TW201200610A - Oxide vapor deposition material and transparent conductive film - Google Patents

Abstract

The oxide vapor deposition material of the present invention is characterized by comprising a sintered body which contains a main component of indium oxide and 0.001 to 0.614 of tin in Sn/In atom ratio. Because of the oxide vapor deposition material with a L* value of 54 to 75 in CIE1976 color system has the most suitable oxygen content, a transparent conductive film having low resist and high transparency within visible range can be produced even if an amount of oxygen gas introduced to the film-forming vacuum tank is less. Because an introducing amount of oxygen gas is less, it is capable of reducing the component difference of the film and the vapor deposition material, and also, it is capable of reducing the variation of film component during mass production or reducing the variation of properties.

Description

201200610 VI. Description of the Invention: [Technical Field] The present invention relates to an oxide vapor deposition material vapor deposition method, an ion plating method, or a high-density plasma auxiliary air vapor deposition method for producing a transparent conductive film. The transparency produced by using this oxide vapor-deposited material is used to manufacture a transparent conductive material which is a high transmittance of a transparent electrode of a solar cell in the visible light region. [Prior Art] The transparent conductive film has high conductivity and transmittance. Moreover, in order to utilize this characteristic, the transparent solar cell, the liquid crystal display element, and other various anti-static films used in the near-infrared region for absorption into the window glass of automobiles or buildings, and the anti-fog of the refrigerated display cabinet, etc. Further, in the transparent conductive film, tin oxide (Sn02), which is generally a dopant of tin or fluorine as a dopant, is used as a dopant of zinc oxide (ΖηΟ); a dopant-containing indium oxide (?n203) or the like. In particular, a tin indium oxide film, i.e., an ln203-Sn film, is referred to as a film, and is widely used because it is easy to obtain a low-resistance transparent guide. - It is used for various kinds of oxide vapor deposition materials and conductive films which are used for electron beam-assisted vapor deposition, etc., for example, high-light-conducting film which is useful in low-resistance and which is used for display film evaporation in the visible light region. It is used for electrodes such as solar light-receiving elements, and can be used as a line-type reflective film or various heat-dissipating bodies. In general, it contains ITO (Indium Tin Oxide) electric film containing aluminum, gallium, indium, tin, tungsten, and titanium as dopants. So far, the industry has been 201200610 and these transparent conductive As a method of producing the film, a vacuum deposition method, a sputtering method, a method of applying a coating liquid for forming a transparent conductive layer, and the like are generally used. Among them, the vacuum vapor deposition method or the sputtering method is effective when a material having a low vapor pressure is used or when a precise film thickness control is necessary, and is industrially useful because it is very simple in operation. Further, when the vacuum distillation method and the sputtering method are compared, the vacuum distillation method can form a film at a high speed, and has excellent mass productivity. However, in general, the vacuum evaporation method is performed in a vacuum of about 1 〇 3 to 10 · 2 Pa, and after heating a solid or liquid of an evaporation source to be temporarily decomposed into gas molecules or atoms, the vacuum deposition method is again performed on the surface of the substrate. The method of condensing as a film. Further, the evaporation source is heated in various ways, and is generally a resistance heating method (RH method) or an electron beam heating method (EB method or electron beam evaporation method). In addition, a reactive steaming method in which a reaction gas such as helium gas is introduced into a film forming chamber (cavity) while performing vapor deposition is known. Further, in the case where an oxide film such as ITO is deposited, the electron beam evaporation method is often used in history. That is, once the ITO oxide evaporation material (also referred to as ITO ingot or ITO 9) is used for the evaporation source, the argon gas of the reaction gas is introduced into the film forming chamber (cavity), and the electric field is used to make the thermal electrons. When the hot electrons jumping out of the filament (mainly W wire) are accelerated and irradiated onto the ITO oxide steaming material, the irradiated portion becomes a local high temperature and evaporates and deposits on the substrate. Further, by using a thermal electron emitter or RF discharge to generate plasma, the plasma or the reaction gas (02 gas or the like) is activated by the plasma, and the activation reactivity of the low-resistance film can be produced on the low-temperature substrate. Steaming 201200610 Plating (ARE method) is also a method for film formation of ITO. In addition, the high-density plasma-assisted vapor deposition method (HDPE method) using a plasma gun has recently become a technique effective for IT film formation, and has been widely used in the industry (see Non-Patent Document 1: " Vacuum", Vol.  44, No.  4, 2001, p.  43 5-439). In this method, an arc discharge is maintained using a plasma generating device (plasma gun) to maintain an arc discharge between a cathode contained in the plasma gun and a crucible (anode) of the evaporation source. The electrons released from the cathode are guided by a magnetic field and concentrated to be irradiated to a portion of the ITO oxide evaporation material that is fed to the crucible. The evaporate evaporates and deposits on the substrate from the portion where the electron beam is irradiated to a local high temperature. Since the vaporized vapor or the introduced helium gas system is activated in the plasma, an IT diaphragm having good electrical characteristics can be produced. In addition, in another classification method of various vacuum evaporation methods, the ionization method associated with the vaporized material or the reaction gas is an ion shovel method (IP method) as an ITO film which obtains low resistance and high light transmittance. The method is effective (see Non-Patent Document 2: "Technology of Transparent Conductive Film", Ohm Corporation, 1999, pp. 205-211). However, regardless of the solar cell of any type used in the transparent conductive film, the transparent conductive film is indispensable on the electrode on the surface side irradiated with light, and it is conventional to use the above-mentioned IT ruthenium film or doped with aluminum, Gallium zinc oxide (ZnO) film. Further, in such a transparent conductive film, characteristics such as low resistance or high light transmittance of solar rays are sought. Further, the method for producing such a transparent conductive film is a vacuum vapor deposition method using the above-described ion plating method or high-density plasma assisted vapor deposition method. 201200610 The oxide evaporation material used in the vacuum vapor deposition method such as the electron beam evaporation method, the ion plating method, or the high-density plasma-assisted vapor deposition method uses a small size (for example, 'the diameter is 10 to 50 mm and the height is The sintered body of a cylindrical shape of about 10 to 50 mm has a limit in the amount of film that can be formed by using one oxide steaming material. In addition, when the amount of consumption of the oxide vapor-deposited material is increased and the amount of the remaining is small, the film formation is interrupted, the air is introduced into the film forming chamber in the vacuum, and the unused oxide film is exchanged, and the film is formed again. The necessity of vacuuming the room becomes the main cause of deterioration in productivity. In addition, a technique which is indispensable in the case of mass production of a transparent conductive film by a vacuum vapor deposition method such as an electron beam evaporation method, an ion plating method, or a high-density plasma-assisted vapor deposition method, and the above-mentioned oxide evaporation may be mentioned. An example of the continuous supply method of a plating material is described in Non-Patent Document 1. In this continuous supply method, the cylindrical oxide evaporation material is connected and stored inside the cylindrical cover, and the height of the sublimation surface is maintained constant, and the oxide evaporation is sequentially performed. The shovel is supplied continuously. Further, by the continuous supply method of the oxide vapor-evaporated material, mass production of the transparent conductive film by the vacuum evaporation method can be realized. In addition, a vapor-deposited material of ITO is described in Patent Document 1 (JP-A-H08-104978). In essence, it has been proposed that the In203-Sn02 system consists of indium, tin and oxygen, and the volume of one particle is 0. 01 to 0. 