TW201013709A - Zinc oxide group transparent conductive film and process for making same - Google Patents

Abstract

This invention provides a zinc oxide group transparent conductive film which exhibits excellent workability and environmental durability. The transparent conductive film of this invention contains a zinc oxide as a major component, and two elements of titanium (Ti) and gallium (Ga), wherein the content of Ti is in the range of 1.1 at% or more, or the content of Ga is in the range of 4.5 at% or more.

Description

[Technical Field] The present invention relates to a zinc oxide-based transparent conductive film containing zinc oxide as a main component and a method for producing the same. [Prior Art] A transparent conductive film, a conductive mask or a display such as a heat-emitting element or a touch switch on an infrared masking plate or an eiectr〇statiCs masking plate (disPla5) The need for a transparent electrode such as a tantalum device is increasing. As such a transparent conductive film, an indium oxide film (IT〇) doped with tin has been used, but it is desirable because of the high price of ιτο. It is possible to develop an inexpensive transparent conductive film. Therefore, a zinc oxide-based transparent conductive film which is a more inexpensive film is attracting attention, and zinc oxide (aluminum zinc oxide) or aluminum oxide added to zinc oxide is added to the zinc oxide. GZ0 (recorded; zinc oxide) and the like are commercially available. ❹ However, such a zinc oxide-based transparent conductive film is inferior in electrical conductivity and durability to ΙΤ0, and therefore is required for high conductivity or stabilization. In the case of adding various elements (refer to Patent Documents 1 to 4, etc.), in particular, it is studied to add Ga (gallium) as an additive element (refer to Patent Documents 5 to 7, etc.). On the other hand, in the case of such a zinc oxide-based transparent conductive film, if the film is to be put into practical use, (4) the etching rate is too fascinating, so that it is difficult to perform patterning and the problem of poor environmental resistance. In addition, as a protective film for optical discs, 3321341 201013709 is added to zinc oxide, which is composed of alumina, gallium oxide, zirconium oxide, titanium oxide, etc. (refer to Patent Document 8), but the protective film is not in a fine manner. The pattern composition is such that the transparent conductive film which is problematic in terms of workability or haze ratio (haze factor ambiguity index, referred to herein as haze ratio) is completely different. [Prior Art Literature] [Patent Literature] [Patents [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. 2002-75062 (Patent Application) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei 10-306367 (Application No.) Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Explanation of the Invention] [Problems to be Solved by the Invention] 321341 201013709 In view of the above, the present invention has been made to provide an oxidized transparent conductive film which is excellent in workability and environmental resistance. [Means for Solving the Problem] The first aspect of the present invention to solve the above-mentioned problems is a zinc oxide-based transparent conductive film characterized by containing zinc (Ti) and gallium (Ga) as a main component of zinc oxide. The two elements, and the two elements are contained in a range of 1. 1 at% (atomic percent) or more than 4. 5 at% or more. In such a first aspect, by containing two elements of titanium (Ti) and gallium (Ga) in a predetermined range, it is possible to obtain a film excellent in workability and environmental resistance. The second aspect of the present invention is the zinc oxide-based transparent conductive film according to the first aspect, wherein the content y (at%) of gallium is a value represented by the content x (at%) of titanium (-0.66x). +5,5) The following range. In such a second aspect, the haze ratio of the film to which the etching is applied is further increased, and it becomes more useful as a transparent conductive film for solar cells. A third aspect of the present invention is the zinc oxide system according to the first or second aspect, wherein the content y (at%) of gallium is represented by the content x (at%) of titanium. The range of the value (-2x+10. 4) or less and the value (-0.5X+1.1) or more of the content of titanium (at%). In the third aspect, the titanium oxide and the gallium are set to a desired range, and the specific resistance of the film is lower, and the electrical conductivity is further improved. A fourth aspect of the present invention is the zinc oxide-based transparent power-producing film according to any one of the first to third aspects, wherein the content y (at%) of the gallium is in the content x (at%) of titanium. The value is not (-χ+3. 4) or less, (x_0. 9) or less, or 5 321341 201013709 (2. 3x+10. 1) or more. In such a fourth aspect, by setting titanium and gallium to a desired range, the carrier density becomes extremely small, and the transmittance of long-wavelength light corresponding to a near inf lared band will be more In order to improve, it is a film that is particularly suitable for solar cell applications. A fifth aspect of the present invention is a zinc oxide-based transparent conductive film, which is a zinc oxide-based transparent conductive film of the fourth aspect, which is characterized by a transparent conductive film for a solar cell. In such a fifth aspect, it is particularly superior to the penetration of long-wavelength light corresponding to the near-infrared region, and is an excellent film for solar cell use. A sixth aspect of the invention is a zinc oxide-based transparent conductive film, which is a zinc oxide-based transparent conductive film according to a fifth aspect, which is characterized in that a surface electrode is formed on a transparent substrate. In the sixth aspect, the surface electrode having excellent workability and environmental resistance can be realized by the zinc oxide system. A seventh aspect of the present invention is a zinc oxide-based transparent conductive film.

