TW201125822A - Tin-doped indium oxide thin films and fabricated method - Google Patents

Abstract

The invention of Eu3+-Y3+codoped tin-doped indium oxide (ITO) thin film were fabricated by sol-gel method. The resulting Eu3+-Y3+ codoped ITO thin film exhibit stronger red 611 nm emission (5D0 → 7F2 transition) by adding more Y3+ ions, and provide the preparation of ITO thin films. Characterization of Eu3+-Y3+ co-doped ITO thin films have strong photoluminescence and high mobility for the efficiency enhancement of solar cell. And the invention also use in thin-film electroluminescent devices can promote performance.

Description

201125822 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an indium oxide tin film which is isoelectrically transparent to a transparent snow-guided junction. The present invention is provided by a sol-gel spin coating method. This 丄# sleep sub-fruit preparation of the aforementioned indium tin oxide film method. [Prior Art] Although the theoretical basis of solar cells is very mature, it is necessary to carry out research and development on a large number of new materials, new knots and new processes to improve the efficiency of solar cells frequently. One way to improve solar cell efficiency is to convert the solar spectrum into a range that the semiconductor absorber layer can absorb. #太阳光入二 After the Earth's atmosphere, the ultraviolet part accounts for about 5%, the visible part accounts for about 45/〇, and the rest is the infrared part. The frequency of most of the absorbing material should be relatively narrow and cannot cover the absorption of sunlight with a broad spectrum. The prior art known to use the following two methods solves the aforementioned problems. The first is to develop stacked solar cells. By using a solar cell stacked in two, three or even four layers, the solar cell in the uppermost layer absorbs the short wavelength portion of the solar spectrum, while the lower solar cell absorbs the longer wavelength in the solar spectrum. In part, the entire solar spectrum can be fully utilized by the solar cells of different layers. Such stacked solar cells can achieve considerable efficiency if they use the ΙΠ_ν family material epitaxy process, but they are often used in space because of their high cost. i Si The first is the development of a fluorescent converter (luminescent s〇iar eoncentrator ' LSC). The development of the fluorescent converter is a kind of fluorescent conversion 3 201125822 replacement material. The fluorescent conversion material can convert the ultraviolet light or the infrared light in the spectrum of sunlight into visible light to absorb the semiconductor absorption layer material. The mechanism for converting ultraviolet light into visible light is called "down_conversion", and the mechanism for converting infrared light into visible light is called "upconversion" (up_c〇nversi〇n) j ^ although using fluorescent conversion materials is in progress The above-mentioned light-converting conversion or up-conversion will have a loss of luminous efficiency, so that its light-transfer efficiency will be lower than that of a stacked solar cell, but since it uses only a single solar cell to absorb the sun in the full frequency band, Therefore, the cost is still lower than that of the above-mentioned three- or four-layer stacked solar cells, that is, a method that can increase the efficiency of the current solar cell without increasing the cost. The solar conversion material can properly utilize the sun. Ultraviolet light/short-wavelength blue light and infrared light in the optical spectrum. The fluorescent conversion layer material described in the prior art is mainly applied. For example, a film of a light-converting material having an up-conversion property and a down-conversion property are prepared. Rongguang conversion material film, Qian will put the #光转换 material with upconversion properties on the solar cell Above the 'the fluorescent conversion material film with the down-conversion property is placed under the solar cell. However, the light emitted by the fluorescent conversion material needs to pass through the multiple interfaces before reaching the semiconductor absorption layer, due to the interface between the interfaces Scattering and total reflection, etc. (4) @The fluorescence intensity of the semiconductor absorption f is weakened. In addition, the addition of the fluorescent conversion layer formed by the film of the above-mentioned camping light conversion material has to be further increased. The manufacturing process complicates the process and lengthens the manufacturing time and increases the manufacturing cost. In addition, in recent years, many literatures have reported the application of rare earth ions in the semi-conductive 201125822, mainly focusing on thin-film electroluminescent elements (thin-film electroluminescent). , TFEL). Conventional electroluminescent elements (EL) can be classified into two different types of fluorescent materials (powder and film) and driving voltage (AC). The aforementioned AC voltage driving thin film electroluminescent elements (AC driven thin-film electroluminescent devices, ACTFEL) and AC electric drive powder electrophoresis AC driven powder electroluminescent devices have been commercially used. Among them, voltage-driven thin film electroluminescent Lu components include a metal- insulator-semiconductor-insulator_metal structure formed on a glass substrate, in other words, a dielectric_semiconductor- , MOSFET (insulator - semiconductor - insulator, DSD) is stacked between the electrodes.