5 cm3 and a relative density of 55% or more. In addition, the bulk density when filling the container is 2. ITO evaporation material below 5 g/cm3. In addition, it is also described that the utilization efficiency of the IT 〇 film which can form a film and stabilized by electron beam evaporation by the electron beam evaporation is 80% or more, and it is not blocked in the supply machine. A vapor-deposited material is obtained which allows it to be continuously supplied. Further, a vapor deposition material composed of indium oxide and tin oxide is also described in Patent Document 2 (JP-A-2007-84881). The tantalum vapor deposition material described in Patent Document 2 has a density of 4. A cylindrical oxide sintered body of 9 g/cm3, a diameter of 30 mm, and a thickness of 40 mm is constructed, and it is described that it can be continuously supplied without being damaged in the supply machine. However, various conventional ITO vapor deposition materials (oxide steaming materials) described in the above-mentioned patent documents and the like are used, and various vacuum vapor deposition methods such as electron beam evaporation, ion plating, or high-density plasma-assisted vapor deposition are used. In the case of producing a transparent conductive film having low electrical resistance and high light transmittance, it is necessary to introduce a large amount of oxygen into the film forming vacuum chamber at the time of film formation (for example, refer to paragraph 0007 and paragraph 0108 of Patent Document 2). It is noted that the following problems mainly occur. First, the composition deviation between the transparent conductive film and the oxide evaporation material becomes large, and the composition design of the transparent conductive film becomes difficult. In general, when the amount of oxygen introduced into the film forming vacuum chamber is increased, the difference in composition between the transparent conductive film and the oxide vapor deposition material tends to be large. In the film formation mass production step, fluctuations in the amount of oxygen in the film formation vacuum chamber are also likely to occur. The influence of the film composition is likely to occur, which is caused by the variation in film characteristics. Further, in the reactive vapor deposition film formation using oxygen, when the amount of oxygen is increased, not only the density of the film is lowered, but also the adhesion of the film to the substrate is weakened, etc., the problem of 201200610. Since the energy disappears when the evaporated metal oxide is oxidized before reaching the substrate, once the proportion of oxidation becomes large, it becomes difficult to obtain a dense and high adhesion film to the substrate. Also, the surface is easily oxidized. When a transparent conductive film is formed on a substrate covered with a metal film or an organic film, when the amount of oxygen introduced into the film forming vacuum chamber is large, the surface of the substrate is oxidized before film formation, so that it is impossible to manufacture high performance. element. This tendency becomes more pronounced as the substrate temperature at the time of film formation is higher. For example, in the case of producing a solar cell to be energy-converted by injecting light from the surface opposite to the substrate, it is necessary to form a transparent conductive film on the PIN element formed using the metal thin film. In the film formation in which the amount of oxygen introduction is large, the element is easily damaged and it is impossible to manufacture a high-performance element. In the case where an organic thin film solar cell or an organic electroluminescence device of a top emission type is formed, the transparent conductive film is formed on the organic light-emitting layer. In the case where the amount of oxygen introduction is large, the organic light-emitting layer is oxidized. Damaged, unable to achieve high performance components. The present invention has been made in view of such a problem, and the subject thereof is to use indium oxide added with tin as a main component, and to provide a low resistance in the visible light region even if the amount of oxygen introduced during film formation is small. An oxide evaporation material having a high light transmittance transparent conductive film, which is a transparent conductive film produced by using the oxide evaporation material. In other words, the oxide evaporation material of the present invention is characterized in that indium oxide is used as a main component and is composed of a sintered body containing tin oxide, and the content of tin 201200610 is the number of atoms of Sn/In. Ratio 0. 001 to 0. The LM in the 614 color system is straight from 54 to 75. Further, in the case where indium oxide is used as a main component, the film is formed using an oxide film formed by an electron plating method or a high-density plasma-assisted vapor deposition method, and the content of tin is Sn. /In atom 0. 614. Moreover, since the oxide evaporation material of the present invention relating to 75 of the CIE 1 976 color system has the most suitable oxide evaporation material, even if it is introduced into the film forming vacuum chamber, low resistance and visibility can be produced by vacuum evaporation. The transparent transparent conductive film and the film-forming method can reduce the difference in composition between the film and the oxide evaporation material, and the film composition can be reduced, and the film composition can be reduced in mass production. Since the amount of oxygen introduced into the film forming vacuum chamber is small, it is possible to damage the substrate due to oxygen. In particular, it does not damage the substrate and can stabilize the high performance film of the solar cell. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the oxide evaporation material of the present invention is added to the oxide evaporation material of the present invention in an embodiment of the present invention. Tin transparent conductive beam evaporation method, ionic crystallographic transparent derivative ratio meter. 001 to L * 値 is 5 4 to the amount of oxygen, and by using a small amount of oxygen, it is also possible to reduce the amount of oxygen in the high-permeability groove in the light region, and it is easy to obtain the change of the mesh or the characteristic, thereby being able to reduce The realization of high-performance manufacturing is useful for illustration. Indium is used as the main -10- to get more than 006 and 201200610 points, and the tin content is calculated by the Sn/In atomic ratio. 001 to 0. The composition of 614. Further, since the composition of the transparent conductive film obtained by the air vapor deposition method using the oxide evaporation material of the present invention is very close to the composition of the oxidized material, the composition of the oxide evaporated ammonium material also becomes indium oxide as the J component. And it is tin-containing only in terms of Sn/In atomic ratio. 001 to the ratio. The reason why tin is contained only in the above ratio is because the mobility of the film can be increased. The composition of the membrane, that is, the composition of the oxide-vaporized ore; the amount (in terms of the atomic ratio of Sn/In) is less than 0. In the case of 001, the effect of increasing the bulk concentration (that is, the effect of increasing the mobility) is small and the film of 1 is not available. In addition, if it exceeds 0. In the case of 614, the amount of tin in the film will be too large: the neutral impurity which is scattered when the electron is moved becomes large, and the low-resistance film which is affected by the decrease in the rate cannot be obtained. In order to exert a higher carrier concentration I, a better tin content to the low-resistance film is based on the Sn/In atomic ratio to 0. 163. Further, the film is a crystalline film. However, a transparent conductive film-based semiconductor containing indium oxide as a main component is required to provide a moderate oxygen shortage for high conductivity and high light transmittance. That is, the amount of oxygen in the membrane is large and! In the case where the amount is small, for example, even if a dopant is contained, it does not show that the conductivity '1 pair exhibits conductivity, and it is necessary to introduce oxygen deficiency into the film; if oxygen is scarce: the light absorption of visible light is increased to cause coloring. Because of the need for the optimal oxygen shortage in j. The oxygen in the film is supplied from the original vapor deposition material as well as the oxygen in the film vacuum chamber at the time of film formation. Moreover, if from oxides. Proportion with true evaporation Mainly 0. 6 14 Indium Tin Contains: Load, resistance, and move to 0. Type 040: and make, shortage:. Needle: too much film-oxygen [into i-plating material-11 - * 201200610 When the supply is small, it is necessary to increase the amount of oxygen introduced into the film-forming vacuum chamber, and increase the amount of introduction into the film-forming vacuum chamber. In the case of oxygen, the above problems will occur. Therefore, an oxide evaporation material having an optimum amount of oxygen will be useful. Further, the most important feature of the oxide vapor-deposited material of the present invention is specified by the L*値 of the CIE 1976 color system. Here, the CIE 1 976 color system is the color space recommended by CIE (International Commission on Illumination) in 1976. Since the color is represented by a coordinate on the equal color space composed of the luminance L* and the color indices a-, b*, it is also simply referred to as CIELAB. The L* of the display brightness is displayed in black when L* = 0, and the white diffused color is displayed when L+ = 100. In addition, a* is indicated by negative 値 for greenish green, with positive 不 for non-biased, b for negative 値 without blue, and for positive for yellow. Further, the surface of the sintered body of the oxide-evaporated material according to the present invention specified by L*値 of the CIE1976 color system is preferably the same as the color of the inside of the sintered body, but it is assumed that the outermost surface is different from the inside. In the case of the vapor deposition material, in the present invention, L*値 is determined for the inside of the sintered body. According to the experiment conducted by the inventors of the present invention, when the C 内部 inside the oxide steaming material is 54 to 75, even if the amount of oxygen introduced into the film forming vacuum chamber is small, both the high conductivity and the visible light region can be obtained. High transmittance transparent conductive film. In addition, the more white, the higher the L*値; conversely, the more black, the lower the L +値. Moreover, it is considered that