polypropylene, and then poured into a ball of chrome oxide of 2ηιηηφ and as a mixed solvent. Ethanol. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold, and pressurized at a pressure of 40 MPa to obtain a disk-shaped formed body. This was placed in an electric furnace, and heat-treated at 1,300 ° C in an Ar atmosphere to obtain a sintered product. The relative density of the sintered product was calculated from the size of the sintered product to be 94.7%. Further, the relative density was determined as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50.8 πππφ and a thickness of 3 mm. 铜 A copper plate was used as a support plate. The obtained sintered product was fixed with indium solder to obtain a sputtering target. The resulting sputter target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 50.8πιιηφ 3mm Thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 2 5 0eC splash Plating power: 30 W Substrate used: Sodium 15 glass (50.8 mm x 50.8 mm x 0.5 mm) The obtained film was dissolved in twice diluted hydrochloric acid, and the film was measured by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). Composition, obtaining a film of almost equal composition to the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the fiber-synthesizing type of C-axis alignment. in. -192- 201200616 The sheet resistance of the obtained film was measured by a four-probe method (Mitsubishi Chemical, surface resistance meter) using "IQ" manufactured by Tencor Corporation, and the resistivity was calculated to be 4.4 χ 10_4 Ω and the resistance was 8.8 Ω / □. . Also, the specific resistance clause on the transparent substrate. The transmittance of the obtained transparent conductive substrate was 89% on average in S 3 80 nm to 780 nm, and 59 % in red 780 nm to 2700 nm. Further, the film-forming substrate has a transmittance of 94% in the visible light region (380 nm to 780 nm) and 94% in the infrared region (780 nm to 2700 nm). The moisture resistance of the obtained transparent conductive substrate was evaluated, and the wet resistance was 1.2 times the surface resistance before the moisture resistance test, which was excellent. Further, the surface resistance after the endurance test of the obtained transparent conductive substrate was evaluated as the surface resistance before the heat resistance test, which was excellent in heat resistance. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the immersion was changed, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the immersion was not changed, and it was found that the acid resistance was excellent. From the above, it is known that the film resistance on the obtained transparent conductive substrate is also a transparent conductive film having chemical durability (heat resistance, moisture resistance, and acid resistance). Further, since it is resistant to alkali, it is presumed that it has an appropriate etching rate at the time of patterning. Alpha-Step • cm 〇 surface cloth is the in-plane light area ( • line area (the previous quartz glass lapse rate is averaged after the transmittance average test) is known as moisture resistance heat, heat resistance 1.2 times , before and after the film quality is not transparent conductive stains before and after the film is transparent and low, alkali resistance, acid resistance -193-201200616 (Example 5 1) so that the ratio of elements of zinc and aluminum and titanium elements is 9 2.5 : 〇·5: 7.0 method for weighing zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), alumina (ai2o3, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), High Purity Chemical Research Institute (manufactured by the company), and poured into a container made of polypropylene, and then poured into a ball of zirconia of 2 ηηηηψ and ethanol as a mixed solvent. The mixture is mixed by a ball mill to obtain a mixed powder. After the mixing operation, the ball is removed. The mixed powder obtained by the ethanol was poured into a mold, and pressurized at a pressure of 40 MPa to obtain a disk-shaped formed body, which was placed in an electric furnace and heat-treated at 1300 ° C in an Ar atmosphere to obtain a sintered product. Ruler The relative density of the sintered product was calculated to be 94.2%. Further, the relative density was determined as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50·8 π ιηηφ and a thickness of 3 mm, which was supported by a copper plate. The plate was fixed with the indium solder to obtain a sputter target. The resulting sputter target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Standard size: 50.8 mm ( j) 3mm thick beach plating device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0xl0_4Pa

Ar pressure: 0.5Pa -194- 201200616

Substrate temperature: 2 5 0 °C

Sputtering power: 30W Substrate used: Nanoglass (50.8mmx50.8mmx0.5mm) The obtained film was dissolved in twice diluted hydrochloric acid, and the film was measured by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). The composition 'obtains a film that is almost equal in composition to the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. The sheet resistance of the obtained film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., surface resistance meter), and the film thickness was measured by "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 5.5 χ 10 · 4 Ω. · cm. The surface resistance is 1 1.0 Ω/□. Further, the specific resistance distribution on the transparent substrate is uniform in plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 780 nm) and 59% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (3 80 ηηη to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. -195-201200616 The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.1 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the film was excellent in acid resistance. From the above, it was found that the film on the obtained transparent conductive substrate was transparent and low. A transparent conductive film that combines electrical resistance with heat resistance (heat resistance, moisture resistance, alkali resistance, and acid resistance). In addition, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning (Example 52) so that the element ratio of the zinc element to the aluminum element and the titanium element is 96.5: 0.5: 3.0. Method for weighing zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.), alumina (Ah〇3, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute). A mixture of raw material powders is obtained. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite, and 1000 ° C for 4 hours. Heat treatment 'obtained a disc-shaped sinter. (Hot press sintering) The relative density of the sintered product was calculated from the size of the sintered product to be 96.6%. -196-201200616 Further, the relative density was obtained as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50·8 ηηπιφ and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputter target was used to form a film by sputtering. The sputtering conditions were as follows, and a film having a thickness of about 500 nm was obtained. Target size: 50·8πιιηφ 3mm Thick sputtering device: “E-200S” manufactured by Canon Anelva Sputtering method: DC magnetic sputtering reaches vacuum degree: 2.0x1 0'4Pa Ar pressure: 0.5Pa substrate temperature: 25 0〇 C Sputtering power: 30W Substrate used: Sodium Han glass (50.8mmx50.8mmx0.5mm) The obtained film was dissolved in twice diluted hydrochloric acid and determined by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). The film is composed of a film having a composition almost equal to that of the target composition. In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used ( TEM-EDX) investigated the doping state of titanium on zinc, and then investigated the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of c-axis aligned bauxite type. It can be understood that titanium substitution is dissolved in zinc. in. -197- 201200616 The sheet resistance of the obtained film was measured by a four-probe method (Mitsubishi Chemical Co., Ltd., surface resistance meter), and the film thickness was measured by "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 3.9 χ 10 4 Ω. · cm. The surface resistance is 7.8 Ω/□. Further, the specific resistance distribution on the transparent substrate is uniform in plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 7 8 Onm) and 59% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The evaluation of the alkali resistance of the obtained transparent conductive substrate, and the film quality before and after the immersion. There is no change, and it is known that it is excellent in alkali resistance. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the film was excellent in acid resistance. From the above, it was found that the film on the obtained transparent conductive substrate was transparent and low. A transparent conductive film that combines electrical resistance with heat resistance (heat resistance, moisture resistance, alkali resistance, and acid resistance). Further, since it is excellent in alkali resistance and acid resistance, it is presumed that it has an appropriate etching rate at the time of patterning. -198-201200616 (Example 5 3 ) Weigh zinc oxide (ZnO, manufactured by Kishida Chemical Co., Ltd.) and alumina (ai2o3) so that the ratio of the element of zinc to the elemental element and the element of titanium is 94.5:0.5:5.0. , manufactured by Sumitomo Chemical Co., Ltd. and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute), to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol was poured into a mold (molre) made of graphite, and vacuum-pressurized at a pressure of 40 MPa using a press machine made of graphite to carry out 1 000 ° C for 4 hours. The heat treatment was carried out to obtain a disk-shaped sintered body. (Hot press sintering) The relative density of the sintered body was calculated to be 9 5.8% from the size of the sintered product. Further, the relative density was determined as in Example 46. The obtained sintered product was subjected to boring and surface honing to obtain a sintered product of 50.8 mm cj) and a thickness of 3 mm. A copper plate was used as a support plate, and the obtained sintered body was fixed using indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions are as follows, and a film having a thickness of about 500 nm is obtained.