The general literature reports the use of rare earth elements doped on transparent conductive films that are mono-doped materials such as Eu (Europe) (Eu3+) doped indium oxide (Ιιΐ2〇3) or erbium ion doped tin oxide. (Sn〇2) film. However, if a sol-gel film is prepared by doping a luminescent element with a tin doped indium oxide (IT〇) as a base material, it can be found that the luminescence property of the single-doped erbium ion is not good, and Indium oxide or tin oxide itself has a lower conductivity than indium tin oxide. 'Indium oxide doped with antimony ions or tin oxide doped ions, although it emits visible light, but the conductivity is not high.

Do Hyung Parki was published in 2006 (10), < ^ (10) plus 153 wrists - 67 pages of literature (hereinafter referred to as 1) refers to A 'oxidation of conductive materials such as tin oxide and Rong" by RF barium ore method The bismuth target is simultaneously plated on the quartz substrate to obtain a conductive, fluorescent film. When the literature 1 t money and (4) are raised, there will be a 201125822 solder-extinguishing effect, causing the conductivity to decrease. Using the pin 1 atomic percentage (Eu丨atom%) as the best parameter, the powder structure and the film structure were measured. The results of the pL measurement showed that the powder structure and the film structure were able to emit light, but the powder structure was excited. The wavelength is 30 nm more than the excitation wavelength of the thin film structure. This is due to the fact that they are formed in different crystal forms, and the probability of a block effect in the film structure is higher than that in the powder structure. Also disclosed in Document 1 is a fluorescent Tcp transparent conductive layer having the luminescent properties of #·like phosphor powder and transparent conductive oxide TCO. When the TCP layer is electronically excited, it will generate fluorescence, which will combine a phosphor thin layer and a TCP layer to form a new thin-film electroluminescent device. The phosphor layer and the TCP layer can be simultaneously excited by electron excitation. The light-emitting characteristic increases the brightness of the light. However, the technical content disclosed in this document still cannot avoid the problem that the single-doped erbium ion has poor luminescence characteristics and low conductivity, and needs to be improved. R. Kudrawiec published in 2003, from the paper (10) 105, 53 _56 (hereinafter referred to as the literature 2) to expose f-type thymus gel (Si), quartz and porous f anode (p_s anodic alumina, A cerium ion doped indium oxide thin film is prepared on the PAA) substrate. The bismuth ion-doped indium oxide film of the literature 2 was subjected to pL measurement on different substrates, and excited by 275 nm light to obtain a light having a radiation wavelength of about 615 (10). However, the transmittance of the film provided in Document 2 is not high in the ultraviolet range, and the conductivity is not ideal. SUMMARY OF THE INVENTION S.1 In view of the problem that the fluorescent conversion material film has poor light-emitting characteristics and low conductivity, the object of the present invention is to provide a film having good light-emitting characteristics and having 6 201125822 film and the indium tin oxide thin film. method. The technical means adopted by the present invention is that the high-conductivity indium tin oxide is thin to achieve the foregoing purpose, and the oxidized tin-coated film includes indium tin oxide, and the content is the indium tin oxide ion; 0.05_5m〇1% of the indium tin oxide. The invention provides a method for manufacturing the indium tin oxide film, which is a method for manufacturing an indium tin oxide film, comprising: a method for forming a film of a tin oxide, a co-doping content of tin oxide, and the foregoing indium tin oxide. The ion and content of -l〇mol% are 5m〇1% of the cerium oxide to prepare the indium tin oxide film. The invention solves the problem that the luminescent property of the fluorescent conversion material film of the single-doped erbium ion is not good, and the cerium-coated film is prepared by using the rare earth element yttrium (YUrium, γ) and yttrium co-doped as the base material of indium tin oxide. Technical means to obtain an indium tin oxide film. By the co-doping operation, the luminescent properties of the indium tin oxide film of the present invention can be greatly improved, and the visible light fluorescence (611 nm) luminescence property of the indium tin oxide film can be greatly improved, and the visible light portion can reach nearly 90%. High penetration rate. Thus, by the technique disclosed in the present invention, an oxidized tin-tin film capable of absorbing ultraviolet light and emitting visible light fluorescence and having a down-conversion function can be fabricated as a transparent conductive film suitable for transparent conduction of a thin film solar cell. Floor. The indium tin oxide film of the present invention differs from the existing phosphor conversion material film by directly doping the luminescent center atoms having the down-conversion mechanism into the crystal lattice of the transparent conductive layer of the solar cell. The luminescent center atom absorbs ultraviolet light and emits visible light fluorescence, and the 7201125822: seeing light fluorescing can be absorbed by a semiconductor absorbing layer disposed under a device such as a solar cell, which has high conductivity and luminescent characteristics. A good conductive layer' can effectively increase the conversion efficiency of the solar cell. Specifically, the oxygen (tetra) (iv) film of the present invention can be used as a transparent conductive film for a fluorescent converter of a solar cell. Moreover, the oxidation-tin film of the present invention has the same conductivity as that of the non-doped state when it is doped with less than 0.5% of ions and is doped with 1% of pin ions. The performance of the luminescence mechanism is a major discovery of the invention. # & 夕卜' The invention discloses that the technology of co-doping ytterbium ions (Y, and pin ions to form a transparent conductive film by indium tin oxide is not limited to the fluorescent converter used in solar cells, and can also be applied to Thin film electroluminescent device. By controlling the doping amount of appropriate ion and cerium ions, the band of radiation visible light can be obtained, thereby improving performance such as brightness, viewing angle and ruggedness. In other words, the main feature of the present invention is that a rare-conducting cerium ion and cerium ion co-doped indium tin oxide can be used to produce a transparent conductive thin enamel having a function of radiating visible light and fluorescent light, which can be used not only in solar energy. The fluorescent converter of the battery can improve the down conversion mechanism, and can also be applied to the effect of improving the performance of the thin film electroluminescent device. By the technology provided by the invention, the rare earth element cerium ion and cerium ion are co-doped with indium tin oxide, An indium tin oxide film with good luminescence properties and germanium conductivity can be produced as a radiation with visible light fluorescence The use of the transparent conductive film of the month b can surely achieve the object of the present invention.