the L*値 system of the oxide evaporation material has a correlation with the oxygen content in the oxide vaporized material, and it is considered that the larger the enthalpy, the more the oxygen content is -12-201200610; the smaller the L*値The less oxygen is contained. The inventors of the present invention changed the production conditions, and tried to use various kinds of L*値 oxide-deposited materials to produce a transparent conductive film by vacuum evaporation, and the larger the L*値, the more suitable oxygen amount to be introduced into the film formation. The smaller the amount of oxygen (in order to obtain a film having low resistance and high transparency). This is because the amount of oxygen supplied from the oxide steaming material itself becomes larger due to the oxide evaporation material having a larger L*値. Further, the more the amount of oxygen introduced, the greater the difference in composition between the display film and the oxide-vaporized material. Therefore, the larger the L*値, the smaller the composition difference becomes. Further, the oxide vapor deposition material of the present invention has conductivity, and the conductivity of the oxide evaporation material depends on the oxygen content, and also depends on the density, the crystal grain size, and the dopant efficiency of the ruthenium. Therefore, the conductivity of the oxide evaporation material does not correspond to 1 to 1 for the L# system. Further, the oxide evaporation material of the present invention containing indium oxide as a main component and containing tin is based on vacuum deposition, mainly in In203. The form of x and Sn02_x generates evaporating particles, and also reacts with oxygen in the chamber to absorb oxygen and form a film on the substrate. Further, the energy of the evaporating particles is a driving source for the movement of the substance when it reaches the substrate and is deposited on the substrate, contributing to the densification of the film and the adhesion to the substrate. Further, since the smaller the L#値 of the oxide evaporation material, the less oxygen in the oxide evaporation material, the oxygen shortage of the evaporated particles becomes large, and it is necessary to introduce a large amount of oxygen into the vacuum chamber to increase before reaching the substrate. The ratio of its oxidation reaction. However, since the evaporating particles consume energy due to oxidation during flight, it is difficult to obtain a film that is dense and has a high adhesion to the substrate in the reactive film introduced by the increase in oxygen. In the ground, it is easier to obtain a highly adherent and high-density film by reducing the reactive vapor-forming film of the introduced oxygen, and the oxide-steamed metal of the present invention can achieve the same. Here, when the L*値 is less than 54, the amount of oxygen in the oxide vapor deposition material is too small, and the optimum oxygen introduction amount for introducing the film into the vacuum chamber in order to obtain a film having low resistance and high transparency is increased. The difference in the composition of the film and the oxide evaporation material becomes large, and the problem that the damage to the substrate becomes large in the film formation also occurs, which is not preferable. On the other hand, when the amount of oxygen contained in the oxide vapor deposition material is too large, the amount of oxygen supplied from the oxide vapor deposition material to the film becomes excessive, and the optimum oxygen cannot be obtained. A shortage of highly conductive films. However, a sputter target of a tin-containing indium oxide sintered body is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 5 - 1 1 2 8 66 (reference publication), which is incorporated herein by reference. The tin-containing indium oxide sintered body produced by the method of the invention has a lanthanum as low as 38 to 49 (see Comparative Example 3). Therefore, when such a sintered body is used as an oxide vapor deposition material, the amount of oxygen introduced into the film forming vacuum chamber for obtaining an optimum film must be increased; and the above problems occur, and the object of the present invention is not achieved. Here, the vapor-deposited oxide sintered body (oxide-evaporated material) of the present invention having an L*値 of 54 to 75 is not manufactured by a conventional technique for producing an ITO sintered body. An oxide evaporation material suitable for use in a moderate amount of oxygen (or oxygen shortage) which is mass-produced by a vacuum deposition method can be produced by the following method. In the case of the sintered body containing tin oxide as a main component, the sintered body containing tin can be used as a raw material of each powder of indium oxide and tin oxide, and these powders are mixed and molded to form a green compact, which is subjected to high temperature. It is produced by firing and sintering and sintering. The respective powders of indium oxide and tin oxide are not particularly preferable, and may be a raw material for an oxide sintered body which is conventionally used. Further, the average particle diameter of the powder used was 1. 5 μπι or less, preferably 〇. 1 to 1. 1 μηι. The mixing of the general raw material powder at the time of producing the above oxide sintered body is also effective in the case of producing the sintered body of the present invention by a ball mill mixing method. The ball mill is a device in which a hard ball (a spherical diameter of 10 to 30 mm) such as ceramics and a powder of a material are placed in a container to be rotated, and the material is also ground while being mixed to prepare a fine mixed powder. The ball mill (pulverized medium) is made of steel, stainless steel, nylon or the like as a can body, and is made of an aluminum oxide, a magnetic material, natural cerium oxide, rubber, a urethane or the like as a lining. The ball may be an alumina ball containing alumina as a main component, a natural vermiculite, a nylon ball in which an iron core is placed, an oxidized pin ball, or the like. The wet and dry pulverization methods are widely used for obtaining and pulverizing the raw material powder of the sintered body. In addition, the bead mill method or the jet mill method is also effective in methods other than ball mill mixing. In particular, since the tin oxide powder is a hard material, it is very effective in the case of using a large average particle diameter raw material or in a case where it is necessary to carry out pulverization and mixing in a short time. The so-called bead mill system will be 70 to 90% of the beads (grinding medium, bead diameter 0. 005 to 3 mm) is preliminarily filled in a container called Vessel, and the bead is operated by rotating the rotating shaft in the center of the container at a peripheral rotation speed of 7 to 15 m/sec. Here, a slurry in which the material to be pulverized, such as the raw material powder -15-201200610, is mixed into the liquid is supplied thereto by the pump, and the beads are impacted to be finely pulverized and dispersed. In the case of a bead mill, if it is combined with the pulverized material to reduce the diameter of the bead, the efficiency will increase. In general, bead mills are capable of micro-grinding and mixing at an acceleration close to one thousand times that of a ball mill. The bead mill thus constructed is referred to by various names, for example, a grinder, an hydrating machine (Aquamizer), an attritor, a pearl mill, an Abex mill, an ultra-viscer mill (Ultra vi sco mill). ), a DYNO mill, a stirring mill, a Coball mill, a Spike mill 'SC mill, etc., in the present invention, any of them can be used. In addition, the jet mill blows high-pressure air or steam injected before and after the sound speed from the nozzle as a super-high-speed jet to impact the pulverized material such as the raw material powder, and pulverizes into particles by the collision of the particles. The method. As described above, the indium oxide powder and the tin oxide powder are first poured into a can for a ball mill at a desired ratio, and dry or wet mixing is carried out to prepare a mixed powder. Then, in order to obtain the oxide sintered body of the present invention, the content of indium and tin is 0. 001 to 0. 614 way to modulate. An organic substance such as water, a dispersion material, or an adhesive is added to the mixed powder prepared in this manner to produce a slurry. The viscosity of the slurry is preferably from 150 to 5,000 cp, more preferably from 400 to 3,000 cP. The granulated powder can be obtained by using the slurry obtained in this manner and drying it by a spray dryer or the like. However, in order to obtain a sintered body having more uniformity and good sinterability, it is more effective when the pulverization and mixing treatment of 16 - 201200610 is carried out by the following bead mill. Namely, the obtained slurry and beads are placed in a container of a bead mill to carry out pulverization and mixing treatment. The beads may be zirconia, alumina or the like, but zirconia is preferred from the viewpoint of abrasion resistance. The diameter of the beads is preferably from 1 to 3 mm from the viewpoint of pulverization efficiency. The number of passes can be one, but it is preferably two or more, and a sufficient effect can be obtained five or less times. Further, the treatment time is preferably 10 hours or less, more preferably 4 to 8 hours. By performing such treatment, the pulverization and mixing of the indium oxide powder and the tin oxide powder in the slurry are good. Next, molding is carried out using the slurry treated in this manner. The molding method can be either a casting molding method or a pressure molding method. In the case of casting, the obtained slurry is cast into a molding mold to produce a molded body. The time from the treatment of the bead mill to the time of casting is preferably within 10 hours. Therefore, the slurry obtained by performing this method can prevent the display from being shaken. Further, in the case of press molding, an adhesive such as polyvinyl alcohol or the like is added to the obtained slurry, and if necessary, moisture is adjusted, and then dried by a spray dryer or the like to be granulated. The obtained granulated powder is filled in a mold of a predetermined size, and then, a press machine is used to 9. A pressure of 8 to 98 MPa (100 to 1000 kg/cm2) is subjected to uniaxial press forming to form a molded body. The thickness of the formed body at this time is considered to be the shrinkage caused by the subsequent firing step, and is preferably set to a thickness at which a sintered body of a predetermined size can be obtained. When the molded body produced from the above mixed powder is used, the oxide sintered body of the present invention can be obtained by a normal pressure sintering method at -17 to 201200610. Further, in the case where the oxide sintered body is obtained by firing by a normal pressure sintering method, the following method is employed. First, the obtained molded body is heated at a temperature of 300 to 500 ° C for about 5 to 20 hours to carry out a debonding treatment. Thereafter, the temperature is raised and sintered. However, in order to effectively release the internal bubble defects to the outside, the temperature increase rate is set to 150 ° C / hour or less, preferably set to! 