Target size: 50·8ιηπιφ 3mm Thick Sputtering device: Sputtered by Canon Anelva: DC magnetic sputtering Hardness reached: 2.Ox 1 0'4Pa Ar Pressure: 0.5Pa Substrate temperature: 2 5 0. . Sputtering power: 30W E-200S j -199- 201200616 Substrate: Sodium consuming glass (5 0.8 mm X 5 0 · 8 mm X 0 · 5 mm) The obtained film was dissolved in twice diluted hydrochloric acid to ICP- AES ("Th erm ο - 6 5 0 0" manufactured by Thermo Sci ent ific) measures the film composition to obtain a film having almost the same composition as the target composition. In addition, an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer ( TEM-EDX) investigates the doping state of titanium on zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 4·4 χ 1 (Τ4 Ω· Cm. The surface resistance is 8.8 Ω / □. Moreover, the specific resistance distribution on the transparent substrate is the in-plane uniformity. The transmittance of the transparent conductive substrate is 89% in the visible light region (380 nm to 780 nm) in the infrared region. The average value of (78 0 nm to 2700 nm) is 59%. Furthermore, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) is 94% on average, and in the infrared region (78〇nm~2700nm). The average transmittance was 94%. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.2 times the surface resistance before the moisture resistance test, and it was found to be excellent in moisture resistance -200-201200616. In addition, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.2 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated. The film quality was not changed, and it was found to be excellent in alkali resistance. The acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after thinning was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. As described above, it is understood that the film on the obtained transparent conductive substrate is transparent and has low electrical resistance, and also has a chemically durable (heat resistance, moisture resistance, alkali resistance, acid resistance) transparent conductive film. Since it is excellent in acid resistance, it is estimated that it has an appropriate etching rate at the time of patterning. (Comparative Example 1 5) Weigh zinc oxide so that the ratio of the element of zinc element to aluminum element and titanium element becomes 9 0.0 : 7.0: 3.0 (Zn〇, manufactured by Kishida Chemical Co., Ltd.), alumina (A1203, manufactured by Sumitomo Chemical Co., Ltd.), and titanium oxide (TiO (II), manufactured by High Purity Chemical Research Institute), and poured into polypropylene In the container, 2 mmc of zirconia balls and ethanol as a mixed solvent were poured. These were mixed in a ball mill to obtain a mixed powder. After the mixing operation, the mixed powder obtained by removing the ball and ethanol was poured into a mold to pressurize at a pressure of 40 MPa to obtain a disk-shaped formed body. Put it in an electric furnace' at an atmosphere of 1 300 in an Ar atmosphere. (: The heat treatment was carried out to obtain a sintered product. The relative density of the sintered product was calculated from the size of the sintered product to be 93.0%. Further, the relative density was obtained as in Example 46. The obtained sintered product was fed into -201 - 201200616. The sinter was obtained by cutting, surface honing, obtaining 5 〇.8 mmcj), thickness of 3 mm, using a copper plate as a support plate, and fixing the obtained sinter with indium solder to obtain a sputtering target. The resulting sputtering target was used to form a film by sputtering. The sputtering conditions are as follows, and a film having a thickness of about 500 nm is obtained. Target size: 50.8mmcj) 3mm thick sputtering device: "E-200S" manufactured by Canon Anelva Sputtering method: DC magnetic splashing reaching vacuum degree: 2.0x1 0 4Pa Ar pressure: 0.5Pa substrate temperature: 2 5 0〇 C Sputtering power: 30W Substrate used: Sodium consuming glass (50.8mmx50.8mmx0.5mm) The obtained film was dissolved in twice diluted hydrochloric acid and determined by ICP-AES ("Thermo-6500" manufactured by Thermo Scientific). The film is composed of a film having a composition almost equal to that of the target composition. In addition, the X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used ( TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. It can be understood that titanium substitution is dissolved in zinc. in. -202-201200616 The sheet resistance of the obtained film was measured by a four-probe method (manufactured by Mitsubishi Chemical Corporation, surface resistance meter) using a "Alpha-Step IQ" manufactured by Tencor Corporation, and the specific resistance was calculated to be 8.2 x 1 0·3Ω · cm. The surface resistance is 164 Ω/□. Further, the specific resistance distribution on the transparent substrate is uniform in plane. The transmittance of the obtained transparent conductive substrate was 89% in the visible light region (380 nm to 78 0 nm) and 50% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. The moisture resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the moisture resistance test was 1.3 times the surface resistance before the moisture resistance test, and it was found that the moisture resistance was excellent. Further, the heat resistance of the obtained transparent conductive substrate was evaluated, and the surface resistance after the heat resistance test was 1.3 times the surface resistance before the heat resistance test, and it was found that the heat resistance was excellent. The alkali resistance of the obtained transparent conductive substrate was evaluated, and the film quality was not changed before and after the immersion, and it was found that the alkali resistance was excellent. Further, the acid resistance of the obtained transparent conductive substrate was evaluated, and the film thickness after the immersion was thinned and dissolved. However, the film quality was not changed before and after the immersion, and it was found that the acid resistance was excellent. From the above, it was found that the film on the obtained transparent conductive substrate was also A transparent conductive film excellent in chemical durability (heat resistance, moisture resistance, alkali resistance, acid resistance) and alkali resistance and acid resistance, but has low near-infrared permeability and high electrical resistance. -203-201200616 (Example 54) As a zinc oxide powder (manufactured by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, 99.99%) Raw material powders were mixed in such a ratio that the atomic ratio of Zn: Ti was 92:8 to obtain a mixture of raw material powders, and then the resulting mixture was