Q. The zinc oxide-based transparent electric film according to any one of the first to sixth aspects, characterized in that the haze ratio is 10% or more. In such a seventh aspect, it is a transparent conductive film capable of achieving a haze ratio of 10% or more. An ninth aspect of the present invention is a zinc oxide-based transparent conductive film, which is a zinc oxide-based transparent conductive film according to a seventh aspect, which is characterized in that the surface is etched by a weak acid after film formation. In such an eighth aspect, a transparent conductive film having a higher haze ratio of 6321341 201013709 can be realized by etching. According to a ninth aspect of the invention, there is provided a method for producing an oxidized transparent conductive film, characterized in that: zinc oxide is a main component, and two elements of titanium (Ti) and gallium (Ga) are contained, and the two elements are The zinc oxide-based transparent conductive film contained in the range of titanium L lat% or more or gallium of 4.5 att / 〇 or more is formed into a film. In the ninth aspect, a film containing two elements of titanium (Ti) and gallium (Ga) in a predetermined range can be formed, and a film excellent in workability and environmental resistance can be produced. The ninth aspect of the present invention is the method for producing a zinc oxide-based transparent conductive film according to the ninth aspect, wherein the zinc oxide is used as a main component and contains two elements of titanium (Ti) and gallium (Ga), and The two elements are formed by sputtering a zinc oxide-based plating target contained in a range of 1.lat% or more of titanium or 3.5 at% or more of gallium, by sputtering or ionizing. In such a tenth aspect, a film of a predetermined range can be formed into a film more easily by using a sputtering target of a predetermined composition and forming a film by sputtering or ion plating. According to an eleventh aspect of the present invention, in the ninth or tenth aspect, the method for producing an oxidized-transparent transparent conductive film, wherein the surface is etched by a weak acid after the film formation, the haze ratio can be increased. In the eleventh aspect, the surface of the transparent conductive film is etched by only a predetermined amount by using a weak acid, whereby a film having an improved haze ratio can be produced. [Effects of the Invention] The zinc oxide-based transparent conductive film of the present invention exhibits workability and resistance to environmental factors of 7321341 201013709 by containing two elements of titanium (Ti) and gallium (Ga) within a predetermined range. The effect of the film. [Embodiment] [Best Embodiment of the Invention] The oxidized transparent conductive film of the present invention, λ ^ ν ^ , and the electric film are based on zinc oxide as a main component, and are added together with gallium, then + The experience is completed... ^Environmental resistance will be significantly improved

The zinc oxide-based transparent conductive film of the present invention is characterized in that the two elements of the group (5) and gallium (5) are added as elements, and the two elements are in the range of l.lat% or more of gallium or 4.5 at% or more of gallium. That is, it must be included in the range in which titanium is excluded from mx and gallium is in the range of 4.5 at% or less. If two substances are contained in such a range, the effect of improvement can be achieved, but if it is outside the range, it is difficult to obtain an effect of improving environmental resistance. As in this case, it has been confirmed that the processing can be carried out smoothly by the system.亦 亦 亦 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 范 范 范 , , , , , , , 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐Film of sex. Furthermore, in the present application, the content of each metal element (at%) is relative to the molar number of all metal elements, and the ratio of the molar numbers of Ti and Ga is (Ti/(Zn+Ti+Ga). ), (Ga/(Zn+Ti+Ga)). Here, the environmental resistance test is performed by measuring the change in the specific resistance before and after the TC and the relative humidity of 90% for 250 hours. If the change (increase) of the specific resistance is within 7%, In the design of the device, it can be judged that there is no big problem, so it can be used to be practical. 8 321341 201013709

A Here, the rate of change (%) of the specific resistance can be expressed by the following equation. Further, if the specific resistance is lowered, since the design of the device does not become a big problem, it is assumed that the change can satisfy the condition of 7% or less. Rate of change of specific resistance (% Μ (specific resistance after environmental resistance test / specific resistance before environmental test) -1] χ 100 On the other hand, if the rate of change of specific resistance exceeds 7%, the equipment design is special. It may be difficult to maintain long-term stability, and there are problems in practical use. For example, when the liquid crystal display is used for a long time, the response of the liquid crystal switch will deteriorate, resulting in an after image feeling in the image. In particular, the content y (at%) of gallium is in the range of the value (τ2 χ + 10.4) of the content x (at%) of titanium, and the content x (at%) of titanium. Χ1 χ1 χ 比 -0 -0 -0 -0 -0 -0 -0 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化(3. 5x+9. The value of y (at%) is a value of -2. 5x+9. 8) Below the range of (-0.5X+1.1) or more, the specific resistance becomes 1. 5x1 (Γ3 Ωcm or less, which is a more favorable film. The resistance is set to 2. 5 χ 10 - 3 Ω (: ηι or less or preferably 1. 5xl0_3 Ω cm or less, for example, in the array side electrode of the liquid crystal display, it is generally considered that the degree of 1 χ 10 _ 3 Ω cm can be used, in practical use. Further, in particular, the content y (at%) of gallium is set to be lower than the value (-x+34) of titanium content X (at%) 321341 201013709, (χ-〇·9). The zinc oxide-based transparent conductive film of the following range or (-2. 3x+l〇. 1) or less is preferable. As a result of containing gallium and titanium in such a range, the carrier density is small and easy to change. It penetrates the film of long-wavelength light in the near-infrared region, and is therefore suitable for use in, for example, a solar cell. Here, the transmittance on the long wavelength side of the near-infrared region is caused by absorption and reflection of light. Plasma oscillation of free electrons (estained ee electrons) will increase in the side of the long wavelength side. The plasma wavelength that can cause plasma oscillation can be expressed by the following formula: 'The lower the carrier density, the more electricity The pulp wavelength will be on the longer wavelength side. [Number 1]