〇 〇. (: / hour or less 'more preferably set to 80 ° C / hour or less. Sintering temperature is set to 丨丨 5 〇 to 1 300 ° C ' is preferably set to 1 2 0 0 to 1 2 5 0 ° C The sintering time is set to 1 to 20 hours, preferably set to 2 to 5 hours for sintering. The debonding treatment to the sintering step is important to be in every 0. The oxygen content of the furnace of 1 m3 is 5 liters/min or more and the oxygen is introduced into the furnace. The introduction of oxygen in the sintering step is carried out because the sintering system easily dissociates oxygen at 1150 ° C or higher and easily reaches an excessive reduction state, thereby preventing the dissociation. In this step, once the sintered body in which the oxygen shortage is excessively introduced is formed, it is then difficult to adjust the oxygen shortage amount of the sintered body to the optimum in the oxygen amount adjusting step. If the firing temperature exceeds the temperature of i3〇oc into fr, 'even in the oxygen environment as described above, 'the dissociation of oxygen will become frequent' and thus it becomes easy to reach an excessive reduction state.] For the same reason, it is not good. . Further, in the case where the firing temperature is 195 ° C, the sintering is insufficient because the temperature is too low, and it is not preferable to obtain a sintered body having sufficient strength. After the sintering, the oxygen amount adjusting step of the sintered body is performed. The oxygen amount adjustment step is important to carry out a heating time of 1 Torr or more at a temperature of 90 to 1 100 ° C', preferably 950 to 105 Ot: -18 - 201200610. The cooling system up to the heating temperature of the oxygen amount adjusting step is cooled while continuing the introduction of oxygen, and is 0. 1 to 20 ° c / min ' is preferably cooled at a cooling rate in the range of 2 to 1 〇〇 c / min." In the oxygen amount adjustment step of the sintered body, the control of the gas atmosphere in the furnace is also particularly important 'introduction into the furnace The gas is important to control the mixing ratio (volume ratio) of oxygen to argon in the range of 〇2/Ar = 40/6 0 to 90/1 0, in each 〇. The inner volume of the furnace is introduced into the furnace at a ratio of 5 liters/min or more. By precisely adjusting such temperature and gas atmosphere and time, it is possible to obtain a sintered body having the L* 规定 defined by the present invention when used as an oxide vapor deposition material. In the case where the heating temperature of the oxygen amount adjusting step is lower than 900 ° C, the reaction of dissociation and adsorption of oxygen is slow, and it is not preferable until the reduction treatment inside the sintered body takes time; if it exceeds 1100 ° C When the temperature is carried out, the dissociation of oxygen will be excessively intense, and the optimum reduction treatment due to the gas environment is not preferable. Further, if the heating time of the oxygen amount adjusting step is less than 1 hr, it is not preferable because the uniform reduction treatment in the sintered body portion is not performed. Further, when the mixing ratio (〇2/Ar) of the gas introduced into the furnace is less than 40/60, the reduction by the dissociation of oxygen becomes an excessive advantage, and thus it becomes a sintered body having an L*値 lower than 54. Not good. On the contrary, if the mixing ratio (〇2/Ar) of the gas introduced into the furnace exceeds 90/10, the oxidation becomes an excessive advantage, and thus it becomes a poor sintered body of more than 75 Å. -19-201200610 In order to obtain the oxide evaporation material of the present invention, as described above, it is important to perform annealing in a gas atmosphere in which oxygen is precisely diluted by using argon gas, that is, in a gas atmosphere in which the oxygen amount is precisely controlled. For the treatment, the ambient gas is not necessarily required to be a mixed gas of oxygen and argon. For example, it is effective to use an inert gas such as helium or nitrogen instead of argon. Further, even in the case where air is used instead of argon, it is effective to precisely control the oxygen content in the entire mixed gas. However, as in the conventional technique, it is generally not effective to introduce oxygen into a furnace which is fired by air because the oxygen content of the gas atmosphere in the furnace cannot be precisely controlled. According to the mode proposed by the present invention, the furnace vapor-filled material having the optimum reduction state can be obtained by introducing a mixed gas of an inert gas having a ratio of oxygen contained in a precise control. Further, after the completion of the oxygen amount adjustment step, it can be taken out from the furnace at room temperature at a temperature of 1 (TC / min to room temperature). The obtained sintered body can be processed to be oxidized by dicing into a predetermined size or the like. In addition, the shrinkage ratio of the sintering is also considered. When a molded body having a predetermined size after firing is used, it can be used as an oxide vapor-deposited material without performing honing processing after sintering. However, it is known that a method of producing a sputtering target is effective as a hot press method for obtaining a high-density sintered body. However, when a hot press method is applied to the material of the present invention, only L*値 is obtained. It is an over-reducing sintered body of 40 or less. The object of the present invention cannot be achieved in such a sintered body. -20- 201200610 Further, for the oxide-evaporated material of the present invention, for example, a diameter of 10 to 50 mm is used. It is also possible to use a cylindrical ingot or a nine-shaped shape having a height of 10 to 50 mm, and it is possible to use a particle shape of about 1 to 1 〇 mm which pulverizes such a sintered body. The vapor deposition material, other elements other than indium, tin, and oxygen may contain, for example, tungsten, molybdenum, zinc, cadmium, tellurium, or the like, and are allowed to be present without impairing the characteristics of the present invention, but among metal ions, When the vapor pressure of the oxide is extremely high as compared with the vapor pressure of indium oxide or tin oxide, it is difficult to evaporate by various vacuum vapor deposition methods, and it is preferably not contained. Or tin oxide as a comparison, for example, metals such as aluminum, titanium, and antimony, because the vapor pressure of these oxides is extremely high, so that it is contained in the oxide evaporation material, so that indium oxide or tin oxide is evaporated together. Therefore, it is difficult to contain it because it remains in the oxide evaporation material and is highly concentrated, and it is not allowed to be contained because it adversely affects the evaporation of indium oxide and tin oxide. When the transparent conductive film is produced by various vacuum deposition methods, the oxygen content in the oxide vapor deposition material is optimally adjusted, and even if the amount of oxygen introduced into the film formation vacuum chamber is small, the maximum amount can be obtained. The transparent conductive film is in short supply of oxygen. Therefore, the difference in composition between the transparent conductive film and the oxide evaporation material is small, and it is also difficult to be affected by the characteristic deviation caused by the variation of the oxygen introduction amount. (2) Transparent conductive The film is made of an oxide evaporation material according to the present invention, which is composed of indium oxide as a main component of -21 to 201200610 and is composed of a sintered body containing tin, and the content of tin is 0 in terms of atomic ratio of Sn/In. 001 to 0. 614 and in the CIE 1976 color system, the r 値 is 54 to 75, and the tin-containing indium oxide crystal film can be produced by various vacuum evaporation methods such as electron beam evaporation, ion plating, or high-density plasma-assisted vapor deposition. (Transparent conductive film). When a crystal film is formed and tin is dissolved in the indium oxide indium position, a high mobility can be exhibited. The crystal film (transparent conductive film) can also be obtained by heating the substrate in the film formation to 180 ° C or higher; but it can also be used at 180 ° C or higher to obtain a film by heating or non-heating. Obtained by the method of film annealing. Got it. Further, the crystalline transparent conductive film of the present invention can be produced from an oxide evaporation material having a small difference in composition between the film and the oxide evaporation material, and contains 0 atomic ratio of Sn/In. 001 to 0. 