poured into a mold, and a uniaxial pressing machine was used to form a pressure of 500 kg/cm2. After molding, a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm was obtained. The formed body was annealed at 400 ° C for 3 hours under an argon atmosphere at a normal pressure (〇.l 〇 13 MPa) to obtain an oxide mixture (32) 〇 an energy dispersive fluorescent X-ray device (Shimadzu Corporation) The "EDX-700L" manufactured by the analysis of the obtained oxidation mixture (32), the atomic ratio of Zn to Ti is Zn: Ti = 92: 8 (Ti / (Zn + Ti) = 0_08). The crystal structure of the oxide mixture (32) was investigated by an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), and it was a mixture of a crystal phase of zinc oxide (ZnO) and titanium oxide (Ti203). Then, the obtained oxide mixture (32) was processed into a disk shape of 5 Οιηιηφ to prepare a target, and a zinc oxide-based film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.9995 % or more). Ar pure gas = 5 N), sputtering was performed under the conditions of a pressure of 0_5 Pa, an electric power of -204 - 201200616, 75 W, and a substrate temperature of 25 Torr, and a zinc oxide-based film having a film thickness of 500 nm was formed on the substrate. For the composition (Zn : Ti ) in the formed zinc oxide-based film, a wavelength-dispersive fluorescent X-ray device ("XRF·1 700WS" manufactured by Shimadzu Corporation) was used, and the fluorescent X-ray method was used. The quantitative analysis was performed for Zn: Ti (atomic ratio) = 92 : 8 (Ti/ ( Zn + Ti ) = 0.08). In addition, the X-ray diffraction apparatus ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.) was used for the transparent conductive film, and X-ray diffraction was performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer was used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. The specific resistance of the zinc oxide-based film on the transparent conductive substrate obtained from the zinc lanthanum was 8·3 χ1 (Γ4 Q.cm, and the surface resistance was 16.6 Ω/□. Further, the specific resistance distribution on the transparent substrate was in-plane uniform. The transmittance of the obtained transparent conductive substrate is 90% in the visible light region (3 80 nm to 7 8 Onm) and 65% in the infrared region (78 0 nm to 2700 nm). Further, the quartz glass substrate before film formation The transmittance in the visible light region (380 nm to 780 nm) is 94% on average, and the transmittance in the infrared region (78 nm to 270 nm) is 94% on average. Next, the formed film is measured at 30 ° C. Immersion in 1% by mass aqueous citric acid solution Film thickness reduction rate (nm/sec) at 60 seconds, adjustment -205-201200616 The etching speed of the film was examined. Further, the film thickness was measured using a stylus film thickness meter ("Alpha-Step IQ" manufactured by Tenco) As a result, the etching rate of the formed film is 27.27 nm/sec. In general, the etching rate is 0.5 nm/sec or less, which is a level that can be sufficiently controlled, and the citric acid aqueous solution is used as the etching liquid for the film. By patterning with a mask of a specific pattern, a good etching pattern can be formed. Therefore, the etching rate can be easily controlled to obtain a conductive zinc oxide thin film pattern. (Example 55) Zinc oxide Powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, purity 99.99%) as raw material powder, etc., so that Zn: Ti The atomic ratio was mixed in a ratio of 97:3 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and formed at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk shape having a diameter of 30 mm and a thickness of 5 mm. Shaped body The formed body was sintered at 80 ° C for 4 hours under an argon atmosphere under normal pressure (1.0 1 325 x 102 kPa) to obtain an oxide sintered product (3 3 ). Energy dispersive fluorescent X-ray The oxidized sintered product (33) was analyzed by the device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti was Zn: Ti = 97: 3 (Ti/( Zn + Ti ) = 0.03 ) . The crystal structure of the oxide sintered product (33) was investigated by an X-ray diffraction device ("206-201200616 RINT2000" manufactured by Rigaku Electric Co., Ltd.), which was a crystal of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). The mixture of phases, titanium oxide is completely absent. Then, the obtained oxide sintered product (33) was processed into a disk shape of 50 mm cj) to prepare a target. A zinc oxide-based film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.999 5 % or more). , Ar pure gas = 5 N), sputtering was carried out under the conditions of a pressure of 55 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a zinc oxide-based film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed zinc oxide-based film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used for inspection. The quantitative analysis was performed for Zn: Ti (atomic ratio) = 97:3 (Ti/(Zn + Ti) = 0.03). In addition, an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) is used for the zinc oxide-based film, and X-ray diffraction is performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer is used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc. The specific resistance of the zinc oxide-based film on the obtained transparent conductive substrate was 4·4 χ1 (Γ4 Ω·cm, and the surface resistance was 8.8 Ω/□. Further, the specific resistance distribution of -207-201200616 on the transparent substrate was in-plane uniformity. The transmittance of the obtained transparent conductive substrate is 89% on average in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (780 nm to 2700 nm). Further, the quartz glass substrate before film formation The transmittance in the visible light region (380 nm to 780 nm) is 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) is 94% on average. Next, by measuring the formed film at 3 (TC 1 quality) The film thickness reduction rate (nm/sec) when immersed in a citric acid aqueous solution for 60 seconds, and the etching rate of the film was investigated. Further, the film thickness was measured by a stylus type film thickness meter ("Alpha-Step IQ" manufactured by Tenco Corporation). As a result, the etching rate of the formed film was 〇40 nm/sec. In general, when the etching rate was 0.5 nm/sec or less, the level of the film was sufficiently controlled, and the citric acid aqueous solution was used as the etching film. Liquid, using a specific map The mask of the type is patterned to form a good etching pattern. Therefore, the etching rate can be easily controlled to obtain a conductive zinc oxide thin film pattern (Comparative Example 