f SI The following is a further detailed illustration of the present invention by way of example with reference to the drawings. It should be noted that the examples are intended to illustrate the inventors and not to limit the scope of the invention in any respect. The indium tin oxide film of the present invention uses a film forming method to co-doped ytterbium ions with indium tin oxide. And the cerium ion to obtain the indium tin oxide film, the foregoing film forming method can be

In addition to the lyogel spin coating method, the present invention can also be applied to sputtering or other liquid phase methods such as metal-organic chemical vapor deposition (Metal-Organic Chemical Vapor decomposition) to produce the oxidation of the present invention. Indium tin film. Since the technique disclosed in the present invention includes the chemical environment change around the erbium ions by the addition of cerium ions, the symmetry of the cerium ions is optimized, and the cerium ions are allowed to emit light, so that not only by the following examples The sol-gel spin coating method and the sputtering method listed above can obtain the above special effects, regardless of the process method for adding strontium ions, that is, using a metal organic vapor deposition method or other method of adding ions, The technical content disclosed by the embodiments of the present invention can be inferred by those having ordinary knowledge in the technical field to which the present invention pertains. [Embodiment 1] This embodiment exemplifies a method for preparing a transparent conductive indium tin oxide film of indium tin oxide co-doped with ife-γ', sub- and strontium ions by a sol-gel spin coating method, the main system of which is formed by coagulation The gel method, which mixes a precursor of indium and a precursor of tin, respectively, and further adds a cerium ion precursor and a cerium ion precursor to form a lyotropic gel solution containing indium tin oxide, cerium ions and cerium ions. Then, it is subjected to lyogel plating and appropriate heat treatment at a temperature such as 400 ° C to obtain an indium tin oxide film of 3 spectroscopy ions and cerium ions. Wherein the sol gel solution can be presented as a clear solution. 1 · The preparation process of the valley gel solution: a• First mix acetic acid (Acetic acid, HAc, C2H402) with ethylene glycol 9 201125822 Monoterpene ether (2-methoxyethanol, 2-MOE 'H0C2H40CH3) 'Unevenly mix 〇 〇 To obtain a mixed solution. b. Indium nitrate (Indium (III) nitrate, In (N03) 3; purchased from Acros, purity 99.995%) as a precursor of indium ions was added to the above mixed solution, and then shocked by a supersonic vibration machine | 2 〇 minutes, And continue to stir for 10 minutes to completely dissolve the indium acid wall.