Where: c: speed of light 3. 0xl01D[cm/s], e: electron charge 4. 8xl0_1°esu (electrostatic unit), ne: carrier density [cm-3], e 〇=7Γ /4, ε = dielectric constant (= square of refractive index, n2 = 2. 02 = 4. 0) ' m*: effective mass of zinc oxide (0. 28x9. lx 1〇28[g] ), A ··mobility [cm2/V · s]. If the carrier density is 4xl02°cnf3, the plasma wavelength is 1650 nm, so long-wavelength light can also penetrate sufficiently. On the other hand, especially when considering the use of thin film germanium (Si) solar cells, the diffusion transmitted light when the light is incident is divided by the value of the total transmitted light 10 321341 201013709 The size of the rate will be an important factor. That is, when the transparent conductive film is formed as a surface electrode formed on the transparent substrate, when the power generation layer is formed thereon, if the haze ratio of the transparent conductive film is high, the light can be sealed in the power generation layer. Therefore, it is generally considered that the power generation efficiency will rise and it is suitable. Ο In this way, when the haze ratio is increased, it is preferred to use a weak acid to etch the surface of the transparent conductive film to form a texture on the surface, in particular, such as the content of marry. When y (at%) is in a range of a value (-0.66X+5.5) of the content of titanium (at%), it is easy to form a suitable texture, and a haze ratio of 10% or more can be achieved. The method for producing a zinc oxide-based transparent conductive film which is an image of the present invention is not particularly limited. For example, a ship method, an ion-electric method, a vacuum plating method, a chemical vapor deposition method, a spray method, an anodization method can be used. , ^ cloth method, sol gel (wipe. gel) method, etc. (4) forming technology. Moreover, the method of adding an element to the zinc oxide-based transparent conductive material is not half.

Γ Γ ^ ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟 惟After the transparent conductive film is formed, the additive element is thermally expanded in the transparent conductive medium, or ion implantation is performed. However, guanamine has a material with added elements in order to: = qualitatively, it is better to use a film, and then: =:::! = into a transparent conductive shake of zinc oxide, and a transparent conductive film with zinc oxide is used. 321341 11 201013709 The same composition of the sinter can be 'but can also be made into a plurality of ships to form a light film. At the same time, = the ship's dry materials at the same time, as long as it is known as a method. Here, the term "so-called" refers to the use of the membrane by the ion-electric material of the film, which is used by the filming of the urethane film. (also known as a pellet). Here, the zinc oxide-based surface (four) used in the formation of the transparent conductive film of the present invention by sputtering or ion plating is described as an example, and the description is merely illustrative, and the manufacturing method is not particularly limited. First, as a composition, a transparent conductive film of the present invention is formed to form a film. The starting materials are generally oxygen powder (ZnO), gallium oxide (Ga2〇〇, titanium oxide (Ti〇2) powder, but can also be zinc, such as simple substances, compounds, composite oxides When a pure substance or a compound is used, a process which can be used as an oxide is carried out in advance, and a method of mixing and molding at a desired mixing ratio can be used, and various conventional wet methods or dry processes can be used. m The raw material powders are not particularly limited by the method. The dry method may be exemplified by a cold press (c〇ld press) method or a hot press (h〇t press) method, etc. In the cold press method, The mixed powder is filled in a molding die to prepare a molded product, and is fired. In the hot press method, the mixture is fired and sintered in a molding die. For the wet method, for example, it is preferably employed. Filtration molding method (refer to 曰12 321341 201013709 *\本特开平11-286002号). This type of filtration type 岑 method is a kind of cleavage from a ceramic magnetic material slurry (slurry) under reduced pressure to produce a split body. Filter molding die made of water-insoluble materials a lower mold for molding having one or more drainage holes, a filter having water permeability supported on the lower mold for molding, and a sealing material for sealing the filter from the upper side The mold for clamping molding is formed, and the lower mold, the molding mold frame, the sealing material, and the filter sheet can be separately assembled in a disassembled manner as described above, and only the dewatering slurry is removed from the surface side of the filter sheet. Moisture 0 filter molding die to prepare a slurry made of mixed powder, ion-exchanged water and organic additives, and injecting the slurry into a filter-formed honey mold, only in the slurry from the side of the transition sheet The water is decompressed and drained to prepare a molded body', and the obtained ceramic molded body is dried and degreased, and then fired. The firing temperature by the cold pressing method or the wet forming method is preferably 1000 to 1500 ° C. 'More preferably, it is 1000 to 130 (rc, and the environment is an atmospheric environment, an oxygen atmosphere, a non-oxidizing atmosphere, or a vacuum atmosphere, etc. On the other hand, when the hot pressing method is used, it is preferably 900 to 1300). Sintered at °C, and its atmosphere is non-oxygen After the firing in each method, the molding is performed by a molding process of a predetermined size to form a sputtering target. The zinc oxide-based transparent conductive film of the present invention can be used in this manner. The sputtering target produced by the composition of the same composition can be suitably prepared by sputtering, and the method for producing the zinc oxide-based transparent conductive crucible of the present invention is not limited to the above. The sputtering target of sputtering or ion plating, etc. The zinc oxide-based transparent conductive film of the present invention can be used as a transparent electrode, an infrared shielding plate or an electrostatic shielding plate surface heating body of various semiconductors of the 321341 13 201013709 device. It is used as a transparent electrode such as a conductive film such as a touch switch or a transparent electrode such as a display device such as a liquid crystal, a plasma, or an EL (electroluminescence), or a solar cell. In particular, a transparent conductive film having a small carrier density and a high transmittance equivalent to long-wavelength light in the near-infrared region is suitable for use in a transparent electrode of a solar cell. Here, an example of a solar cell structure using the zinc oxide-based transparent conductive film of the present invention as a transparent electrode will be described with reference to Fig. 10 . As shown in Fig. 10, the thin film solar cell 10 is provided with a transparent electrode 12 made of the zinc oxide-based transparent conductive film of the present invention on a transparent substrate 11 made of glass or the like. The transparent electrode 12 may be a film formed by sputtering or the like of a zinc oxide-based transparent conductive film, or may have a textured structure by etching the surface with a weak acid. Further, on the above, a power generation layer 13 made of an amorphous silicon p layer 13a, an i layer 13b, and an η layer 13c, and a back electrode 14 made of a metal are provided. When the solar cell 10 is introduced with sunlight from the transparent substrate 11 side, power is generated in the power generation layer 13. However, when the haze ratio of the transparent electrode 11 is high, the light is blocked in the power generation layer 13, and as a result, This light blocking effect increases the power generation efficiency. In addition, the power generation layer structure of the amorphous tantalum solar cell is a basic example as described above, but is not particularly limited thereto, and the zinc oxide-based transparent conductive film of the present invention can of course be transparent as various solar cells. Use with electrodes. For example, as a thin film solar cell, a compound such as CIGS (p-Cu 14 32.1341 201013709 Λ (InGa) Se2) (copper indium gallium selenide) or Cd_Te (a ruthenium iridium) is known as a solar cell, for example, on a glass substrate. The zinc oxide-based transparent conductive film of the present invention can be applied to a window layer having a back surface electrode, a power generation layer made of (p-Cu(InGa)Se2), and a window layer into which light is introduced. In this case, since the zinc oxide-based transparent conductive film of the present invention is used because of the environmental resistance, the environmental resistance can be improved. Further, the zinc oxide-based transparent conductive film of the present invention can be applied not only to a thin film solar cell but also to a transparent conductive film of another solar cell. [Embodiment] Hereinafter, the present invention will be described based on an embodiment in which a film formed by a sputtering method is exemplified. However, the present invention is not limited to this embodiment. (Spray target production examples 1 to 50) BET (surface area measured by Bruner-Emmeri-Teller method) = ZnO powder of 3.59 m 2 /g, BET = 7. 1 Οιπ Ti〇2 powder and Ga2〇3 powder with βΕΤ=13. 45id /g, according to the molar ratio of relative to the total metal element, the molar ratio of Ti and Ga. (Ti/(Zn+Ti+Ga) , in the mixing ball mixer (the molar ratio of the molar ratio of the samples shown in Tables 1 and 2) is about 1.0 kg. Mix in ball mill). Then, a 4 wt% aqueous solution of a polyethylene glycol as a binder was added to 6% by weight with respect to the mixed powder, followed by mixing, and cold pressing to obtain a molded body. The molded body was heated in the air at a temperature elevation rate of 60 ° C / hour, and degreased at 600 ° C for 10 hours. Then, in the atmosphere, the temperature is raised from room temperature to 1300 ° C at a temperature increase rate of 10 ° C / hour, and then calcined at 1300 ° C for 8 15 321341 201013709 hours ' and then cooled to room temperature by HHTC / hour. A sintered product is obtained. As a result, the sinter is subjected to a surface rubbing HPlaingrinding), and the dried stalk of x6 mmt is obtained. _ Furthermore, the results of the sinter obtained by ICP knife cutting confirmed that the composition of the raw material and the material were almost the same. (ΑΖ0 sputtering target production example) BET = 3.59 m2 / g of Zn0 powder, BET = 3. 89 m2 / g of Ah 〇 3 powder, according to the number of moles of A1 relative to the total metal element The proportion of the ratio (Α1/(Ζη+Α1))^^ 2, such as %, is prepared in a total amount of about 1.0 kg and this is tolerated in the ball mill. Then, the 聚乙烯% polyvinyl alcohol aqueous solution as a binder was added to the mixed powder with a weight of 6. _ after mixing and cold pressing to obtain a molded body. The molded body was raised in the atmosphere at a heating rate of 6 〇 t > c / hour: the dish was at 600 °C. Lower degreasing 1. hour. Next, it was raised to 13 Torr in the air at room temperature to C at a rate of temperature increase of 100 C/hour. The crucible was calcined for 8 hours, and then cooled to room temperature by loot/hour to obtain a sintered product. The resulting sinter was subjected to surface grinding to obtain a splash of 0.1 GGmm x 6 mmt. 13 (film formation example 1) On the dc (direct current) magnetron sputtering device of the 4 吋 cathode, the sputtering target and the AZ0 sputtering target of each manufacturing example were respectively mounted, and the oxygen was divided at a substrate temperature of 25 〇. The transparent conductive film was prepared by pressing at 0 to 2. 〇sccm (standard cubic centimeters per minute) under a change of 0.5 sccm (corresponding to 〇 to 6 6xl 〇 -3 Pa (Pa)). The transparent conductive film obtained in this manner is a zinc oxide-based transparent conductive film having the same composition as that of the sputtered transparent conductive film 321341 16 201013709. The composition analysis of such a zinc oxide-based transparent conductive crucible can be carried out by ICP (inductively coupled plasma) after the single film is completely dissolved. In addition, when the film itself is formed into a device, if necessary, the cross section of the corresponding portion is cut by fib (focusing ion beam) or the like, and the SEM or TEM (transmission electron microscope) is used. An analysis device (EDS (Energy Dispersive Spectrometer) or WDS (Wavelength Long Dispersion Spectrometer), Auger Analysis, etc. is specified. The condition of the Tibetan bond is made in the following manner to obtain a thickness of 1200 A (Angstrom) β The film is reduced by the size. Must be = 1 〇〇, t (thickness) = 6mm. Key reduction method: DC magnetron reduction clock exhaust device, rotary 杲 (r〇tary pump) + cryo pump (cryo pump) The degree of vacuum reached: 3xl (less than T5pa)

Ar (argon) pressure: 4. OxlOla oxygen partial pressure: 0 to 6. 6xl (T3Pa

^ Substrate temperature: 250 °C 〇 Sputtering power: 130W (watt) (power density 1.6W / CIH2) Use substrate: Corning #1737 (glass for liquid crystal display) 50mmx50mmx0. 8mmt Transparent film formed by changing oxygen partial pressure The conductive film was cut to a size of 10 mm x 10 mm, and the specific resistance was measured according to the Vander Pauw method (Hall coefficient measuring device (Resi Test 8300) manufactured by Toyo Technology Co., Ltd.) In b), the specific resistance of the ZnO (AZO) film doped with aluminum (A1) as a comparative example is 321341, 201013709. 2. 4at% is dependent on oxygen partial pressure. Thus, the specific resistance oxygen partial pressure is in 〇sccm (Equivalent to 〇xl (T3pa), the specific resistance is the lowest. Also, in Fig. 1(a), the ZnO film doped with titanium (Π) doped 2at% and gallium (Ga) doped lat% The specific resistance of sample A24) is dependent on oxygen partial pressure. The partial pressure dependence of oxygen in sample A24 indicates the same characteristics as that of AZ0 film. The TiGa-based ZnO film in other sample compositions also shows the same characteristics. Therefore, the characteristic values shown in Tables 1 and 2 are as oxygen partial pressures in Osccm (phase Data of 〇xl (T3pa) [Test Example 1] (Environmental resistance test) Each of the transparent conductive films formed by 分sccm (equivalent to 0xl (T3Pa) formed by oxygen partial pressure was cut into l 〇mmxl〇mm size, first, according to the Van der PaUW method (Dongyang Technology, Hall coefficient measuring device Resi Test 8300) to determine the specific resistance, and then sealed in a constant temperature and humidity device (PR-2KP made by EspEC) 'placed in 60. 〇 90% RH (relative humidity) in the environment after 25 ' hours 're-measure the specific resistance to calculate the rate of change of the specific resistance before and after the placement. At the same time 'when the temperature is controlled by the constant temperature and humidity device, by the temperature The sample A1 in the range of less than 1. lat% and gallium in the range of 4.5 at least or less, and the result is shown in Table 1 and Table 2. The samples A16 and A22 with a gallium content of 〇% have a rate of change of specific resistance of more than 7%, but the rate of change of the sample other than the range is 7% or less. That is, 'from the data in Table 1 If the titanium is above 1.2at%, the rate of change of the specific resistance will become 7% or less, but the rate of change of the specific resistance will become 7% or less of titanium is above 丨. lat%, and gallium is at 4.5 at or above. 321341 201013709 \ Real, can be understood by data other than those shown in Tables 1 and 2. In Figure 2, resistance The environmental test results are indicated by 〇 in samples of 7% or less, and the samples in 7% or more are indicated by #. [Test Example 2] (Measurement of specific resistance) Each of the transparent conductive films formed by Osccm (corresponding to 0xl (T3Pa)) was cut into a size of 10 mm x 10 mm by Van der.