16) with zinc oxide powder (ZnO; Wako Pure Chemical Industries Co., Ltd., special grade) and titanium oxide powder (Ti203; manufactured by High Purity Chemical Research Institute, 99.99% purity) as raw material powder, so that the atomic ratio of Zii : Ti becomes Mixing 99:1 to obtain a mixture of raw material powders -208 - 201200616 Next, the obtained mixture was poured into a mold, and formed at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk shape having a diameter of 30 mm and a thickness of 5 mm. The molded body was annealed at 40 (TC for 3 hours under an atmospheric pressure (0.1013 MPa) argon atmosphere to obtain an oxide mixture (C14). Energy dispersive fluorescent X-ray device (Shimadzu Corporation) Manufactured "EDX-700L") Analyzed oxidized mixture (C14), the atomic ratio of Zn to Ti is Zn: Ti = 99 : 1 (Ti / ( Zn + Ti ) = 0.01) ο Next, the resulting oxidation Material mixture (C14) processing A disk shape of 50τηπιφ was used to prepare a target, and a zinc oxide-based film was formed by sputtering using the target to obtain a transparent conductive substrate. That is, the target and the transparent substrate (quartz glass substrate) were separately placed on the sputtering substrate. In the plating apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), Ar gas (purity of 99.9995 % or more, Ar pure gas = 5N) was introduced at 12 SCCm, and the pressure was 0.5 Pa, the electric power was 100 W, and the substrate temperature was 130 °C. Under the conditions of sputtering, a zinc oxide-based film having a thickness of 200 nm is formed on the substrate.

For the composition (Zn : Ti ) in the formed zinc oxide-based film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used for inspection. The quantitative analysis was performed for Zn: Ti (atomic ratio) = 99: 1 (Ti/(Zn + Ti) = 0.01). In addition, X-ray diffraction apparatus ("RINT2 000" manufactured by Rigaku Electric Co., Ltd.) was used for the zinc oxide-based film, and X-ray diffraction was performed using an accessory for film measurement, and energy dispersive X-209- was used. 201200616 ray microanalyzer (TEM-EDX) investigates the doping state of titanium to zinc 'reuse electric field radiation electron microscopy (FE-SEM) to investigate the crystal structure' as a single phase of the C-axis aligned wurtzite type. The specific resistance of the zinc oxide-based thin film on the transparent conductive substrate obtained by dissolving titanium in a zinc-soluble cerium was 2.25 χ 10·3 Ω·ί: ηη, and the surface resistance was 112.5 Ω/□. Furthermore, the specific resistance distribution on the transparent substrate is uniform in-plane. The transmittance of the obtained transparent conductive substrate was 90% on average in the visible light region (3 8 〇 11111 to 78 〇 11111), and 70% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 78 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. Next, as in Example 54, the etching rate of the formed film was investigated to be 1.2 nm/sec. In the case of the film, the etching rate is 1. 〇nm/sec or more, so that it is difficult to control, and the same citric acid aqueous solution as in Example 1 is used as an etching liquid for the film, and the pattern is patterned using a mask of a specific pattern. It is difficult to form a good etching pattern. (Comparative Example 1 7)

A zinc oxide film doped with aluminum atoms was formed on soda lime glass (thickness 〇.7 mm) by a DC magnetron sputtering method using a target for zinc oxide sputtering containing 2% by mass of alumina. Further, the sputtering was carried out at a power of 75 W -210 - 201200616 at the time of film formation, a film formation pressure of 0.5 Pa, an oxygen partial pressure of OPa, a substrate temperature of room temperature, and a film formation time of 30 minutes. Next, as in Example 54, the etching rate of the formed film was investigated to be 1.5 nm/sec. In the case of the film, since the etching rate is 1. Onm/sec or more, it is difficult to control, and the same citric acid aqueous solution as in Example 1 is used as an etching liquid for the film, and the pattern is patterned by a mask of a specific pattern. It is difficult to form a good etching pattern. (Example 56) As a raw material, zinc oxide powder (manufactured by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): manufactured by High Purity Chemical Research Institute, purity: 99.99%) The powder was mixed in such a ratio that the atomic ratio of Zn: Ti was 92:8 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a molding pressure of 500 kg/cm 2 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The molded body was annealed at 400 t for 3 hours under an argon atmosphere of a normal pressure (1.013 MPa) to obtain an oxide mixture (34)0. The energy dispersive fluorescent X-ray device (manufactured by Shimadzu Corporation) EDX-700L") analysis of the obtained oxidation mixture (34), the atomic ratio of Zn to Ti is Zn: Ti = 92: 8 (Ti / (Zn + Ti) = 0.08). The oxide mixture (the crystal structure of 3〇) was investigated by an X-ray diffraction device ("211 - 201200616 RINT2000" manufactured by Rigaku Electric Co., Ltd.), which is a crystal phase of zinc oxide (ZnO) and titanium oxide (Ti203). Next, the obtained oxide mixture (34) is processed into a disk shape of 50 ΐΏΐηφ to prepare a target, and a zinc oxide-based film is formed by sputtering using the target to obtain a transparent conductive substrate. The target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 SCCm (purity of 99.9995% or more, Ar pure gas = 5 Ν). The sputtering was carried out under the conditions of a pressure of 0.5 Pa, a power of 75 W, and a substrate temperature of 250 ° C to form a zinc oxide-based film having a thickness of 500 nm on the substrate. The composition (Zn : Ti ) in the formed zinc oxide-based film, Using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation), quantitative analysis using a calibration curve using a fluorescent X-ray method is Zn: Ti (atomic ratio) = 92 : 8 ( Ti / (Zn + Ti ) = 0.08). Further, the zinc oxide-based film was subjected to X-ray diffraction using an X-ray diffraction device ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.). At the same time, the doping state of titanium to zinc was investigated by energy dispersive X-ray microanalyzer (TEM-EDX), and the crystal structure was investigated by electric field emission electron microscopy (FE-SEM), which was a C-axis aligned bauxite type. In the single phase, it is understood that the titanium substitution is solid-dissolved in the zinc. The specific resistance of the zinc oxide-based film on the obtained transparent conductive substrate is 7.6 x 1 (T4 Q.cm' surface