c. After the indium nitrate is completely dissolved, the tin tetrachloride (SnC14) mixed with anhydrous alcohol (Ethyl Alcohol 'C2H50H) as a precursor of tin ions is uniformly stirred, and then the indium nitrate solution is added again to make tin: indium Moerby is 9:1. d. Add cerium nitrate as a precursor of cerium ions (Ymium is stirred for 3 minutes. e. Add cerium nitrate as a precursor of cerium ions) and stir for 3 minutes.

f. Finally, after uniformly stirring at room temperature for 1 hour, a solution of lyogel containing indium tin oxide, cerium ions and cerium ions is obtained. 2. Preparation procedure of the thin crucible: a. The above sol gel solution was uniformly dropped on a glass substrate, and spin-coated with the first to HKKIrpmms and the second to 4 rpm/3 〇 s. ' b·钱完- layer coating, first | soft drying on the hot plate to evaporate each agent, "5 t / min # heating rate will increase the tube to 400 ° C, 3 seconds to advance the furnace tube / JBL |〇里' will launch the tube in 20 minutes to remove the 201125822 organics from the thin pot. If necessary, repeating the bonding film/calcining step described in a and b of the preparation process of the above film, a pure indium tin oxide having cerium ions and cerium ions co-doped in indium tin oxide and having fluorescent conductivity can be obtained. Thin film, in addition to the niobium pin, other such as: europium carbonate, europium chloride, europium oxalate, europium acetate or isopropyl Europium isopropoxide can also be used.

The foregoing cesium ion precursor, in addition to cerium nitrate, such as Yttrium carbonate, Yttrium chloride, Yttrium acetate, Yttrium oxalate or isopropyl alcohol in B ( Yttrium isopropoxide) is also suitable. The indium ion precursor may be used in addition to indium nitrate, such as indium chloride, indium ethoxide, indium isopropoxide or indium butoxide. The tin ion precursor may be used in addition to tin chloride, such as: tin ethoxide, tin isopropoxide or tin butoxide. Because of these different kinds of compounds (for example, tin chloride), other such as: tinthoxide, tin isopropoxide or tin butoxide are all dissolved. The compounds which are commonly used in the formulation of the gel solution, and thus the technical contents exemplified in the present embodiment are sufficient for those skilled in the art to understand and use these compounds to practice the present invention. In other words, the modification of the present invention to the present invention, such as the modification of the commonly used compounds in the formulation of general lysate solutions, has not yet escaped from the present invention [ς} 11 201125822. [Embodiment 2] This embodiment exemplifies the properties of the indium tin oxide film of the present invention. As shown in the first figure, a small amount of bismuth ions (〇, 〇丨, 〇 3 mole%), 钇 ions (0, 0.5, Bu 2, 4 m〇le%) of indium tin oxide film, The intensity position of peak(222) in the XRD pattern of each process parameter is similar. The crystallinity of the ytterbium ion and ytterbium ion co-doped indium tin oxide film obtained by each process parameter is the same, so the doping 铕 ion (〇, 〇1) 〇3 卜 ions (0, 0.5, 1, 2, 4 mole%) do not significantly destroy the oxidized steel tin lattice. As shown in the second A to D D, doping a small amount of strontium ions, strontium The ions can slightly increase the grain size of the oxidized tin. As shown in the third A to c. c, as the doping amount of cerium ions increases, the stronger 611 nm red light is excited by 254 nm light. As shown in the fourth figure, it can be seen that the two at 239 nm and 469 nm