614 tin indium oxide film. If the tin content of the film (in terms of Sn/Iri atomic ratio) is less than 0. In the case of 001, the effect of increasing the carrier concentration (i.e., the effect of increasing the mobility) is small and a low-resistance film cannot be obtained. In addition, if it exceeds 0. At 614, the amount of tin in the film is too large, and the neutral impurity which is scattered when the electrons move becomes large, and a low-resistance film which is affected by the decrease in the mobility is not obtained. In order to further obtain a transparent conductive film having a high carrier concentration, a more preferable tin content is 〇· 〇 40 to 0 in terms of the atomic ratio of Sn/In.  The 1 6 3 ' film is a crystalline film. By obtaining a crystal film of such a composition range, The transparent conductive film can be realized as follows: the carrier concentration is 7. 2x1 〇20 cm — 3 or more, and the specific resistance is 3. 5xl〇_4Qcm or less. Further, the transparent conductive film of the present invention has a very high average transmittance of 90% or more in the film itself having a wavelength of 400 to 800 nm, which is 90% or more. Hereinafter, the embodiment of the present invention will be specifically described. [Examples 1 to 4] [Production of Oxide Steamed Material] The average particle diameter was 0. 8 μιη Ιη203 powder and Sn02 powder having an average particle diameter of 1 μπι as a raw material powder, and the atomic ratio of S n / In becomes 0. The Ι203 powder and the Sn02 powder were blended in a ratio of 048, placed in a resin can, and mixed by a wet ball mill. At this time, a hard Zr02 ball was used, and the mixing time was set to 20 hours. After mixing, the slurry is taken out, and an adhesive of polyvinyl alcohol is added to the obtained slurry, and dried by a spray dryer or the like to be granulated. Using this granulated product, a uniaxial compression molding was carried out at a pressure of 98 MPa (1 ton/cm2) to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 40 mm. Next, the obtained molded body was sintered in the following manner. That is, in the air in the sintering furnace, it is heated at a temperature of 300 ° C for about 1 hour to carry out the debonding treatment of the molded body, and then every 0.  The gas atmosphere in which the internal volume of the furnace of 1 m3 is 5 liters/min or more and introduced with oxygen is heated at a rate of 1 °C/min and sintered at 1250 °C for 2 hours (normal pressure sintering method). At this time, in the case of cooling after sintering, oxygen is introduced, and the temperature is lowered by 1 (TC/min to l〇〇〇t:. Then, the introduced gas is switched to a mixed gas of oxygen and argon at 1000 °C. While heating is maintained for 15 hours (hereinafter, this step is referred to as a sintered body oxygen amount adjustment-23-201200610 step), the temperature is lowered to room temperature at 1 〇t / minute. Moreover, by making the mixed gas oxygen and argon The mixing ratio of the mixture is changed to obtain various oxide sintered bodies (oxide vapor deposition materials) of L*値. That is, the oxide evaporation material of the first embodiment is in an oxygen/argon flow ratio (that is, The volume ratio) was produced under the conditions of "40/60", and the oxide vapor deposition material of Example 2 was produced under the condition that the volume ratio was "60/40", and the oxide of Example 3 was steamed. The plating material was produced under the condition that the volume ratio was "80/200", and the oxide vapor-deposited material of Example 4 was produced under the condition that the volume ratio was "90/10". Yes, the volume and weight of the obtained oxide sintered body (oxide evaporation material) are measured. After the density, it is 4. 8 to 5. 7 g/cm3. Further, from the observation by a scanning electron microscope based on the fracture surface of the oxide sintered body, the average 値 of any one of the crystal grain sizes in the oxide sintered body was determined to be 3 to 10 μm. In addition, for the electron beam irradiation surface of the oxide sintered body, the four-terminal probe method resistivity is utilized. The specific resistance was calculated to be 1 kD cm or less by measuring the surface resistance. Further, after analyzing the composition of all the oxide sintered bodies by ICP luminescence analysis, it was found that the composition was present. Further, the surface of the sintered body and the inside of the sintered body were measured by a color difference meter (Specrto Guide, E-6834, manufactured by BYK-Garadner GmbH, Inc.), and L*値 in the CiEi 9 7 6 color system was measured to show almost the same flaw. The oxygen/argon flow ratio (i.e., volume ratio) of the mixed gas introduced in the sintered body oxygen amount adjusting step, and the obtained oxide sintered body-24-201200610 (oxide vapor-deposited material) L +値 is shown in Table 1(a), Table 1 (b) and Table 1 (c) below. Table 1 (a) Sn/In atomic ratio of oxide evaporation material 02/Ar flow ratio in the oxygen content adjustment step of the sintered oxide 1/値 of the oxide evaporation material The optimum oxygen mixing amount Example 1 0. 048 40/60 54 9 Example 2 0. 048 60/40 62 8 Example 3 0. 048 80/20 70 5 Example 4 0. 048 90/10 75 2 Comparative Example 1 0. 048 30/70 49 15 Comparative Example 2 0. 048 100/0 79 0 Comparative Example 3 0. 048 — 38 42 Example 5 0. 102 40/60 55 8 Example 6 0. 102 60/40 61 7 Example 7 0. 102 80/20 69 4 Example 8 0. 102 90/10 73 3 Comparative Example 4 0. 102 30/70 50 15 Comparative Example 5 0. 102 100/0 82 0 Comparative Example 6 0. 102 — 49 42 Example 9 0. 001 60/40 67 7 Example 1〇 0. 009 60/40 65 7 Example 11 0. 028 60/40 63 6 Example 12 0. 163 60/40 60 6 Example 13 0. 230 60/40 61 5 Example 14 0. 614 60/40 62 5 Comparative Example 7 0. 102 — 49 42 Comparative Example 8 0. 102 100/0 79 0 -25- 201200610 Table 1 (b) Membrane characteristics specific resistance (μΩοιη) in the optimum oxygen mixture. Carrier concentration (cm'3) Hole mobility (cm2/V s ) Visible light region of the film itself Transmittance (%) Example 1 150 1. 19χ1021 35 90 Example 2 150 1. 3〇χ1021 32 90 Example 3 150 1. 26x1021 33 90 Example 4 150 1. 13χ1021 37 90 Comparative Example 1 190 9. 14x1ο20 36 90 Comparative Example 2 230 7. 76χ1020 35 90 Comparative Example 3 210 8. 04x1020 37 90 Example 5 180 1. 24χ1021 28 90 Example 6 180 1. 29χ1021 27 90 Example 7 180 1. 24x1021 28 90 Example 8 180 1. 34χ1021 26.  90 Comparative Example 4 210 1. 06χ1021 28 90 Comparative Example 5 310 7. 75χ1020 26 90 Comparative example ό 220 1. 14χ1021 25 90 Example 9 750 1. 52χ1020 55 90 Example 10 675 1. 82χ1020 51 90 Example 11 470 2. 96χ1020 45 90 Example 12 350 7·14χ1020 25 90 Example 13 520 5. 72χ1020 21 90 Example 14 780 4. 71 χΙΟ20 17 90 Comparative Example 7 220 8. 12Χ1020 35 90 Comparative Example 8 220 9·8〇χ1020 29 90 -26- 201200610 Table 1 (c) Sn/In atom of the crystalline film of the cracked film of the film-specific oxide evaporation material in the optimum oxygen mixture amount Adhesion of the film to the substrate Example 1 Crystal film '0. 048 Strong Uncleared Example 2 Crystalline film 0. 048 Strong Uncleared Example 3 Crystalline film 0. 048 Strong Uncleared Example 4 Crystalline film 0. 048 Strong Uncleared Comparative Example 1 Crystalline film 0. 075 weak uncleared comparative example 2 crystalline film 0. 048 Strong Uncleared Comparative Example 3 Crystalline film 0. 095 weak cracking Example 5 crystalline film 0. 102 strong uncleared Example ό Crystalline film 0. 102 strong uncleared Example 7 crystalline film 0. 102 strong uncleared Example 8 crystalline film 0. 102 strong uncleared comparative example 4 crystalline film 0. 122 weak uncleared comparative example 5 crystalline film 0. 102 strong uncleared comparative example 6 crystalline film 0. 118 weak cracking Example 9 crystalline film 0. 001 Strong Uncleared Example 10 Crystalline film 0. 009 Strong Uncleared Example 11 Crystalline film 0. 028 Strong Uncleared Example 12 Crystalline film 0. 163 strong uncleared Example 13 crystalline film 0. 230 strong uncleared Example 14 crystalline film 0. 614 strong uncleared comparative example 7 crystalline film 0. 114 weak cracking Comparative Example 8 Crystal film 0. 102 Strong uncleared [Production of transparent conductive film and film property evaluation, film formation evaluation] (1) A magnetic field bias type electron beam evaporation device is used for the production of a transparent conductive film. The vacuum exhaust system consists of a low vacuum exhaust system caused by a rotary pump and a high vacuum exhaust system caused by a cryopump, which can be exhausted up to 5 X 1 (Γ5 Pa. The electron beam is heated by the filament The generation is accelerated by an electric field applied between the cathode and the anode, and is bent in a magnetic field of a permanent magnet, and then irradiated to an oxide evaporation material provided in a crucible made of tungsten. -27-201200610 The voltage can be adjusted by changing the voltage applied to the filament. When the acceleration voltage between the cathode and the anode is changed, the irradiation position of the electron beam can be changed. The film formation is carried out under the following conditions. 02 gas is introduced into the vacuum chamber to maintain the pressure at 1. 