resistance is 15·2 Ω/□. Further, the transparent substrate The specific resistance distribution is uniform in-plane. -212- 201200616 The transmittance of the obtained transparent conductive substrate is 90% in the visible light region (3 80 nm to 7 8 Onm) and averaging in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was on average, and the transmittance in the infrared region (780 nm to 27 Å nm) was 94% on average. Next, by measuring the formed film at 3 (TC The film thickness reduction rate (nm/sec) when immersed in a 1% by mass citric acid aqueous solution for 60 seconds, and the uranium engraving speed of the film was investigated. Further, the film thickness was measured by a stylus type film thickness meter (Alpha-Step manufactured by TenCO). As a result, the etching rate of the formed film was 27.27 nm/sec. In general, when the etching rate is 0.5 nm/sec or less, the level can be sufficiently controlled. For the film, the citric acid aqueous solution is used as an etching solution, and the mask is patterned by a specific pattern to form a good pattern. Etched pattern. Therefore, the etching rate can be easily controlled to obtain a conductive zinc oxide thin film pattern. (Example 57) As a raw material, zinc oxide powder (made by ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): High Purity Chemical Research Institute (purity)) The powder was mixed in such a ratio that the atomic ratio of zn : Ti was 97:3 to obtain a mixture of raw material powders. Then, the obtained mixture was poured into a mold, and molded at a molding pressure of 500 kg/cm 2 at -213 to 201200616 by a uniaxial pressing machine to obtain a disk-shaped formed body having a diameter of 30 mm and a thickness of 5 mm. The formed body was sintered at 800 ° C for 4 hours under an argon atmosphere under a normal pressure (1.0 1 325 x 102 kPa) to obtain an oxide sintered product (35). The oxidized sintered product (35) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn: Ti = 97: 3 (Ti/ (Zn + Ti) = 0.03). The crystal structure of the oxide sintered product (35) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) as a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04). Titanium oxide is completely absent. Then, the obtained oxide sintered product (35) was processed into a disk shape of 50 mnuj) to prepare a target, and a zinc oxide-based film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sccm (purity of 99.9995 % or more). Ar pure gas = 5 N), sputtering was performed under the conditions of a pressure of 0.5 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a zinc oxide-based film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed zinc oxide-based film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used for inspection. The quantitative analysis was performed for Zn: Ti (atomic ratio) = 97:3 (Ti/(Zn + Ti) = 0.03). In addition, the zinc oxide-based film is subjected to X-ray diffraction using an X-ray diffraction package (RINT2000) manufactured by Rigaku Electric Co., Ltd., and an energy dispersive type is used. X-ray microanalyzer (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM), which is a single phase of the C-axis aligned wurtzite type. The specific resistance of the zinc oxide-based film on the transparent conductive substrate obtained by dissolving titanium in a zinc-soluble cerium was 4.2 x 10 - 4 Q.cm, and the surface resistance was 8.4 Ω / □. Furthermore, the specific resistance distribution on the transparent substrate is in-plane uniform. The transmittance of the obtained transparent conductive substrate was 89% on average in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 270 nm) was 94% on average. Next, the film formation rate was measured by measuring the film thickness reduction rate (nm/sec) when the formed film was immersed in a 1 mass% citric acid aqueous solution at 30 ° C for 60 seconds. Further, the film thickness was measured using a stylus type film thickness meter ("Alpha-Step IQ" manufactured by Tenco Corporation). As a result, the uranium engraving speed of the formed film was 〇.40 nm/sec. In general, when the etching rate is 〇.5 nm/sec or less, it is a level that can be sufficiently controlled. For the film, the citric acid aqueous solution is used as an etching liquid, and patterning is performed by using a mask of a specific pattern. Good etching pattern. Therefore, the etching rate can be easily controlled to obtain a conductive zinc oxide-215-201200616-based film pattern. (Example 5 8 ) Manufactured by zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (T i O (11): High Purity Chemical Research Institute), purity 99, 99%) As a raw material powder, these were mixed at a ratio of the atomic ratio of Zn:Ti to 97:3 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the ball and the ethanol is poured into a mold (mold) made of graphite, and vacuum-pressurized at a pressure of 40 MPa by a press machine made of graphite to carry out 1 〇〇〇 ° C, Heat treatment was carried out for 4 hours to obtain a disk-shaped oxide sintered product (36). The oxide sintered product (36) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was

Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03). The crystal structure of the oxide sintered product (36) was investigated by an X-ray diffraction device ("RINT2000" manufactured by Rigaku Electric Co., Ltd.), which was a crystal phase of zinc oxide (ZnO) and zinc titanate (Zn2Ti〇4). The mixture, titanium oxide, was completely absent. Then, the obtained oxide sintered product (36) was processed into a disk shape of 50 ηηηιφ to prepare a target, and a zinc oxide-based film was formed by sputtering using the target to obtain a transparent conductive substrate. That is, the target and the transparent substrate (quartz glass substrate) were respectively placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva), and Ar gas was introduced at i2 sccm (pure-216-201200616). A degree of 99.9995 % or more, Ar pure gas = 5 N) was sputtered under the conditions of a pressure of 0.5 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a zinc oxide-based film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed zinc oxide-based film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used for inspection. The quantitative analysis was performed for Zn: Ti (atomic ratio) = 97:3 (Ti/(Zn + Ti) = 0.03). Further, the zinc oxide-based film was subjected to X-ray diffraction using an X-ray diffraction apparatus ("RINT 2 000" manufactured by Rigaku Electric Co., Ltd.), and an energy dispersive X-ray microanalysis was used. The instrument (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. The specific resistance of the zinc oxide-based film on the transparent conductive substrate obtained from cerium in zinc was 4.2 x 10 4 Q.cm, and the surface resistance was 8.4 Ω / □. Further, the specific resistance distribution on the transparent substrate is an in-plane uniform sentence. The transmittance of the obtained transparent conductive substrate was 89% on average in the visible light region (380 nm to 780 nm), and 60% in the infrared region (780 nm to 2700 nm). Further, the transmittance of the quartz glass substrate before film formation in the visible light region (380 nm to 78 nm) is 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) is 94% on average. The film formed was measured by immersing 6 (the film thickness reduction rate (nm/sec) at the time of leap seconds at 1% by mass of a 30% by mass of a lemon-217-201200616 citric acid aqueous solution, and investigating the etching rate of the film. It was measured using a stylus type film thickness meter ("Alpha-Step IQ" manufactured by Tenco Corporation). As a result, the etching speed of the formed film was 〇.40 nm/sec. In general, the etching rate was at 〇5 μm/sec. The following is a level that can be sufficiently controlled. For the film, the citric acid aqueous solution is used as an etching solution, and a mask of a specific pattern is used for patterning, whereby a good etching pattern can be formed. Therefore, the etching rate can be easily controlled. A conductive zinc oxide thin film pattern was obtained. (Comparative Example 1 8 ) Zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): high purity chemical 硏Institute (stock) manufacturing, purity 99.99% As a raw material powder, the mixture is mixed in a ratio of the atomic ratio of Ζι : Ti to 88:12 to obtain a mixture of raw material powders. After the mixing operation, the mixed powder obtained by removing the spheres and ethanol is poured into graphite. In the mold (mold), a press machine made of graphite was used, and vacuum-pressurized at a pressure of 40 MPa, and heat treatment was performed at 10 ° C for 4 hours to obtain a disk-shaped oxide sintered product (C15). The oxide sintered product (C15) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti was Zn : Ti = 88 : 12 ( Ti / ( Zn + Ti ) = 0.12 ). The crystal structure of the oxide sintered product (C15) was investigated by an X-ray diffraction device ("218-201200616 RINT2〇00" manufactured by Rigaku Electric Co., Ltd.) as zinc oxide. A mixture of (ZnO) and a crystal phase of zinc titanate (zn2Ti〇4), titanium oxide is completely absent. Next, the obtained oxide sintered product (C15) is processed into a disk shape to prepare a target, and the target is used. Film-forming zinc oxide film by sputtering method A conductive substrate. That is, the above target and the transparent substrate (quartz glass substrate) are disposed in a sputtering apparatus (

In "E-200" manufactured by Canon-Anelva Co., Ltd., Ar gas (purity of 99.9995% or more 'Ar pure gas = 5N) was introduced at i2sccm, and the pressure was 0_5Pa, electric power 75W, and substrate temperature of 250 °C. By sputtering, a zinc oxide-based film having a film thickness of 500 nm was formed on the substrate. The composition (Zn: Ti) in the formed zinc oxide-based film is detected by a fluorescent X-ray method using a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) The quantitative analysis was performed for Zn: Ti (atomic ratio) = 88 : 12 (Ti/ ( Zn + Ti) = 0.12). In addition, an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.) is used for the zinc oxide-based film, and X-ray diffraction is performed using an accessory for film measurement, and an energy dispersive X-ray microanalyzer is used. (TEM-EDX) investigates the doping state of titanium to zinc, and then investigates the crystal structure by electric field emission electron microscopy (FE-SEM). It is a single phase of the Zinc-aligned wurtzite type. In zinc. The specific resistance of the zinc oxide-based film on the obtained transparent conductive substrate was 2.1 x 1 (Γ2 Ω·cm, and the surface resistance was 420.0 Ω/□. Further, the specific resistance distribution on the transparent substrate-219-201200616 was in-plane uniform. The transmittance of the obtained transparent conductive substrate is 89% in the visible light region (380 nm to 780 nm) and 60% in the infrared region (780 nm to 2700 nm). Further, the quartz glass substrate before film formation is in the visible light region ( The transmittance in the range of 380 nm to 780 nm is 94% on average, and the transmittance in the infrared region (780 nm to 27 Å Onm) is 94% on average. Next, the film formed by measuring the mass ratio of 3% by mass of citric acid aqueous solution The film thickness reduction rate (nm/sec) when immersed for 60 seconds, and the etching rate of the film were investigated. Further, the film thickness was measured using a stylus type film thickness meter ("Alpha-Step IQ" manufactured by Teuco Corporation). The etching rate of the formed film is 0.16 nm/second. In general, the etching rate is 〇.5 nm/sec or less, which is a level that can be sufficiently controlled. For the film, the citric acid aqueous solution is used as an etching solution, and the specificity is utilized. Pattern cover Since the mask is patterned, a good etching pattern can be formed. Therefore, the etching rate can be easily controlled, and a conductive zinc oxide thin film pattern can be obtained. The etching rate can be sufficiently controlled, but the electric resistance is high. The raw material powder is produced by using zinc oxide powder (ZnO; Wako Pure Chemical Industries, Ltd., special grade) and titanium oxide powder (TiO (II): High Purity Chemical Research Institute (purity) to produce 'purity 99_99%). The mixture of the raw material powders is obtained by mixing the atomic ratio of zn: Ti to 97: 3. -220- 201200616 After the mixing operation, the mixed powder obtained by removing the balls and ethanol is poured into a mold composed of graphite (die) In the press, a press made of graphite was vacuum-pressurized at a pressure of 40 MPa, and subjected to heat treatment at 10 ° C for 4 hours to obtain a disk-shaped oxide sintered product (37). The oxide sintered product (3 7 ) was analyzed by a fluorescent X-ray device ("EDX-700L" manufactured by Shimadzu Corporation). The atomic ratio of Zn to Ti is