The apparent absorption peak is increased with the increase of the doping amount of the ion. As shown in the fifth figure, the resistance of the indium tin oxide film doped with 〇·5 m〇le% ions is about 15% higher than that of the undoped copper oxide tin film; doping! The resistance of the copper oxide tin film of the coffee is higher than that of the undoped indium tin oxide film; the resistance of the doped tin oxide film of 4 mole% ion is higher than that of the undoped indium tin oxide film The resistance is about *❺. It is known that the more heterogeneous ions doped, the higher the resistance of the indium tin oxide film. It can be seen from the above that when the content of _ sub is the amount of OJ-lOmol% of indium tin oxide, the amount of indium tin oxide is 0 05_5m 〇 lc /. At that time, the object of the invention can be achieved by providing a high light transmittance and high conductivity indium tin oxide film, and the content of barium ions is 0.5_4 m〇1% of indium tin oxide and is contained in barium ions. When the indole-tin oxide is 0.05_0 5〇1〇1%, better conductivity characteristics can be obtained. The invention also uses a material in which indium tin oxide is co-doped with cerium ions and cerium ions to form a transparent conductive indium tin oxide film, which has high light transmittance and high conductivity, and absorbs ultraviolet light of less than 400 nm in sunlight. It emits fluorescence with a wavelength of 61 ^ nm, so it can be applied to a transparent conductive layer in a solar cell. At the same time, * Because the indium tin oxide film of the present invention has the function of down-conversion, it can also be used to increase the photoelectric conversion efficiency of the solar cell. The indium tin oxide film of the present invention can also be applied to a thin film electroluminescent device to increase the luminance of the light to enhance properties such as brightness, viewing angle and durability. Further, as shown in the production method disclosed in the present invention, in the production of the indium tin oxide film of the present invention, the process does not require a vacuum environment, which is advantageous in terms of manufacturing cost, and it is understood that the present invention is industrially usable. The invention uses a material of indium tin oxide to promote the hybrid ion and the ion-plated material to form a transparent conductive indium tin oxide film. The invention discloses that the erbium ions and the erbium ions are simultaneously doped, and the cesium ions can enhance the energy conversion of the lanthanum ions by the lanthanum ions, and the technology for generating the fluorescence is the first in the world, which is not found in the prior art, and has not been found. A similar report has been exported to domestic and foreign publications or patent search materials. Therefore, the present invention is indeed novel. S1 The invention uses a material of oxidized steel tin to replace the heterogeneous ion and the ytterbium ion to form a transparent conductive indium tin oxide film, which is different from the film in which the single-doped ytterbium ion does not emit light, which can be produced by co-doping ytterbium ions. Camp light with a wavelength of 611 nm. That is, by the technical means of the present invention, it is possible to provide a special effect which is not available in the prior art. Since the present invention uses indium tin oxide to co-doped ytterbium ions and locks 13 201125822 ion transparent conductive indium tin oxide thin ruthenium "field-bound film ^• has the above characteristics, it is also suitable for use in thin film electro-generated well-producing film The invention is also a special effect of the indium tin oxide thin k of the present invention. The above special effects are based on the invention provided by the invention, and are not taught or taught by the prior art, so the invention is indeed progressive. .

Based on the above results, the present invention has industrial applicability, newness and progress. Although the embodiments of the present invention have been disclosed in the foregoing description of the present invention, the following description is intended to illustrate the technical scope of the present invention and not to limit the scope of the present invention. Any person skilled in the art will be able to make changes and fullness in the art of the present invention without departing from the spirit of the invention and the invention has not yet departed from the scope of the invention. [Simple description of the diagram] The first picture is a pin-ion ion (〇, 〇. 1, 〇3 m〇ie%), and the ion (〇, 〇5, 1, 2, 4 mole%) co-doped indium tin oxide film XRD pattern under annealing conditions of 4 〇〇〇 c / 丨 hour. The second A picture is a scanning electron microscopy (SEM) photograph of a pure indium tin oxide film annealed at 4 〇〇 / 1 hour, and its magnification is i5 〇 k. The second B picture is a pure indium tin oxide film annealed 400. (:/1 hour scanning electron microscope (SEM) photograph, the magnification is 200k. The second C diagram is the pin ion (0.1%), the ion (1 mole%) co-doped indium tin oxide film is annealed at 400 ° Scanning electron microscopy (SEM) photographs at C/1 hour, with a magnification of 150k. The second D is a cesium ion (0.1%), strontium ion (1 mole%) co-doped indium tin oxide film in annealed 400 Scanning electron microscope (SEM) photographs at °C/1 hour, the magnification is 200k. 201125822 The third A map is a pin ion (〇, 〇卜〇2, 〇3 is 16%), 钇 ion (〇, The room temperature fluorescence emission spectrum of 〇·5, 丨, 2, 4 doped indium tin oxide thin films is annealed at 40 (TC / 1 hour, ^, ^ v , J yue with 254 nm light excitation conditions. Figure B shows the variation of the luminescence intensity of the (4) sub-doped indium tin oxide film in the wavelength (10) for the cesium ion and the ionic ion concentration. The third C picture is the 4th A of the third A picture /放大 A magnified view of the partial spectrum of the co-doped oxygen (tetra) tin film with solid bismuth ion (0.1 mole%) and strontium ion (1 # climbing m〇le%). The ion-doped (〇, 0.1 mole%), epi-ion (〇, 〇5, 1, 2, 4 m〇le%) co-doped indium tin oxide film under the condition of annealing 400t / 丨h, corresponding to 5〇0-4 ^Excitation spectrum of the transition (5Dq — transition) ° The resistivity of the yttrium ion co-doped indium tin oxide film at different co-doping concentrations. The fifth figure is 铕 ion, fire 400 ° C / 1 hour,

[Main component symbol description] None m 15

Claims (1)

201125822 VII. The scope of the patent application: 1. A film of indium tin oxide, including indium tin oxide; 3 is the amount of indium tin oxide. 1 -1 Omol% of barium ions; 3畺 system of indium tin oxide 0.05-5 mol% of cerium ions. For example, in the indium tin oxide film described in claim 1, the content of the foregoing ions is 0.5-4 mol% of indium tin oxide; The content of the pin ions is 0.05-0.5 mol% of indium tin oxide. 3) A method for manufacturing an indium tin oxide film, comprising: using a film forming method to co-doped indium tin oxide with a content of the indium tin oxide: M〇m〇1% of ions and content of the indium oxide 0.1-5 mol% of tin ions of tin to prepare a film of indium tin oxide. 4. The method for producing an indium tin oxide film according to claim 3, wherein the film forming method is selected from the group consisting of a rotary film recording method and a metal organic vapor deposition method. Phase method. 5. The method for producing an indium tin oxide film according to claim 3, wherein the film forming method is a sputtering method. 6. The method for producing an indium tin oxide film according to claim 4, wherein the film forming method is a molten gel spin coating method, comprising: mixing a precursor of indium and a precursor of tin and separately adding An ion precursor and a helium ion precursor are formed to form a sol gel solution containing tin oxide, barium ions and barium ions; indium tin oxide is coated with the gel and heat treated to obtain a film. S.1 7. The method for producing an indium tin oxide film according to claim 6 of the patent application is a method of the above-mentioned heat treatment, which is 400. The temperature of the crucible is carried out. 8. If you apply. And the method for producing the oxidized tin-coated film according to the seventh item of the present invention, comprising: mixing ethylene glycol monomethyl ether with acesulfame, uniformly stirring to obtain a mixed solution; and adding the above mixture/cold solution After the indium nitrate precursor is indium nitrate, ultrasonic vibration is performed; after the indium nitrate is completely dissolved, 'the tin tetrachloride mixed with the absolute alcohol as the tin ion precursor is uniformly mixed, then the indium acid solution is added again to make the tin and the tin The molar ratio of indium to 90: 1 〇; the cerium nitrate as the precursor of the ion and the 4 acid pin as the precursor of the cerium ion are obtained at room temperature for four hours, and then obtained - containing indium tin oxide, cerium ions And a solution of cerium ions in a gel solution. The solute solution is evenly dropped on a glass substrate, and spin-coated under the conditions of first rotation rpm/10s and second rotation 4000 rpm/30 s; ^ after plating-layer coating, 'first in 2 Hey. The crucible hot plate was soft baked to raise the tubular furnace to 4 Torr at a heating rate of 5 C / min. After that, the furnace tube was advanced for 30 minutes, and the furnace tube was pushed out for 2 minutes, and the residual organic matter in the film was removed to obtain an indium tin oxide film. 9. The method for producing an indium tin oxide film according to claim 6, 7 or 8, wherein the cesium ion precursor is selected from the group consisting of cerium nitrate, cerium carbonate, gasification pin, oxalic acid, vinegar shaft and isopropyl alcohol. The group formed by 铕. 1. The method for producing a film of indium tin oxide according to claim 6, 7 A, wherein the barium ion precursor is selected from the group consisting of barium nitrate, barium carbonate, barium chloride, barium acetate, A group consisting of bismuth oxalate and bismuth isopropoxide. 11. The method for producing an indium tin oxide film according to claim 6, 7 or 8, wherein the precursor of indium is selected from the group consisting of indium nitrate, indium chloride, indium ethanol, indium isopropoxide and indium butyrate. The group that makes up. 12. The method for producing an indium tin oxide film according to claim 6, 7 or 8, wherein the precursor of tin is selected from the group consisting of tin chloride, tin ethoxide, tin isopropoxide or tin butoxide. group. Eight, schema: (such as the next page) [S1 18