The Pauw method (manufactured by Dongyang Science and Technology Co., Ltd., Hall coefficient measuring device Resi Test 8300) measures the specific resistance.将此 This result is shown in Tables 1 and 2. From this result, it is understood that the content y (at%) of gallium is in the range of the value (−χ6〇·4) of the content of titanium (at%), and the content of titanium is x (at%). a transparent conductive film having a value of not more than -0. 5x+l. 1 or more, and a specific resistance of 2. 5 χ 1 (Γ3 Ω οηη or less. On the other hand, samples outside the range are known. The ratio of the ratio of the specific resistance (-2x+1〇4) below the specific resistance x (at%) below 2 5xl 〇 -3Qcin is that the yt content of gallium is in the titanium content. The value indicated by x(at%) (the fact of the range above -(〇.5χ+1.: 〖)' can be judged comprehensively by data including those shown in Tables 1 and 2. Fig. 3 The results of the environmental resistance test are less than 7%, and the specific resistance is 2.5xl (T3Qcm or less, to indicate the specific resistance of 2. 5x10 Qcm or more, and the environmental resistance test is indicated by Lu). The result is a sample of 7% or more. In particular, it is understood that the content y (at%) of gallium is less than or equal to the value (-2.5x+98) of the content x (at%) of titanium and (_〇) 5χ+ιι) above range 19 321341 201013709 The specific resistance of the sample is 1.5 χ 1 (Γ3 Ω αη or less. Further, the value indicated by the content x (at%) of titanium which is 1. 5×10 3 〇cm or less is (-2X+10.4) or less. The range of the range is that the content y of gallium is in the range of titanium content x (at a value of at ° / 〇 (-2. 5x + 9.8) and (-0. 5 χ + 1) above). The fact can be judged by a combination of data other than those shown in Tables 1 and 2. In Fig. 4, the specific resistance is 1.5 χ1 (the sample of Γ3 Ωαη or less is represented by ◊. Test Example 3] (Measurement of Hall's coefficient) 各 Each transparent conductive film formed by partial pressure of oxygen on 〇sccm (corresponding to 〇x13-3Pa) was cut and measured from the Hall coefficient of Van der Pauw method (Dongyang Science and Technology, Hall coefficient measuring device Resi Test 8300), the carrier density and carrier mobility of each film were measured. The results are shown in Tables 1 and 2. The results show that the content of gallium y ( At%) is a value (-χ+3.4) or less, (x-〇.9) or less, or (-2.3χ+1〇·1) or more in the content of titanium (at%). Carrier density in the sample On the other hand, in the case of samples other than the above, the carrier density is greater than that of 4.0xl02°cnT3. Further, the carrier density becomes 4. 〇x W cm The following dry circumference is the content y (at%) of gallium, which is below the value (-x+3.4) of the content of titanium x (at; 0/〇), below (χ-〇·9), or -2. 3x+l〇.i) The fact of the above range ' can be judged by a combination of data other than those shown in Tables 1 and 2. Figure 5 is a test result of environmental resistance test of 7% or less, wherein 20 321341 201013709 △ indicates a carrier density of 4.0xl02 () cnr3 or less, and ▲ indicates a carrier density of 4. 0xl02 °cnf3 or more. The sample shows a sample having an environmental resistance test result of 7% or more. [Table 1] Ο ❹

Ti addition amount (at%) Ga addition amount (at%) Environmental resistance test result (%) Specific resistance (Ω · cm) Carrier density (cm-3)

21 321341 201013709 [Table 2]

Ti addition amount (at%) Ga addition amount (at%) Environmental resistance test result (%) Specific resistance (Ω · cm) (cm

2.2 E+20 1.3 EJj〇1.2 E+20 1. 3 E-021. 0 E+20 2. 0 E-02|〇^+2〇 (film formation example 2) The same method as the above production example is as follows The sputtering targets manufactured in the compositions of Tables 3 and 4 were respectively mounted on a 4 吋 cathode team magnetron sputtering device. Under the substrate temperature of 2503⁄4, the oxygen partial pressure was set to 〇sccm (equivalent to 0x10 Pa). And forming a film to produce a transparent conductive mold. The transparent conductive film obtained in this manner is a zinc oxide-based transparent conductive film of the same composition of a sputtering target, which is a transparent conductive film 22 321341 201013709 which is sputtered. The composition analysis of such a zinc oxide-based transparent conductive film can also be carried out by ICP after the total amount of the single film is dissolved. In addition, when the film itself is formed in the element structure, if necessary, the cross section of the corresponding portion is cut by FIB or the like, and an elemental analysis device (EDS or WDS, Ogg analysis, etc.) attached to SEM or TEM is used. ) can also be specified. The conditions of the sputtering were prepared in the following manner to obtain a film of 5 Å A. Tibetan plated dry size: 0=l〇〇mm, t=6mm ❹ Splash clock mode: DC magnetron splash clock

Exhaust device: rotary pump + cryopump reach vacuum: 5xl (T5Pa below Ar pressure: 4. Oxli^Pa Oxygen partial pressure: 0xl (T3Pa substrate temperature: 250 °C sputtering power: 130W (electricity density Lew / cV) ❹ Use substrate: Corning #丨737 (glass for liquid crystal display) 50mmx50mmx0. 8mmt '[Test Example 4] (The relationship between the amount of money and the haze rate) About (Ti at%, Ga lat%) (Bl), ( Ti 3at%, Ga 3at%) (B10), and (Ti 5at%, Ga lat%) (B18) transparent conductive film, with wire and gap (L/S)=20/ on each surface A sample of a /m comb-shaped resist pattern (resistance: manufactured by Tokyo Chemical Industry Co., Ltd., TFR 970) was immersed in 1 vol% acetic acid at 3 〇χ: dissolved zinc oxide powder 100 mg/丨The etching solution (echant) of the liquid is up to 23 321341 201013709, and the contact height difference and low gauge (P-l5 manufactured by Tim Cole) is used to measure the etching amount, and the echi ng rate is measured. Then, The residual liquid is used to prepare a sample for changing the etching amount of each sample to measure the haze ratio. Further, for comparison, it is used for the above-mentioned ΑΖ0. The sputtering target produced in the plating target production example (AlAZn+Al)) is a sputtering target having a ratio of 2.4 at%, and the film-formed sample is obtained in the same manner between the etching amount and the haze ratio. The relationship between Fig. 6 shows the relationship between the etching amount and the haze ratio.

The haze rate was determined by measuring the center of the sample according to JIS K-7136 (2000) using a haze meter (NDH-200: manufactured by Sakamoto Denki Kogyo Co., Ltd.). From this result, it is understood that the higher the etching amount, the higher the haze ratio, and the zinc oxide-based transparent conductive crucible of the present invention increases the haze ratio as the etching amount increases. Further, in the zinc oxide transparent conductive film of the present invention, the same side amount ', if the composition is different, the rate of increase in the haze ratio is

Not in the same order (Tl lat%, Ga lat%) (Bl), (Ti 5at%, Galat« (B18), (Ti 3at%, Galat%) (B1〇), with the amount of money The increase rate of the haze rate will increase. It is also known that, in any case, the haze rate is almost linear (1) brewing mode, so it is known that if the haze rate is to be increased When the time is 2,000 to 3000 a, the * * * » Α is preferably 3000 Α to etch. The surface at the time of (Ti 3at%, Ga lat%) (B10) 15〇〇A, 3000 A is shown in Fig. 8 (a) to (c), and is shown in Fig. 7 (a) to (c). In the middle, the etching amount of the film was changed to 500 A and an SEM image. Further, for the sake of comparison, 321341 24 201013709 • 'The SEM image when the etching amount of the AZ0 (2.4 at%) film was changed in the same manner. As a result, it has been found that the surface morphology of the film changes when the (Ti 3at%, Ga lat%) (B10) film increases the amount of money, and the haze ratio is improved to about 60%. On the other hand, it can be seen that in the AZ0 (2.4 at%) film, even if the name is engraved, the surface morphology hardly changes, so that the haze rate is only about 2%. [Test Example 5] (Measurement of haze ratio) For the transparent conductive film of B1 to B23, a resist pattern of a comb-shaped shape with a wire and a gap (L/S) = 20 #m was provided on the surface (resistance· - A sample of TFR 970) manufactured by Tokyo Chemical Co., Ltd. was used for 3 days (TC immersion in an etching solution prepared by dissolving a zinc oxide powder of 1 〇〇mg/1 in 1% by volume of acetic acid for a predetermined period of time. A high and low difference meter (p_15 manufactured by Tim Cole) was used to measure the etching amount, and the rate of the etching was measured. The etching rate determined in this manner was used as a reference, and the transparent conductive films of B1 to B36 were respectively etched by about 300 Å. For the measurement of the haze ratio, each sample was obtained by measuring the center of the sample according to JIS K-7136 (2000) using a haze meter (NDH-2000; manufactured by Nippon Denshoku Industries Co., Ltd.). The results of the haze and the rate are shown in Tables 3 and 9. Here, in the ninth figure, a sample indicating a haze ratio of 1% or more is represented by ♦ of 1% by mass. From this result, it is understood that the content y (at%) of gallium is particularly high in the range of the content x (at%) of titanium (-0.66X+5.5) or less, and it is possible to achieve 1〇/ ° Furthermore, from the range of 10% or more of the haze ratio of the glass as the transparent electrode 3131341 25 201013709, it indicates that it is possible to be practical: in fact, the haze rate is 10%. When the results of Test Example 1 are combined, it can be seen that the range of y1% or more of gallium or 4.5at% of gallium (except for 〇at% and gallium 〇^% of titanium) and the content of y (at%) of gallium are The range below the value of x (at%) of titanium (-0.66+5·5) is a suitable fact. [Table 3]

Ti addition amount (at%) Ga addition amount (at%) __Parametric rate Β1 1 1 __ 20 Β2 1 4 ___30 Β3 1 6 _ 8 Β4 2 1 ______ 61 Β5 2 2 __73 Β6 2 4 ._11 Β7 2 5 __ 2 Β8 2 6 _ 1 Β9 2. 5 4 _____ 8 Β10 3 1 __ 51 Β11 3 2 Β12 3 4 _ 4 Β13 3.5 3 ______ 12 Β14 4 0.5 __54 Β15 4 3 __ 5 Β16 4 5 1 Β17 4 6 2 Β18 5 1 ___31 Β19 5 2 __ 14 Β20 5 2.5 __5 Β21 5 4 __2 Β22 6 1 __ 12 Β23 6 3 ^ 4 321341 26 201013709 « [Simplified illustration] Figure 1 (a) and (b) are shown in the implementation The graphs of the specific resistance and oxygen partial pressure dependence of the film formed in the examples and the comparative examples. 'Fig. 2 is a graph showing the measurement results of the environmental resistance test. Fig. 3 is a graph showing the results of environmental resistance test and specific resistance measurement. Fig. 4 is a graph showing the results of environmental resistance test and specific resistance measurement. ❹ Fig. 5 is a graph showing the results of environmental resistance test and carrier density measurement. Fig. 6 is a graph showing the relationship between the etching amount and the haze ratio in Test Example 4. Fig. 7 (a) to (c) show the surface SEM image when the amount of money of the ΒΙ0 (shed indium oxide) film is changed. Fig. 8 (a) to (c) show the surface SEM image when the etching amount of the ΑΖ0 film is changed. ^ Fig. 9 is a graph showing the measurement result of the haze ratio of Test Example 5. Fig. 10 is a view showing an example of a structure of a thin film tan solar cell using the oxidized transparent conductive film of the present invention. [Major component symbol description] 10 Thin film solar cell 11 Transparent substrate 12 Transparent electrode 13 . Power generation layer 13a Amorphous germanium P layer 13b Amorphous germanium i layer 13c Amorphous germanium n layer 14 Back electrode 27 321341

Claims (1)

201013709 VII. Patent application scope: 1. A zinc oxide transparent conductive film characterized by: zinc oxide as a main component, containing two elements of titanium (Ti) and gallium (Ga), and the two elements are titanium 1 % lat% (atomic percent) or more than gallium 4. 5at% or more. 2. The zinc oxide-based transparent conductive film according to item 1 of the patent application, wherein the content y (at%) of gallium is below the value of x (at%) of titanium (-0.66x+5.5). range. 3. The zinc oxide-based transparent conductive film according to item 1 of the patent application, wherein the content y (at%) of gallium β is equal to or less than the value (-2x+10.4) of the content x (at%) of titanium. The range and the value indicated by the content x (at%) of titanium (-0·5χ+1·1) or more. 4. The oxidized-transparent transparent conductive film according to item 2 of the patent application, wherein the content y (ai:%) of gallium is below the value (-2X+10.4) of the content x (at%) of titanium. The range and the value indicated by the content of titanium (at%) (-0. 5x+l. 1) or more. 5. For the zinc oxide-based transparent conductive film of the first application of the patent scope, the content y (at%) of gallium is the value indicated by the content of titanium x (at%) (-x+3.4) Hereinafter, the range of (x-0. 9) or less, or (-2. 3χ+10·1) or more. 6. The zinc oxide-based transparent conductive film of claim 2, wherein the content of y (at%) of gallium is below the value of x (at%) of titanium (-Χ+3.4) , (x-0. 9) or less, or (-2. 3x + 10.1) or more. 7. A zinc oxide-based transparent conductive film according to item 5 of the patent application, which is a transparent conductive film for a solar cell. 28 321341 201013709 8. The oxidized transparent conductive film of claim 6 is a transparent conductive film for a solar cell. 9. A zinc oxide-based transparent conductive film according to item 7 of the patent application, which is formed as a surface electrode on a transparent substrate. 10. A zinc oxide-based transparent conductive film according to item 8 of the patent application, which is formed as a surface electrode on a transparent substrate. The zinc oxide-based transparent conductive film according to any one of claims 1 to 10, wherein the haze ratio is 10°/◦ or more. ❹ 12. The zinc oxide-based transparent conductive film of the eleventh aspect of the patent application is formed by forming a film and then performing surface etching using a weak acid. 13. A method for producing a zinc oxide-based transparent conductive film, characterized in that: zinc oxide is used as a main component, and two elements of titanium (Ti) and gallium (Ga) are contained, and the two elements are based on titanium 1. lat% The zinc oxide-based transparent conductive film contained in the above range or in a range of 4.5 to 5 at% or more of gallium is formed into a film. 14. The method for producing a zinc oxide-based transparent conductive film according to claim 13, wherein two elements of titanium (Ti) and gallium (Ga) are contained as a main component of oxidation, and the two elements are titanium. 1. A zinc oxide-based sputtering target contained in a range of 1 at% or more or gallium of 4.5 at least or more, and formed into a film by sputtering or ion plating. 15. The method for producing a zinc oxide-based transparent conductive film according to claim 13 or 14, wherein after the film formation, surface etching is performed using a weak acid to thereby increase the haze ratio. 29 321341