Zn : Ti = 97 · 3 ( Ti / ( Zn + Ti ) = 0.03 ) ° The crystal structure of the oxide sintered product (37) was investigated by an X-ray diffraction apparatus ("RINT2000" manufactured by Rigaku Electric Co., Ltd.). As a mixture of zinc oxide (ZnO) and zinc titanate (Zn2Ti04), titanium oxide is completely absent. Then, the obtained oxide sintered product (37) was processed into a disk shape of 50 mm cj) to prepare a target, and a zinc oxide-based film was formed by sputtering using the target to obtain a transparent conductive substrate. In other words, the target and the transparent substrate (quartz glass substrate) were placed in a sputtering apparatus ("E-200" manufactured by Canon-Anelva Co., Ltd.), and Ar gas was introduced at 12 sCCm (purity of 99.9995 % or more). Ar pure gas = 5 N) was sputtered under the conditions of a pressure of 55 Pa, an electric power of 75 W, and a substrate temperature of 250 ° C to form a zinc oxide-based film having a film thickness of 500 nm on the substrate. For the composition (Zn : Ti ) in the formed zinc oxide-based film, a wavelength-dispersive fluorescent X-ray device ("XRF-1 700WS" manufactured by Shimadzu Corporation) is used, and the fluorescent X-ray method is used for inspection. The quantitative analysis was performed for Zn: Ti (atomic ratio) = 97:3 (Ti/(Zn + Ti) = 0.03). In addition, the zinc oxide-based film is placed in an X-ray diffraction package -221 201200616 ("RINT2〇00" manufactured by Rigaku Electric Co., Ltd.), and X-ray diffraction is performed using an accessory for film measurement, and energy dispersion is used. X-ray microanalyzer (TEM-EDX) was used to investigate the doping state of titanium to zinc, and then the electric field radiation electron microscope (FE-SEM) was used to investigate the crystal structure, which is a single phase of the C-axis aligned wurtzite type. Learn that titanium replacement is dissolved in zinc. The specific resistance of the zinc oxide-based film on the obtained transparent conductive substrate was 4·2 χ1 (Γ4 Ω·(: ηη, surface resistance was 8.4 Ω/□. Further, the specific resistance distribution on the transparent substrate was transparent in-plane β). The transmittance of the conductive substrate is 89% in the visible light region (380 nm to 7 8 Onm) and 60% in the infrared region (78 0 nm to 2700 nm). Further, the quartz glass substrate before film formation The transmittance in the visible light region (380 nm to 780 nm) was 94% on average, and the transmittance in the infrared region (780 nm to 2700 nm) was 94% on average. Next, the film formed by measurement was measured at 20 °C. The film thickness reduction rate (nm/sec) when immersed in an aqueous solution of 1 mol/l of acetic acid for 120 seconds, and the etching rate of the film was investigated. Further, the film thickness was measured by a stylus type film thickness meter (Alpha-Step, manufactured by Tenco Corporation). As a result, the etching rate of the formed film was 0.33 nm/sec. In general, the uranium engraving speed was at a level of sufficient control if it was 0.5 nm/sec or less, and the above-mentioned citric acid aqueous solution was used for the film. As an etchant, use a specific pattern of masking By patterning, a good etching pattern can be formed. Therefore, the etching rate can be easily controlled to obtain a conductive zinc oxide-222-201200616 film pattern. (Comparative Example 1 9) Using 2% by mass of alumina The zinc oxide sputtering target is a zinc oxide film doped with aluminum atoms on a soda lime glass (thickness 0.7 mm) by DC magnetron sputtering. Further, the sputtering is performed by film formation. 75 W, the film formation pressure was 0.5 Pa, the oxygen partial pressure was OPa, the substrate temperature was room temperature, and the film formation time was 30 minutes. Next, in the same manner as in Example 1, the uranium engraving speed of the formed film was examined and found to be 1 . 5 nm / sec. Next, the film etch rate was investigated by measuring the film thickness reduction rate (rim / sec) when the formed film was immersed in an aqueous solution of 1 mol / 1 of acetic acid at 20 t for 120 seconds. The stylus type film thickness meter ("Alpha-Step IQ" manufactured by Teuco Co., Ltd.) was measured. As a result, the etching rate of the formed film was 2.42 nm/sec. In the case of the film, since the etching rate was l. Onm/sec or more, Difficult to control, relative to the film, with Example 59 The same aqueous acetic acid solution as the etching solution is patterned by using a mask of a specific pattern, and it is difficult to form a good etching pattern. [Schematic Description] FIG. 1 is a view showing an ion plating apparatus which can be preferably used in the present invention. -223- 201200616 [Explanation of main component symbols] 10: Ion plating apparatus 12: Vacuum vessel 14: Plasma gun 1 4a: Cathode 1 4b, 1 4c: Intermediate electrode 1 4 d: Electromagnetic coil 14e: Control coil 16: anode member 1 6 a : ground line 16b: auxiliary anode 18: conveying mechanism 18a: conveying path 18b: roller 19: oxygen container 20a: carrier gas introduction path 2 0b: atmosphere gas supply path other than oxygen 20c: supply path of inert gas 2〇d: exhaust system 2 1 : mass flow meter 22: vapor deposition material 24a: permanent magnet 24b: coil W: substrate - 224 - 201200616 WH : substrate holding member PB : plasma beam TH :through hole

Claims (1)

201200616 VII. Patent application scope: 1. An oxide sinter consisting essentially of zinc, titanium and oxygen, and the atomic ratio of titanium to titanium/titanium is Ti/(Zn + Ti) More than 0.02 and less than 0.1. 2. The oxide sinter of claim 1 is composed of a zinc oxide phase and a zinc titanate compound phase. 3. An oxide sinter of the first aspect of the patent application, which is composed of a zinc titanate compound phase. 4. The oxide sinter of claim 1 which is substantially free of a crystalline phase of titanium oxide. 5 · The oxide sinter of the first application of the patent scope, wherein the titanium valence is less than 4 valence. 6. The oxide sinter of claim 1 of the patent scope, which also contains gallium, aluminum, tin, antimony, bismuth, chromium and at least one element selected from the group consisting of The method of applying the oxide sinter of any one of the above items (1) to (6), after forming the raw material powder containing the following (A) and/or (B), and molding the obtained molded article in an inert atmosphere , a method of sintering at 600 ° C to 1 500 ° C in a vacuum or a reducing atmosphere or an inert atmosphere, (A) a mixed powder of titanium oxide powder and zinc oxide powder, or a mixture of titanium oxide powder and zinc hydroxide powder Powder, (B) zinc titanate compound powder. 8. A method of producing an oxide sinter of -226-201200616, as in any one of claims 1 to 6, which is formed by forming a raw material powder containing the following (A) and/or (B) Thereafter, the obtained shaped product is sintered at 600 ° C to 1 500 ° C in an atmospheric atmosphere or an oxidizing atmosphere, and then further annealed in an inert atmosphere, in a vacuum or in a reducing atmosphere, (A) titanium oxide powder a mixed powder with zinc oxide powder, or a mixed powder of titanium oxide powder and zinc hydroxide powder, (B) a zinc titanate compound powder. 