5x10 · 2 Pa. At this time, the characteristics of the transparent conductive film obtained by changing the mixing ratio of the Ar gas and the 02 gas introduced into the vacuum chamber were evaluated. The cylindrical oxide steaming materials of Examples 1 to 4 were placed upright in a crucible made of tungsten, and the electron beam was irradiated onto the central portion of the circular surface of the oxide evaporation material at a thickness of 1. A transparent film with a thickness of 200 nm was formed on a 1 mm Corning 705 9 glass substrate. Set the voltage setting of the gun to 9 kV, the current 値 to 150 mA, and the substrate heating to 250 °C. (2) The characteristics of the obtained film (transparent conductive film) were evaluated in the following order. First, the surface resistance of the film (transparent conductive film) was measured by a four-terminal probe method resistivity meter Loresta EP (manufactured by DIA Instruments, Inc., MCP-T3 60 type), and the film thickness of the film (transparent conductive film) was contacted. The surface roughness meter (manufactured by Tencor) was evaluated by measuring the difference between the film formation portion and the film formation portion, and the "specific resistance (μΩ cm)" was calculated. Further, using a hole effect measuring device (ResiTest manufactured by TOYO CORPORATION), the "carrier concentration (cm·3)" and "hole mobility (cm2) of the film obtained by the van der Pauw method at room temperature at room temperature. /vs)". Then, the rate (TL + b (%)) of the film containing the glass substrate (glass substrate B with film L) was measured by a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.) -28-201200610, and the same was used. In the method, the transmittance of the film itself was calculated from the transmittance (TB (%)) of the measured glass plate (glass substrate B) by [TL + B + TB (%)]. Further, the crystallinity of the film was evaluated by X-ray diffraction measurement. In the diffraction apparatus, X 'Pert PROMPD was used (the measurement conditions by PANalytical Co., Ltd. were measured by wide-area measurement, and the CuKa line was used, and the measurement was performed using a voltage of 45 mA at 40 mA. The crystallinity was evaluated by the presence or absence of the X-ray diffraction peak. The results are also shown in "crystallinity of the film in Table 1 (c). Next, the composition of the film (in terms of the atomic ratio of Sn/In) is measured by luminescence analysis. Further, the adhesion of the film to the substrate is based on Evaluation of C002 1. Evaluation of the absence of film peeling is considered good (strong film peeling is considered insufficient (weak). The results of these are also shown in Table 1 (c) "by Sn/In In the respective columns of the atomic ratio and the film-to-substrate adhesion, the specific resistance and transmittance of each film (transparent conductive film) are based on the mixing ratio of Ar gas and 02 gas introduced into the film forming vacuum chamber. The mixing ratio of 丨 gas [〇2/ ( Ar + 02 ) ( % )] is changed from 50% per 1%, and the mixing ratio of 〇2 gas showing the lowest specific resistance is determined by the optimum oxygen mixing amount. This result is shown in the column of “oxygen blending amount” in Table 1 (a). A film prepared by mixing a small amount of oxygen (transmission glass base X 1 00 X line [) 'kV, estimated film column ICP JIS 丨), the film forming tower of the display panel 2 〇 to the optimum transparent -29- 201200610 Conductive film) is not only poor in conductivity but also low in transmittance in the visible light region. The film (transparent conductive film) produced by the optimum oxygen mixing amount is not only excellent in conductivity but also high in transmittance in the visible light region. (3) Using the oxygen-evaporated material of Examples 1 to 4, the optimum oxygen mixing amount at the time of performing the film formation evaluation described above, and the specific resistance of the film at this time, in the visible light region (wavelength 400 to 800 nm) The average transmittance of the film itself. The results of the evaluations are shown in Table 1 (b), "Specific Resistance (μη (:η〇) and "Transmittance (%) of the visible light region of the film itself"" in the use of Examples 1 to 4 In the case of film formation of an oxide evaporation material, in order to obtain a transparent conductive film having the lowest resistance and high transparency, the optimum oxygen mixing amount to be introduced into the film forming vacuum chamber is extremely small. This is because each oxide evaporation material contains In addition, the film system produced in the optimum oxygen mixture amount is the same as the composition of the oxide steamed material, and exhibits not only a very low specific resistance but also a high transmittance in the visible light region. The film was confirmed to be an indium oxide crystal film of a buckhamite type structure, and the adhesion to the substrate was strong enough to be practical. Further, the set voltage of the electron gun was 9 kV, and the current enthalpy was set to 150 mA. After the beam was irradiated for 60 minutes, the oxide evaporation material was visually observed for cracking or cracking in the oxide steaming material (the oxide evaporation material durability test). The oxide evaporation materials of Examples 1 to 4 were continuously used. Also not produced Rift ("Evaluation of Uncracked"). Such a transparent conductive film is very useful as a transparent electrode for a solar cell, -30-201200610. [Comparative Examples 1 to 2] In Examples 1 to 4, only the change was made. In the sintered body oxygen amount adjusting step, the mixing ratio of the introduced gas was used to produce an oxide sintered body. That is, in Comparative Example 1, the 02/Ar flow ratio was set to 30/70; in Comparative Example 2, The obtained sintered body was evaluated for density, specific resistance, crystal grain size, and composition in the same manner as in Examples 1 to 4. The surface and internal color of the obtained oxide sintered body were obtained. The results were the same, but after measuring L*値, the results are shown in Table 1 (a). Next, film formation evaluation was carried out in the same manner as in Examples 1 to 4. The results are also shown in Tables 1(a) to (c) above. Comparative Example 1 has the following features: an oxide evaporation material showing 値(49) which is smaller than the specified range (54 to 75) of the present invention; and oxidation with Examples 1 to 4. For comparison, the optimum oxygen mixing amount at the time of film formation is (1 5 ). Compared with Examples 1 to 4 The film properties of the optimum oxygen mixture amount are the same, but the specific resistance is somewhat higher. It is considered that the main cause is that the composition of the film is largely shifted. Furthermore, compared with Examples 1 to 4, comparison is made. The film system of Example 1 has a weaker adhesion to the substrate. It is considered that this is caused by a slight introduction of oxygen film formation at the time of film formation. Due to such an oxide-vaporized material, the obtained film composition is highly biased. It is difficult to design the film composition. In addition, since it is necessary to introduce oxygen slightly into the film forming vacuum chamber, once it is used in the mass production step of the film formation, the composition or characteristics are changed by the influence of the oxygen concentration fluctuation in the vacuum chamber. Therefore, it was confirmed that the oxide evaporation material of Comparative Example 1 201200610 is not suitable for film formation mass production. Further, Comparative Example 2 is an example of an oxide vapor-deposited material of 値(79) which is L*値 is more preferable than the present invention. The maximum amount of film formation was 〇%, and the specific resistance of the film was higher than that of Examples 1 to 4. Since the amount of oxygen supplied from the oxide-vaporized ammonium material to the membrane is too large, a large amount of membranes can be introduced, and an optimum oxygen shortage amount can be introduced. Therefore, it has been confirmed that even if the oxide deposited material is formed into a film, a film having high conductivity which is originally possessed by the vapor deposited material cannot be obtained. [Comparative Example 3] Next, a tin-containing sintered body was produced in accordance with the technique for producing a sintered body of a sputtering target described in Japanese Patent Publication No. Hei 5-112866. First, In2〇 having an average particle diameter of 1 μm or less was used. (3) Sn02 powder having a powder diameter of 1 μm or less is used as a raw material powder, and I n2 〇3 powder and final powder are blended in a ratio of 子_〇4 8 in a subratio to be placed in a resin can. The ball mill was mixed with a hard Z r Ο 2 ball, and the mixing time was set to 20 hours. The slurry was mixed, filtered, dried, and then granulated. Then, using the obtained granulated powder, 1 96 t ο n / was applied. The pressure of c m2 ) was applied by pressurization under a low temperature hydrostatic pressure, and the obtained molded body was placed in a sintering furnace and allowed to stand in air for 5 hours. The obtained sintered body was processed to have a diameter of 30 mm and a thickness range of a large oxygen mixture. 3 The amount of oxygen in this system was used. The composition was used to perform indium oxide and the average particle Sn/In original I Sn02 ί. At this time, after the combination, take MPa (2, further 1 520 ° C burn 40 mm large -32- 201200610 small cylindrical shape. The density of the sintered body is 6. 0 g/cm3, and the specific resistance is m Ω c m. Further, the crystal grain size is from 1 2 to 15 μm, and the composition is approximately the same as the composition. The surface of the obtained sintered body and the color of the inside, etc., but after measuring L * ' 'as shown in Table 1 ( a ), is extremely low 値 (: This means that the amount of oxygen in the oxide evaporation material is very high Next, film formation evaluation was carried out in the same manner as in Examples 1 to 4. The results are also shown in the above Tables 1 (a) to (c). Comparative Example 3 shows that L + 値 is within the prescribed range of the present invention ( 5 4 3 is obviously small 値 (3 8 ). Compared with the vapor-deposited materials of Examples 1 to 4 of the same composition, the optimum oxygen mixing amount at the time of film formation is (42) often. A comparison of 1 to 4 shows that the transmittance of the optimum oxygen mixing amount is the same, but the specific resistance is high. It is considered that the composition is mainly such that the composition of the film is shifted. Further, the film of the comparative example 3 is on the substrate. The strength is weaker than those of Examples 1 to 4. It is considered that this is caused by film formation with a slight introduction of oxygen at the time of film formation, and it is difficult to design a film composition because the composition obtained by the oxide evaporation material system is large. Since it is necessary to introduce oxygen into the film forming vacuum tank, once the mass production step of the film formation is used, the oxygen concentration in the vacuum tank is changed. The composition or the characteristic was increased by the ringing. Further, after the durability test of the vapor deposition material was carried out under the same conditions as in Examples 1 to 4, the oxide vaporized material was cracked after the continuous film formation ("cracking" "Evaluation". When continuous film formation is carried out using such a crack-forming vapor deposition material, a problem such as a large film formation rate is caused, and film formation cannot be stably performed. 