9. The method of claim 7 or 8, wherein the titanium oxide powder is a powder of low valence titanium oxide represented by the formula: Ti02.x (Χ = 〇·1~1). The method of claim 8, wherein the annealing treatment atmosphere is at least one atmosphere selected by a group consisting of nitrogen, argon, helium, carbon dioxide, ammonia and hydrogen or is a vacuum. An oxide mixture composed of zinc oxide and titanium oxide, and having a total atomic ratio of Ti/(Zn + Ti) of titanium to titanium of more than 0.02 and not more than 0.1. 12. The oxide mixture according to the scope of claim 2, wherein the ruthenium in the ruthenium oxide is less than 4. 1 3 · The oxide mixture of the η item of the patent application also contains at least one element selected from the group consisting of gallium, methane, tin, antimony, bismuth, zirconium and the group. A method for producing an oxide mixture according to any one of claims 1 to 13, which comprises a mixed powder of titanium oxide powder and zinc oxide powder or titanium oxide powder and zinc hydroxide powder. Mixed powder-227- 201200616 After the formation of the raw material powder, the obtained shaped body is annealed at 50 ° C or more and less than 600 eC in an atmosphere, an oxidizing atmosphere, an inert atmosphere, a vacuum or a reducing atmosphere. The method of processing. 15. The method of claim 14, wherein the titanium oxide powder is a powder of low valence titanium oxide represented by the formula: Ti02-x (X = 0.1~1). 16. The method of claim 14, wherein the annealing treatment atmosphere is at least one atmosphere selected by a group consisting of nitrogen, argon, helium, carbon dioxide and hydrogen or is a vacuum. 17. A target, which is a target for forming a film by sputtering, ion plating, pulse laser deposition (PLD) or electron beam (EB) evaporation. It is obtained by processing an oxide sintered product according to any one of claims 1 to 6 or an oxide mixture according to any one of claims 1 to 13. 18. A method of using a target, which is formed by using one selected from the group consisting of a pulsed laser deposition method (PLD method), a sputtering method, an ion plating method, and an electron beam (EB) evaporation method. A method of using a zinc oxide-based transparent conductive film, wherein the target system is substantially composed of zinc, titanium, and oxygen, and the atomic ratio of titanium to total of zinc and titanium is more than 0/(Zn + Ti ). 〇2 is obtained by processing an oxide sinter or an oxide mixture of 0.1 or less. 19. The method of claim 18, wherein the titanium is derived from titanium bismuth-228-201200616, which is represented by the formula: Ti〇2_x ( Χ = 〇·1~1 ). The method of claim 19, wherein the low valence oxidization is oxidized by titanium dioxide (TiO) or titanium oxide composed of trivalent titanium (T i 2 Ο 3 ). 2 1. A zinc oxide-based transparent conductive film formed by the method of any one of items 18 to 20 of the patent application. A transparent conductive substrate comprising a zinc oxide-based transparent conductive film according to claim 21 of the patent application. 23. The transparent conductive substrate according to claim 22, wherein the transparent substrate is a glass plate, a resin film or a resin sheet. A zinc oxide-based transparent conductive film forming material comprising an oxide mixture or an oxide sintered body, wherein an atomic ratio of titanium to a total of titanium and titanium in an oxide mixture or an oxide sintered body is Ti / ( Zn + Ti) exceeds 〇·〇2 and is 0.1 or less, containing zinc oxide as a main component, and contains at least one of gallium and aluminum oxides and titanium oxide, and the ratio of the number of atoms of gallium or aluminum is relative to all The number of metal atoms is 0.5% or more and 6% or less, and the titanium oxide is a low valence titanium oxide represented by the formula Ti02.x (X = 0.1 to 1). 25. The zinc oxide-based transparent conductive electric film forming material according to claim 24, wherein the titanium atomic valence in the low valence titanium oxide is divalent or trivalent. 26. The zinc oxide-based transparent conductive film forming material according to claim 24, wherein the oxide sintered compact has a relative density of 93% or more. 27. A target, which is a target for forming a film by sputtering, ion plating, pulse-229-201200616 laser deposition (PLD) or electron beam (EB) evaporation. It is obtained by processing a zinc oxide-based transparent conductive film forming material according to any one of claims 24 to 26. 28. A method of forming a zinc oxide-based transparent conductive film using a target as in claim 27 of the patent application, by sputtering, ion plating, pulsed laser deposition (PLD) or electron beam ( EB) A zinc oxide-based transparent conductive film is formed by a vapor deposition method. A transparent conductive substrate comprising a zinc oxide-based transparent conductive film formed on a transparent substrate by a method of forming a transparent conductive film according to the twenty-eighth aspect of the patent application. 3 〇. A patterning method for patterning a zinc oxide-based film by acid etching, wherein the zinc oxide-based film is mainly composed of zinc oxide, and the total number of atoms of titanium relative to zinc and titanium The film having a specific ratio of Ti/(Zn + Ti) of more than 0.02 and not more than 0.1. 31. The patterning method according to claim 30, wherein the zinc oxide-based film is a film obtained by processing an oxide sinter or an oxide mixture substantially composed of zinc, titanium, and oxygen as a film. The material is formed into a film. 32. A method of patterning according to claim 30, wherein the titanium is derived from titanium having a low valence titanium oxide represented by the formula TiO2.x (X = 0.1 to 1). 33. The patterning method according to claim 32, wherein the low valence titanium oxide is titanium oxide (Ti0) composed of divalent titanium or titanium oxide (Ti203) composed of trivalent titanium. The method of patterning according to claim 30, wherein the zinc oxide-based film is a film formed by a vacuum film formation method. 35. The method of patterning according to claim 34, wherein the vacuum film forming method is a sputtering method, an ion plating method, a pulse laser method (PLD method) or an electron beam (EB) evaporation method. -231 -