6 The material group is the same as I 8 b 75 ) Oxidation, when the membrane gas of the membrane is slightly different, the oxygen in the oxidation oxidation is changed -33 - 201200610 Therefore, it is confirmed that the oxide evaporation material of Comparative Example 3 is not suitable. Mass production in film formation. [Examples 5 to 8] When the Ιη203 powder and the 311〇2 powder were blended, the ratio of the Sn/In atomic ratio was set to be 0. In addition to the ratio of 102, the oxide sintered bodies (oxide-steamed materials) of Examples 5 to 8 were produced under the same conditions as those of Examples 1 to 4 under the conditions of adjusting the amount of oxygen in the sintered body. That is, the oxide evaporation material of Example 5 was produced under the condition that the oxygen/argon flow ratio (i.e., volume ratio) was "40/60", and the oxide evaporation material of Example 6 was used. It is produced under the condition that the volume ratio is "60/40", and the oxide evaporation material of the seventh embodiment is produced under the condition that the volume ratio is 280/20", and the related embodiment 8 is The oxide evaporation material was produced under the condition that the volume ratio was 90/10/10. Then, with respect to the obtained oxide sintered bodies (oxide vapor-deposited materials) of Examples 5 to 8, the density, the specific resistance, the crystal grain size, and the composition were evaluated in the same manner, and any one of them was the same as Examples 1 to 4. Equivalent. Further, the surface of the obtained oxide sintered body was equivalent to the color inside. The results of measuring L + 値 are shown in Table 1 (a) above. Further, film formation evaluation was carried out in the same manner as in Examples 1 to 4. The results are also shown in Tables 1 (a) to (c) above. In the film formation using the oxide vapor-deposited materials of Examples 5 to 8, the optimum oxygen mixing amount to be introduced into the film forming vacuum chamber in order to obtain the transparent conductive film having the lowest electrical resistance and high transmittance is the same as in Examples 1 to 4. Very little land. -34- 201200610 This is due to the optimum oxygen content in the oxide steamed material. Further, the film system produced by the optimum oxygen mixing amount showed the same composition as the oxide vapor deposition material, and showed not only a very low specific resistance but also a high transmittance even in the visible light region. Further, all the film systems are crystal films of a perovskite-type crystal structure of indium oxide, and the adhesion of the film to the substrate is also strong enough to be practical. Further, even if the oxide evaporation materials of Examples 5 to 8 were continuously used, cracks did not occur. Such a transparent conductive film is very useful as a transparent electrode for a solar cell. [Comparative Examples 4 to 5] In Comparative Examples 1 to 2, except that the Sn/In atomic ratio was made to 0 when the In2〇3 powder and the Sn02 powder were blended. An oxide steamed material was produced under the same conditions as in Comparative Examples 1 to 2 except for 102. That is, in Comparative Example 4, the condition for adjusting the oxygen content of the sintered body was 〇2/Ar flow ratio was set to 3 0/70; and in Comparative Example 5, it was set to 100/0. The density, specific resistance, crystal grain size, and composition of the obtained sintered body were evaluated in the same manner as in Examples 5 to 8. Further, the surface of the obtained oxide sintered body was equivalent to the color inside. After measuring L*値, it is shown as Table 1 (a). Next, film formation evaluation was performed in the same manner as in Examples 1 to 4. The results are also shown in Tables 1 (a) to (c). Comparative Example 4 shows an oxide-vaporized ore material having a smaller 値(50) than L*値 in the specified range (54 to 75) of the present invention, and a case where the oxide-deposited materials of Examples 5 to 8 were used. In comparison, the optimum oxygen content during film formation is as high as -35 - 201200610 (15). In comparison with Examples 5 to 8, the transmittance is approximately the same at optimum characteristics, but slightly higher than the resistance. Due to the large compositional shift of the film, the film contains excess tin. The film of 4, the adhesion to the substrate was larger than that of Examples 5 to 8 due to the large compositional shift and low adhesion due to the formation of oxygen. The composition of the film obtained is biased due to the composition of the film. In addition, since oxygen must be slightly introduced, once it is used in the mass production step of film formation, it is significantly affected by the change in the degree of truth, and the composition is confirmed to be easily formed. Therefore, the oxide evaporation material of Comparative Example 4 was confirmed. In addition, Comparative Example 5 shows an example in which L*値 is an oxide vapor-deposited material of ruthenium (82) of the present invention. The amount of film formation was 〇%, but the specific resistance of the film was higher than that of Examples 5 to 8 due to the excessive supply of oxygen from the oxide evaporation material to the film, and the optimum oxygen shortage amount could not be introduced. Therefore, it was confirmed that the oxide-vaporized ore material was formed into a film, and a film having high conductivity which is exhibited by the composition itself was not obtained. [Comparative Example 6] In Comparative Example 3, the ratio of the Sn/In atomic ratio was set to 0 in addition to the blending of In2〇3 powder 5. An oxide vapor deposition material was produced under the same conditions except for 102. The density, specific resistance, crystal grain size, and composition 3 were evaluated in the same manner as obtained. Further, the film of the surface of the obtained sintered body and the amount of oxygen mixed was considered to be the reason, and the comparative example was weak. In such a film, it is slightly larger and it is difficult to set the fluctuation of the oxygen concentration characteristic in the film forming vacuum chamber. t is mass produced in film formation. The specified range is a large optimum oxygen mix. It is considered that the amount of oxygen in the film is the same as that of the Sn02 powder and the sintered body obtained in Comparative Example 3, but it is equivalent to the color system of the comparative example-36-201200610, but it is measured. After L *値, it is displayed as shown in Table 1 (a). Next, film formation evaluation was performed in the same manner as in Examples 1 to 4. The results are also shown in Tables 1 (a) to (c). Comparative Example 6 also shows that L*値 is smaller than the specified range of the present invention (54 3 is a small enthalpy (49). Compared with the oxidized plating materials of Examples 5 to 8 of the same composition, the optimum oxygen mixing amount at the time of film formation It is (42), not much. The transmittance of the film characteristics of the optimum oxygen mixing amount is the same as that of the examples 5 to 8 of the oxide evaporation material of the same composition, but compared with the implementation to 8 The specific resistance is high. It is considered that the main cause is that the composition shift is large. Furthermore, the adhesion of the film system of Comparative Example 6 to the substrate is weaker in Examples 5 to 8. It is considered that this is due to a slight increase in film formation. Since the film composition is greatly different in composition, it is difficult to design a film composition in such an oxygen evaporation material. In addition, since oxygen must be slightly introduced into the film vacuum chamber, once the film is formed, In the production step, the composition or the characteristic is increased by the influence of the fluctuation of the oxygen concentration in the vacuum chamber, and the oxygen vapor deposition material endurance test is carried out under the same conditions as in the first to fourth embodiments. Crack in the oxide evaporation material after the film ("evaluation of the crack"). If used When a vapor deposition material having a crack is formed and continuous film formation is performed, a problem that the film formation rate is largely changed and film formation cannot be stably formed. From the above, it was confirmed that the oxide evaporation material of Comparative Example 6 was not formed into a film. [Examples 9 to 14] 75) The product is usually steamed: compared with the case where the membrane is more solid than the oxygen, and the oxidative activity is affected by the change of the material. -37-201200610 In addition to the reconciliation of Iri2〇 3 The blending ratio of the powder to the Sn02 powder 'is 〇 in the atomic ratio of S n /1 η .  〇 〇〗 (Example 9), 〇.  〇 〇 9 (Example 1 〇), 0.  〇 2 8 (Example 1 1 ), 〇 ” 6 3 (Example 1 2 ), 0. 230 (Example 13) and 0. In the manner of 614 (Example 14), the oxidation of Examples 9 to 14 was carried out under the same conditions as in Example 2 (that is, the oxygen/argon flow ratio was "60/40"). Sintered body (oxide evaporation material). Then, the density, specific resistance, crystal grain size, and composition of the obtained oxide sintered bodies (oxygen vapor-deposited materials) of Examples 9 to 14 were evaluated in the same manner as in Example 2. Further, the surface of the obtained oxide sintered body was equivalent to the color inside. The results of measuring L*値 are shown in Table 1 (a) above. Further, film formation evaluation was carried out in the same manner as in Examples 1 to 4. The results are also shown in Tables 1 (a) to (c) above. In the case of film formation using the oxide steaming materials of Examples 9 to 14, in order to obtain a transparent conductive film having the lowest electrical resistance and high transmittance, the optimum oxygen mixing amount to be introduced into the film forming vacuum chamber is extremely small. This is due to the optimum amount of oxygen contained in the oxide evaporation material. Further, the film system produced by the optimum oxygen mixing amount showed the same composition as the oxide vapor deposition material, and showed not only a very low specific resistance but also a high transmittance in the visible light region. Further, all of the films were confirmed to be a crystal film of a perovskite-type crystal structure of indium oxide, and the adhesion to the substrate was also strong enough to be practical. Further, the oxide vapor deposition material endurance test was carried out under the same conditions as those of Examples 1 to 4, and the oxide vapor deposition materials of Examples 9 to 38-201200610 I4 were not cracked even if they were continuously used. Such a transparent conductive film is very useful as a transparent electrode of a solar cell. [Comparative Example 7] The IT Ο oxide vapor-deposited material described in Japanese Laid-Open Patent Publication No. Hei 08-1 0497 (Patent Document 1) was produced and the same evaluation was carried out. That is, the ratio of the atomic ratio of Sn/In is made 0. The method of 102 is to incorporate a tin oxide powder having an average particle diameter of 1 μη into an average particle diameter of 0. 1 μm of the indium oxide powder was added with 2% by mass of a vinyl acetate-based adhesive. In a wet ball mill, after mixing, drying and pulverizing these materials for 16 hours, a granulated powder is prepared. Further, this granulated powder was used to form a cylindrical molded body by applying a pressure of 49 MPa (500 kgf/cm2) under a low temperature hydrostatic pressure. The sintering of the shaped body is carried out in the atmosphere. The sintering step was carried out from room temperature to 70 ° C for 10 hours, and the temperature was raised to 1 450 ° C for 4 hours and 40 minutes. Then, it was kept at 1 450 ° C for 1 hour to obtain a sintered body. The obtained sintered body was processed into a cylindrical shape having a diameter of 30 mm and a thickness of 40 mm to prepare an ITO oxide vapor-deposited material. The density of the sintered body is 4. 4 g/cm3, specific resistance is 1. 2 mDcm. Further, the crystal grain size is 12 to 16 μm, and the composition is approximately the same as the composition of the feed. The surface of the obtained sintered body was equivalent to the inner color, but after measuring L * ,, as shown in Table 1 (a), it was an extremely low enthalpy (49). This means that the amount of oxygen in the oxide evaporation material is very small. -39-201200610 Next, film formation evaluation was carried out in the same manner as in Examples 1 to 4. The results are also shown in Tables 1 (a) to (c) above. As described above, Comparative Example 7 also clearly shows that L*値 is smaller than the specified range (54 to 75) of the present invention (49); compared with the oxide evaporation materials of Examples 5 to 8, The optimum oxygen mixing amount at the time of film formation is (42), which is very much. In comparison with Examples 5 to 8, the film properties of the optimum oxygen mixing amount were the same, but the specific resistance was high. This system is believed to be mainly due to the large offset of the composition of the film. Further, in comparison with Examples 5 to 8, the film of Comparative Example 7 was weaker than the adhesion to the substrate. It is considered that this is caused by a slight introduction of oxygen into the film at the time of film formation. Due to such an oxide steaming material, the obtained film composition is highly biased and it is difficult to design a film composition. Further, since a small amount of oxygen must be introduced into the film forming vacuum chamber, the composition or the characteristic fluctuation of the vacuum tank is affected by the fluctuation of the oxygen concentration in the vacuum chamber when it is used in the mass production step of the film formation. Further, after the oxide vapor deposition material endurance test was carried out under the same conditions as in Examples 1 to 4, cracks were formed in the oxide vapor deposition material after continuous film formation ("evaluation of "cracking"). When continuous deposition is carried out by using such a crack-producing oxide evaporation material, a problem such as a large fluctuation in the deposition rate occurs, and film formation cannot be performed stably. From the above, it was confirmed that the oxide vapor-deposited material of Comparative Example 7 was not suitable for film formation mass production. [Comparative Example 8] The IT Ο oxide vapor-deposited material described in JP-A-2007-84881 (Patent Document 2) was produced and evaluated in the same manner. -40-201200610, that is, a tin oxide powder having an average particle diameter of 1 μm or less is incorporated into an indium oxide powder having an average particle diameter of 1 μm or less so that the atomic ratio of Sn/In is 0·102. Further, a 2% by mass of a vinyl acetate-based adhesive was added. In a wet ball mill using a hard Zr02 ball, these materials were mixed, dried and pulverized for 18 hours to prepare a granulated powder. Further, this granulated product was applied to a cylindrical molded body by applying a pressure of 94 MPa (3 to n/cm2) under a low temperature hydrostatic pressure. The obtained shaped body is placed in a sintering furnace at a rate of 0. The furnace of 1 m3 was introduced into a gas atmosphere at a ratio of 5 liters/min. The mixture was sintered at normal pressure at 1100 °C for 2 hours. At this time, the temperature is raised at 1 ° C / min, the oxygen introduction is stopped during cooling after sintering, and the temperature is lowered to 1000 ° C at 10 ° C / min. The obtained sintered body is processed into a vertical composite machine. A cylindrical shape having a diameter of 30 mm and a thickness of 40 mm was measured for volume and weight to calculate density. The density of the sintered body is 4. 8 g/cm3. Further, the surface of the sintered body is equivalent to the color inside, but after measuring L*値, it is shown that L*値 is larger than the predetermined range (54 to 75) of the present invention. The amount of oxygen in the plating material is very large. Film formation evaluation was carried out in the same manner as in Examples 1 to 4 using the oxide evaporation material produced in this manner. Although the optimum oxygen mixing amount at the time of film formation was 〇% as in Comparative Example 2, the specific resistance of the film was higher than that of Examples 5 to 8. It is considered that this is because the amount of oxygen in the film is too large due to the excessive supply of oxygen from the oxide evaporation material to the membrane, and it is impossible to introduce an optimum oxygen shortage amount to -41 - 201200610. Therefore, it has been confirmed that a film having high conductivity which is originally possessed by the composition of the vapor deposition material cannot be obtained even if a film is formed using such an oxide vapor deposition material. [Probability of Industrial Use] By using the oxide evaporation material according to the present invention, it is possible to produce a transparent conductive material exhibiting high conductivity by vacuum deposition by exhibiting high light transmittance in a visible light region. The film has an industrial use possibility as an oxide vapor deposition material for forming transparent electrodes of various solar cells. [Simple description of the diagram] te 〇 [Description of main component symbols] None. -42-

Claims (1)

201200610 VII. Patent application scope: 1. An oxide evaporation material characterized in that indium oxide is used as a main component, and is composed of a sintered body containing tin oxide, and the content of tin is measured by atomic ratio of Sn/In. 0.001 to 0.614' LM in the CIE 1976 color system is straight from 54 to 75. 2. The oxide evaporation material according to claim 1, wherein the tin content is from 0.040 to 0.163 in terms of atomic ratio of Sn/In. 3. A transparent conductive film characterized in that indium oxide is used as a main component, and an oxide vapor-deposited material of the first aspect of the patent application is used as a raw material in a tin-containing transparent conductive film, and is steamed by an electron beam. A crystalline transparent conductive film formed by a ruthenium method, an ion plating method, or a high-density plasma-assisted vapor deposition method, and the tin content is 0.001 to 0.614 in terms of an atomic ratio of Sn/In. 4. The transparent conductive film of claim 3, wherein the oxide steamed material of the second aspect of the patent application is used as a raw material by using electron beam evaporation, ion plating or high density plasma assisting The crystalline transparent conductive film formed by the vapor deposition method is composed of a tin content of 0.040 to 0.163' of a Sn/In atomic ratio of 3.5 x 1 Ο·4 Qcm or less. -43- 201200610 IV. Designation of Representative Representatives (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 0 y>\\ V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: