TW200926207A - Indium oxide tranparent conductive film and method for making same - Google Patents

Abstract

This invention provides a transparent conductive film, which is an amorphous film formed by using a sputtering target having a sintered oxide which contains indium oxide, and optional tin, and an additive element (excluding Ba, Mg, and Y) which has an oxygen bonding energy in the range of 100 to 350kJ/mol, the additive element being in the amount of from 0.0001 mole or more to less than 0.10 mole with respect to 1 mole of the indium. The transparent conductive film contains indium oxide, optional tin, and the above said additive element.

Description

200926207 VI. Description of the invention: [Technical field to which the invention pertains] and a method of manufacturing the same, which is transparent to form an amorphous film, which is easy to have electrical resistance and high transmittance. The present invention relates to a transparent conductive tantalum conductive film which is easily patterned by weak acid etching, and further, the crystallized film has a low [Prior Art] "Indium Oxide - Tin Oxide (In2〇3_Sn〇2 composite oxide, In the following, the "IT0" film is widely used for the liquid crystal display (5) or the anti-condensation heat-generating film or the infrared-reflective film 4, because it has high visible light transmittance and high conductivity. There is still a problem that it is difficult to form an amorphous film. On the other hand, an indium oxide-zinc oxide (ΪΖ0) transparent conductive film is known as an amorphous film, but the transparency of the film is still inferior to that of the enamel film and yellowing. Therefore, the present applicant has previously proposed a transparent conductive film in which an amorphous film is formed by forming a film under a specific condition by adding ο ο 膜 ( (refer to Patent Document 1), but there is a case where 矽 is added. The problem of the tendency to increase resistance. [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a transparent conductive material. a film and a method of manufacturing the same, wherein the transparent conductive film contains 3 320647 200926207, which is easily patterned by weak acid etching to form an amorphous germanium, and further, the crystallized film has low electrical resistance and 铋 = easy, '°曰曰(means to solve the problem). Rate of incidence. In order to solve the above-mentioned problems, the inventors of the present invention have found that an indium oxide-based transparent conductive film of yttrium is used, and an amorphous film having a good clarity and a good affinity is easily formed by weak acid etching. Therefore, the application has been filed previously and 095,783). Industry (Japan's special wish 2007- However, it has been found that as an additive element for film formation of an amorphous film, not only Ba' but also various age elements exist, if the energy of oxygen bonding is from 1 350 to 350 kJ/mol The element of the range is an additive element, and the amorphous film can be formed into a film. Thus, the first aspect of the present invention is a transparent conductive film which is formed by using a sputtering target having an oxide sintered body. The transparent conductive film of the film, the oxide sintering system contains indium oxide and the necessary tin, and contains at least 0.0001 mol and less than 0.10 m of oxygen binding energy to the indium bismuth. An additive element (except Ba (钡), Mg (magnesium), Y (钇)) in the range of 1 〇〇 to 350 kJ/m 〇 1 , which is characterized by containing indium oxide and tin as necessary, and containing the foregoing In the first type, the amorphous film is formed by the inclusion of a specific additive element. The second aspect of the present invention is a transparent conductive film according to the first aspect, wherein the additive element is From Sr (锶), Li (lithium), La (镧), At least one selected from the group consisting of Ca (calcium) 4 320647 200926207 In the second type, the transparent conductive material described in the type 2 is used by the electric film. The G-to-G.3-mole tin is used in the third type of towel, and is a transparent conductive film containing tin, and is required to be in the form of a film. The type 4 is the second type. Or the transparent production force described in the third type, the tone, and the material tb y of 1 mole are represented by the molar ratio x of indium added by the above-mentioned added halogen pair! The value of = is equal to or greater than the value of (a)·~1): In the film, in the rm state, when the shoe is not full, it is crystallized when it is an amorphous film t 〇〇 to the shoe for annealing.第 The fifth aspect of the present invention is the transparent conductive film described in the second or third aspect, wherein the additive element is Sr, and the tin to the molar ratio of 1 mole is less than that of Sr#1. The range of indium moir (_=Ln(1)-9.aki-6. 7x10) below the value. In the fifth type, when the film is not full, it is amorphous, and when it is annealed in S 300t:, it can be crystallized. The sixth aspect of the present invention is the transmissive (four) electric film according to the second or third aspect, wherein the additive element is Li, the molar ratio of tin to indium of ymole is y, and the pair is located in Li 1 Mohr indium molar ratio, expressed above 320647 200926207 (_1. 6x10 1η(χ)-5. 9x1ο-1) and above (_2. 5χ1〇^η(χ) -5. 7χ10_1) The range below the value. In the sixth type, it is less than one. When the ruthenium is formed into a film, it is an amorphous film, and when it is annealed at 100 to 300 t:, it can be crystallized. The seventh aspect of the present invention is the transparent conductive film of the second or third aspect, wherein the additive element is La, and the indium molar ratio y' of indium to j-m is located in La pair 1 Mohr's indium molar ratio is expressed by ο (-6. 7xlG-2Ln(x)-2. 2X1G-1) and is (a).3xl(r)Ln(x) -7· 7x1ο— 1) The range below the value. In the seventh type, when it is less than 1 〇{rc, it is an amorphous film, and when it is annealed at 100 to C, it can be crystallized. The eighth aspect of the present invention is the transparent conductive film according to the second or third aspect, wherein the additive element is Ca, and the tin is in contrast to y, and is located at a ratio of Ca to 1 Å and is added to the sulphide (- 4.1χ1〇Λπ(χ)-9 3χ1〇-2)ίΓ ' ' ❹

The value of ... ... is above the value of (-UxlO-iLnOO -5· 7x10 ). In the film 8 type, 'below less than 100. . When the film is formed, it is an amorphous film, and when it is annealed at 100 to medium, it can be crystallized. The ninth aspect of the present invention is a transparent conductive film in the first to eighth modes, wherein the water pressure is (5) and the film is formed under the condition of "two 10 Pa or less." The transparent conductive film described in the ninth mode of the tenth aspect of the present invention is formed by a film formed at a specific state, and 320647 6 200926207 contains hydrogen. In the form of the ίο, by the specific moisture The transparent conductive film containing hydrogen in a bonded state can be formed by pressing the film formation. The eleventh aspect of the present invention is a transparent conductive film according to any one of the first to tenth aspects, wherein After the film of the crystal film is crystallized by annealing, in the eleventh mode, after the film of the amorphous film is formed, it can be easily crystallized by annealing, and the weak acidity is imparted. The twelfth aspect of the present invention is the transparent conductive film according to the eleventh aspect, wherein the crystallization by the annealing is performed at 100 to 300 ° C. In the twelfth mode, it is easy to be 100 to 300. The amorphous film is crystallized in ° C. The thirteenth aspect of the invention is a method for producing a transparent conductive film, which is characterized in that The film is formed by using a sputtering target having an oxide sintered body, and the oxide sintering system contains indium oxide and tin as necessary, and the indium of 1 ^ mol contains 0.0001 mol or more and less than 0. 10 molar oxygen bonding energy in the range of 100 to 35OkJ / mo 1 of the addition of elements (except Ba, Mg, Y), thereby obtaining indium oxide and the necessary tin, while containing the aforementioned additional elements It is an amorphous transparent conductive film. In the thirteenth aspect, the amorphous film can be formed by containing a specific additive element. The fourteenth aspect of the present invention is transparent as described in the thirteenth aspect. The method for producing a conductive film, wherein the film is formed under the conditions that the water pressure is 1.0xl0_4Pa or more and 1.0 χ10_1 Pa or less. 7 320647 200926207 In the 14th mode, by forming a film under a specific water pressure, The fifteenth plastic state of the present invention is a method for producing a transparent conductive film according to the thirteenth or fourteenth aspect, which is formed by annealing to form a transparent crystallized film. Conductive film. In the 15th type, 'is forming amorphous After that, it can be more easily crystallized by annealing. The method of producing a transparent conductive film according to the fifteenth aspect of the present invention is a method of producing a transparent conductive film of a weakly acidic type, which is amorphous. After the film is etched, it is annealed and crystallized. In the 16th type, after the "formation of the amorphous film," it is etched with a weakly acidic shoe polish, and then annealed to crystallize it. The method of producing a transparent conductive film according to the fifteenth or sixteenth aspect of the present invention is a method of performing crystallization by the annealing in 100 to 30 {rc. In the 17th mode, it is easy to crystallize the amorphous film in 100 to 3 Å. (Effects of the Invention) - According to the present invention, the oxygen-bonding energy is added to the film of the indium oxide added to the (10) i qing kj/m 〇 1 2, thereby achieving the following, that is, easy to weaken Patterning to form an amorphous film 'Crystalized film is low-resistance and high-permeability [Embodiment] 320647 8 200926207 Used to form the indium oxide-based transparent conductive film of the present invention, the permeable ore-dried material is an oxidation surface An oxide sintered body which is a main body and which, if necessary, and contains an oxygen-bonding energy at a side of 35 〇 kJ/nK)i, may be a complex of the oxide itself or a solid solution. There is no particular limitation on the existence. Oxygen Here, the oxygen bonding energy has been recorded as an additive element in the range of /_, which is the same as that of the previously proposed application, and is: ❹ The transparent conductive film functions as an amorphous film, for example, (oxygen bonding energy' :, junction energy: 134kJ/mol), u (oxygen bonding energy, islkj/ 'i: 242kJ/m〇1) ', ,. 〇月匕里.134kJ/mc) 1), Mg (oxygen bonding energy) :i55k仏(4), bonding energy··209kJ/mol), etc. ❹ In this case, the element having a large oxygen-bonding energy is easily formed by a single oxide. The glass-forming element (glass-forming element) 1 is added to the indium oxide-based transparent conductive film 'because the bonding strength with the milk is strong', so even Annealing is optimal, does not change, and has properties that can hardly be modified by annealing to determine the electrical properties. However, the oxygen bonding energy is relatively low at (10) to swollen J/m〇1. Since the element of the range has a small bonding force with oxygen, it can be presumed to have an effect of becoming an amorphous film. Further, although Na (oxygen bonding energy: 84_〇1) or κ (oxygen bonding energy: along仏(4) Yes!Γ, but if you add force, indium oxide is a transparent conductive film, then ΓΓ=characteristics have an adverse effect, or damage to environmental resistance, the picture is not good (two reference Nanfu edited the glass of the invitation '' non Introduction to Crystal Science-Industrial Books (^) ρ. 34 to 36). 320647 9 200926207 Adding 70 gram content, it is ideal to use indium for i-mole with right 0 Γ 1 - Moule and less than G. ί 的 f formed by 1G Moh material. If the right is less than this amount, the addition effect is less significant. Further, when the amount is more than this, the electric resistance of the formed transparent conductive film tends to increase, and the yellowing tends to be deteriorated. By the above-mentioned sputtering, the transparent:::: force: the content of the element 'The content is the same as the content of the used one. The content of tin is set to the range of the film formed by the use of a copper containing moir to 0.3 mol. In the case of tin, it is preferable to form a film by using a bismuth plating material having a range of 〇〇〇1 to 〇·3 摩尔 in the indium of i. In this range, the control of the money forging is appropriately controlled. The electron carrier density and the mobility are such that the conductivity is maintained in a good range. Further, when the amount is more than this range, the mobility of the electron carrier of the sputtering target is lowered to deteriorate the conductivity, which is not preferable. The content of tin in the transparent conductive film formed by the sputtering target is the same as the content of the splashing dry material used. The sputtering target has a The resistance value of the sputtering is performed by DC magnetron sputtering, so the phase can be used. Cheap DC magnetron sputtering for sputtering 'Of course can also be carried out using a high frequency magnetron sputtering device. By using this transparent conductive film with a sputtering target', an oxidized marriage transparent conductive film of the same composition can be formed. The composition analysis of the indium oxide-based transparent conductive film can completely dissolve the single-layer film and analyze it by lCP (lnductively Copied has1118: inductively coupled plasma). In addition, when the film itself is formed into a component, it can be necessary to Fib (Focus Ion Beam: focus from 10 320647 200926207 beam), etc. Cut the section of the section and use it attached to SEM (Scanning

Elemental analysis device (EDS (Energy Dispersive X-ray) such as Electron Microscopy: Scanning Electron Microscope) or TEM (Transmission Electron Microscopy)

Spectrometer: Energy Dispersive Xenon Beam Spectrometer) or WDS (Wavelength Dispersive X-ray Spectrometer), Oujie Electron Spectrometer, etc.). ❹

The indium oxide-based transparent conductive film of the present invention contains a specific amount of a specific additive element, and although it differs depending on the content, it can be formed at a temperature of room temperature or higher and lower than the crystallization temperature, for example, The temperature condition lower than ·t is preferably less than 15 (the temperature of rc: film formation under the temperature of the shoe, whereby the amorphous enamel can be used in amorphous = SSL). The advantage of _ is weak acid = ^. Here, in the nucleot, the button "匕3 in the pattern forming step" is used to obtain a specific pattern. Class, line resistance, transfer element Species: There are 1 different, but the crystallization temperature of the film with a resistivity of 1.0# to L〇xlr U · cm 〇 is different because it contains the amount of (5) produced by the first (four) ❹, crystallization G 2: If the annealing process is carried out at a temperature of 100 i3a0t, the temperature field is used in the general semiconductor range, and the process towel crystallizes it. At the same time, it is ideal. For crystallization from 100 to 30 (TC, more reasonable 320647 11 200926207 is 150 to 250 ° C is crystallized and crystallized. Especially ideal is 2〇〇

Up to 250 ° C Here, the known annealing, refers to the female ★ in the air, etc., heating at the desired temperature - in the gas: true gas - usually for a few minutes to a few hours, such as = so-called Time, ideal for the short-term silk (4), the transparent conductive film which is crystallized by annealing can improve the transmittance on the short-wavelength side, for example, the wavelength of 400 to 5 〇〇 is short-wavelength side 〇.. , , , .L Μ , , , ν ^ ^ nm The average transmittance is 85% or more. Further, by this, the film such as IZ is not yellowed. Generally, the higher the transmittance on the short-wavelength side, the better. On the other hand, the crystallized transparent conductive crucible can improve the resistance to the engraving, and it can be made into a weakly acidic (tetra) agent, which makes it impossible to reproduce the amorphous film. Thereby, the corrosion resistance of the subsequent steps or the financial environment of the device itself can be improved. As described above, in the present invention, the content of the ruthenium can be changed by a change, and the crystallization temperature after the film formation is set to a desired temperature. Therefore, the crystallization temperature can be prevented from being formed after the film formation. The heat treatment at a temperature is maintained in an amorphous state. Alternatively, after pattern formation after film formation, heat treatment is performed at a temperature equal to or higher than the crystallization temperature and crystallization is performed to change the etching resistance. Here, when the additive element is Sr, when the film is formed below the film, it is formed into an amorphous film 'after 100 to 30 (the annealing composition in TC, the composition range of crystallization is tin-pair) 1 molar indium molar ratio y (mole), located in Sr to 1 mol of indium molar ratio X (-4. Ιχΐ 〇 'η (χ) -9. 2x10-2) Above the value and the value of (-2. 9χ10'η(χ)-6·7ΧΗΓ1) is in the range of 320647 12 200926207. In addition, in this range, especially in the tin to 1 molar indium molar ratio y (mole) is in the range of (r. 2 x lO_2Ln(x) - 1.9xlO_1) expressed by Sr to 1 mol of indium molar ratio X, when the annealing temperature is less than 200 ° C, Since it is impossible to crystallize, it is preferable to crystallization in the annealing process of 200 ° C or more in consideration of the film forming process. Further, in the above range, it is more preferable to use tin to 1 m. The molar ratio of indium to y is 0.15 m or more and 0. 28 m or less, the specific resistance after annealing at 250 ° C ❹ is 3.0 χ 10 -4 Ω · cm or less. When Li is formed, when filming is less than 100 ° C, When formed into an amorphous film and then annealed at 100 to 300 ° C, the composition range of crystallization is a molar ratio of tin to 1 mol of indium to y (mole), located at 1 to 1 mol of Li The indium molar ratio of indium is greater than or equal to the value of (-1. 6xlO_1Ln(x) - 5. 9xl0-1) and is in the range of (-2. 5xlO_1Ln(x)-5. ϊχΙίΓ1). In addition, in this aspect, especially in the tin to 1 molar indium molar ratio y (mole) is expressed in Li to 1 mole of indium molar ratio X (-7. OxlO_2Ln (x )-l. δχΙίΓ1) In the above range, when the annealing temperature is less than 200 ° C, it is impossible to crystallize. Therefore, when considering the film formation process, it is preferable to crystallize in an annealing of 200 ° C or more. Further, in the above range, it is more preferable that the molar ratio y of tin to 1 mol of indium is 0.28 m or less, and the molar ratio of Li to 1 mol of indium is X. When it is below 0. 015 mol, the specific resistance after annealing at 250 ° C is 3. Ox 10_4 Ω · cm or less. 13 320647 200926207 ' When the additive element is La, when film formation is less than 100 ° C, Formed as an amorphous film, After annealing at 100 to 300 ° C, the composition range of crystallization is the molar ratio y of tin to 1 mol of indium, which is expressed by the molar ratio X of indium of La to 1 mol ( -6. The value of 7x10-2Ln(x)-2. 2xl0_1) is equal to or greater than the range of (-3. 3xlO_1Ln(x)-7. 7x10-〇). Further, in this range, especially in the case where tin to 1 molar indium molar ratio y (mole) is represented by La to 1 molar indium molar ratio X (-8. 7 xl (T2Ln (x)-2. 0χ10_1) In the above range, when the annealing temperature is less than 200 °C, crystallization cannot be performed. Therefore, it is preferable to anneal to 200 ° C or more when considering the film formation process. Further, in the above range, it is more preferable that when the molar ratio of tin to 1 mol of indium molar ratio y (mole) is 0.23 mol or less, after annealing at 250 ° C The specific resistance is 3.0 χ1 (Γ4 Ω · cm or less. When the additive element is Ca), when the film is formed at less than 10 ° C, it is formed into an amorphous film, and then after annealing at 100 to 30 (TC) The crystallized group U is in the range of tin to y in molar ratio of tin to 1 mol, which is represented by the molar ratio X of indium in Ca to 1 mol (-4. 1χ1〇Λη(χ) -9. The value of 3χ1(Γ2) is above the range of (-2. 5xlO_1Ln(x)-5. 7x10—〇. In addition, in this range, especially in the case of tin to 1 mole of indium Ear ratio y (mole) is located at Ca to 1 m The molar ratio is represented by X (-8. 7 xl (T2Ln(x) - 2.0 × 10, in the above range, when the annealing temperature is less than 200 ° (:, it cannot be crystallized, so consider In the film formation process, it is preferably a range of crystallization in annealing at 200 ° C or higher. Further, in the above range, it is more desirable to be a tin to 1 m of indium 14 320647 200926207 'Moerby y (mole) is 〇. When the temperature is below 28 m, the specific resistance after annealing at 250 ° C is 3. 0 χ 1 (Γ 4 Ω · cm or less. Thus, by adding an additive element, a specific effect can be obtained, but an additive element is added. The range of the specific effects that can be obtained is also slightly different. The common range of the above-mentioned elements of Sr, Li, La, and Ca is formed into an amorphous film at a film thickness of less than 100 ° C, and is 100 to 300 °. When annealing in C, the composition range of crystallization is the molar ratio y (mole) of tin to 1 mol of indium, which is expressed by the molar ratio X of the indium added by the additive element to 1 mol ( -9. 3x ❹ l (T2Ln(x)-2. 1x10—The value above 且 and below the value of (-2. 5χ1〇Λη(χ)-5. 7x 10_1). 0x10—4Pa, preferably 1. In order to increase the crystallization temperature after film formation as an amorphous film, the water pressure at the time of film formation can be controlled. Film formation is carried out under a water pressure of OxlO_5Pa or less, but film formation may be carried out under the conditions of a water pressure of 1.0xx0_4Pa or more and 1.0xx0_1Pa or less. Oxl0_4Pa or less, preferably less than 1. 0xl0_4Pa, more preferably 1. 0xl0 - 5Pa or less, if the water pressure is 1. Oxl (T4Pa or more). When the film formation is carried out by pressing, the crystallization temperature of the amorphous film can be increased, and in particular, in the low region where the content of the additive element is small and the crystallization temperature is 100 ° C or lower, the crystallization temperature is increased by increasing the water pressure. When it is raised, it is easy to form an amorphous film. In order to control the water pressure in the above range, it is possible to introduce an ambient gas (generally Ar) into the film formation reaction chamber at the time of film formation by a mass flow controller or the like. If necessary, use an oxygen-containing gas, for example, about 10_4Pa, 15 320647 200926207 ^ pressure), and introduce water vapor. When the vacuum is reached, the internal gas system is set to = force. The vacuum is 10 - 4 to 1〇-3% of 丨 / The main component of the pressure is water. That is, 'Because of the true:: It is almost the same as the water pressure, so it is not necessary to introduce the state of water pressure. 35虱, It is also possible to achieve the desired description of the present invention. Use splashes Ο ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ® ^ m "Use a single element, a compound, or a composite oxide as a raw material. When a monomer or a compound is used, a process capable of forming an oxide can be carried out in advance. The fabric powder is given a specific (four) ratio. (4) The combination is not particularly limited. It can be used in various wet or dry methods known in the past. Dry methods such as Cold Press and hot pressing (H〇t)

Press), ,, /. In the cold press method, a mixed powder is filled in a forming mold to prepare a molded body and read it. In the hot press method, the mixed powder is fired and sintered in a forming mold. For example, the wet method is preferably a filter forming method (refer to Japanese Patent Publication No. Hei 28-28). The squeezing mold used in the subtractive molding method is a filtration molding die formed by water-insoluble material from the ceramic raw material slurry to obtain a molded body, which is formed of a water-insoluble material. The molding system consists of: a forming bottom having more than one drainage hole, a water-passing filter placed above the forming bottom mold; and 320647 16 200926207 « sealed by a seal for sealing the filter The material is formed from the upper side of the r-forming mold frame, and the molding base mold and the molding die, the sealing material, and the filter, which are lost in holding, are separately foldable. From the side of the filter, the water in the slurry is reduced and drained, and the mold is only used; then a slurry composed of mixed powder, ion-exchanged water and organic hexagram is prepared, and the mixture is gathered. The liquid injection is applied to the filter and the overmolding mold, and the water in the slurry is drained under reduced pressure to form a molded body, and the obtained ceramic formed body is dried and degreased and then fired. ° The firing temperature of the person formed by the cold pressing method and the wet method is preferably 1300 to 1650 ° C, more preferably 1500 to 165 (TC. The environment is, for example, an atmospheric environment, an oxygen atmosphere, a non-oxidizing environment, On the other hand, in the hot press method, it is preferable to perform sintering in the vicinity of 12001: the environment is, for example, a non-oxidizing environment or a vacuum environment, etc. After the firing in each method, ' The present invention will be described with reference to the following examples, but is not limited thereto. (Spray target manufacturing example 1) (Sr - ITO) (Adding Sr ΙΤ0, Sr=0. 02-Sn=0. 1) Preparing purity > 99.99% I112O3 powder, Sn〇2 powder, and purity > 99.9% SrC〇3 powder. , with 1112〇3 powder as 65. 3wt% and SrC〇3 powder in the ratio of 34.7 wt%, the whole amount is prepared to be 200g, and the ball mill is mixed in a dry state, and is carried out in the atmosphere at 1200 ° C. After 2 hours of calcination, the SrIm〇4 powder was obtained. 17 320647 200926207 Next, the SrIn2〇4 powder was 2. 2wt%, and the In2〇3 powder was 86. 6wt%, Sn〇2 powder is 11. 2wt% ratio 'preparation of the total amount is about 1.0kg (the composition of each metal atom is In = 88. Oat%, Sn = 10 · Oat%, Sr = 2 · Oat%), this is ball milled and mixed. Then add pvA (p〇lyvinyl

Alcohol: Polyvinyl alcohol) water money reducer is good to mix, money, and cold pressed to obtain the molded body. In the atmosphere, at 6 〇〇. The kneaded body was subjected to a deceleration of 10 hours at a heating rate of rc/h for 10 hours, and then baked in an oxygen atmosphere at 1550 C for 8 hours to obtain a sintered body. On the other hand, the 5 series was heated from room temperature to 8 〇 c at a temperature increase rate of 20 〇C/h, and the temperature was raised from _° C. to 155 (TC at a temperature increase rate of 4 〇〇 ° C/h, and after holding for 8 hours, 100 The temperature lowering condition of °C/h was cooled from the degeneration to room temperature. The sintered body was processed to obtain a hiding material. The density at this time was 7.G5g/cm3. Similarly, SpO.OOOOI, Sr=〇 were separately produced. .〇i, Sr=0.05 minus i ore dry material. In addition, the dry ore material having the composition shown in Table j was produced in the same manner. 〇320647 200926207 [Table 1]

Sample No. Composition (at%) vs. I n : 1 mo 1 ratio [mol ] In Sn Sr Sr Sn al 94. 5 5. 0 0· 5 0. 005 0. 053 a2 89. 5 10. 0 0. 5 0. 006 0. 112 a3 84. 5 15. 0 0· 5 0. 006 0. 178 a4 79. 5 20. 0 0. 5 0. 006 0. 252 a5 94. 0 5· 0 L 0 0. Oil 0. 053 a6 89. 0 10. 0 1. 0 0. Oil 0. 112 a7 84. 0 15. 0 1.0 0. 012 0. 179 a8 79. 0 20. 0 1. 0 0. 013 0. 253 A9 93. 0 5. 0 2. 0 0. 022 0. 054 alO 88. 0 10. 0 2.0 . 0. 023 0. 114 all 83. 0 15. 0 2. 0 0. 024 0. 181 al2 78. 0 20.0 2. 0 0. 026 0. 256 al3 92. 0 5. 0 3. 0 0. 033 0. 054 al4 87. 0 10. 0 3_ 0 0. 034 0. 115 al5 82. 0 15. 0 3 0 0. 037 0. 183 al6 77. 0 20. 0 3. 0 - 0. 039 0. 260 al7 90. 0 5. 0 5. 0 0. 056 0. 056 al8 85. 0 10. 0 5. 0 0. 059 0. 118 al9 80. 0 15. 0 5. 0 0. 063 0. 188 a20 75. 0 20. 0 5. 0 0. 067 0. 267 a21 85. 0 5. 0 10. 0 0.118 0. 059 a22 80. 0 10. 0 10. 0 0.125 0. 125 a23 75. 0 15. 0 10. 0 0. 133 0. 200 a24 70. 0 20. 0 10. 0 0. 143 0. 286 a25 89.999 10. 000 0. 001 0·000011 0· 111112 a26 84.950 15.000 0. 050 0.000589 0.176574 a27 81.900 18. 000 0. 100 0.001221 0.219780 a28 82. 000 17. 000 1. 000 0.012195 0.207317 a29 89. 900 10. 000 0. 100 0.001112 0·111235 a30 76. 000 22. 000 2. 000 0.026316 0.289474 19 320647 200926207 (spray target manufacturing example 2) (Li-IT0) (addition of Li ΙΤ0, Li=0. 02-Sn=0. 1) Preparation purity> 99. 99% of In2〇3 powder, Sn 〇2 powder, and purity of 99.9% of Li2C〇3 powder. First, the Im〇3 powder is 79. Owt% and the Li2C〇3 powder is 21. Owt%, and the whole amount is prepared to be 200 g, and the mixture is ball milled in a dry state, and is carried out in the atmosphere at 1000 ° C. The Li In〇2 powder was obtained by calcination for 3 hours. Okg( Each metal atom is prepared by the above-mentioned Li In〇2 powder is 2. 2wt%, In2〇3 powder is 86. 8wt%, Snn2 powder is 11. Owt% ratio, the total amount is about 1. Okg (each metal atom) The dry matter was produced in the same manner as in the case of Sr-ITO (Sr=0. 02) except that the composition was In=88. Oat%, Sn=10. Oat%, Li=2. Oat%). However, the firing temperature was 1450 °C. Further, the density at this time was 6.85 g/cm3. A sputtering target having the composition shown in Table 2 below was also produced. ❹ 20 320647 200926207 [Table 2]

Sample No. Composition (at%) vs. In : Imol ratio [mol ] In Sn Li Li Sn bl 94.5 5. 0 0· 5 0. 005 0. 053 b2 89· 5 10. 0 0. 5 0. 006 0 112 b3 84. 5 15. 0 0. 5 0. 006 0. 178 b4 79. 5 20. 0 0 5 0. 006 0.252 b5 94. 0 5. 0 1.0 0. Oil 0. 053 b6 89. 0 10 0 1.0 0. Oil 0. 112 b7 84. 0 15. 0 1.0 0. 012 0. 179 b8 79. 0 20. 0 1.0 0. 013 0. 253 b9 93. 0 5. 0 2. 0 0. 022 0. 054 blO 88· 0 10. 0 2. 0 0. 023 0. 114 bll 83. 0 15. 0 2. 0 0. 024 0.181 bl2 78. 0 20. 0 2. 0 0. 026 0. 256 bl3 92. 0 5. 0 3. 0 0. 033 0. 054 bl4 87. 0 10. 0 3. 0 0. 034 0. 115 bl5 82. 0 15. 0 3. 0 0. 037 0. 183 bl6 77. 0 20. 0 · 3. 0 0. 039 0. 260 bl7 90. 0 5. 0 5· 0 0. 056 0.056 bl8 85. 0 10. 0 5. 0 0. 059 0. 118 bl9 80. 0 15. 0 5_ 0 0. 063 0. 188 b20 75. 0 20. 0 5. 0 0. 067 0. 267 b21 85. 0 5. 0 10. 0 0. 118 0. 059 b22 80. 0 10. 0 10. 0 0. 125 0. 125 b23 75. 0 15. 0 10. 0 0. 133 0. 200 b24 70. 0 20. 0 10. 0 0.143 0.286 b25 89. 995 10.000 0. 005 0·000056 0. 111117 b26 82.800 < 17. 000 0. 200 0.0 02415 0·205314 b27 89.900 10. 000 0. 100 0·001112 0· 111235 b28 84.900 15. 000 0. 100 0. 001178 0.176678 b29 82. 000 17. 000 1. 000 0.012195 0·207317 b30 80.000 18. 000 2 . 000 0.025000 0_ 225000 21 320647 200926207 (spray target manufacturing example 3) (La-IT0) (addition of La ΙΤ0, La=0. 02-Sn=0. 1) Preparation purity > 99. 99% of In2 〇3 powder, Sn 〇 2 powder, and a purity of 99. 99% of La2(C〇3)3 · 8M) powder. First, 'Iri2〇3 powder is 31.6 wt% and La_2(C〇3)3 · 8H2O powder is 68.4 wt%, and the whole amount is prepared to be 200 g, and the mixture is ball milled in a dry state, and in the atmosphere, The calcination was carried out at 1200 ° C for 3 hours to obtain LaIn 〇 3 powder. Okg (The composition of each metal atom is In, the ratio of each metal atom is 1. In the case of the above-mentioned LalnOs powder, the composition of each metal atom is In. Owt%, the composition of each metal atom is In. In the same manner as Sr-ITO (Sr=0.02), a dry material was produced, except that Oat%, Sn=10. Oat%, and La=2. Oat%). The density at this time is 7. 04g/cm3. A sputtering target having the composition shown in Table 3 below was also produced. 22 320647 200926207 [Table 3]

Sample No. Composition (at%) vs. I n : 1 mo 1 ratio [mo 1 ] In Sn La La Sn cl 94. 5 5. 0 0. 5 0. 005 0. 053 c2 89. 5 10. 0 0 · 5 0. 006 0. 112 c3 84. 5 15. 0 0. 5 0. 006 0. 178 c4 79. 5 20. 0 . 0.5 0. 006 0. 252 c5 94. 0 5. 0 1.0 0. Oil 0. 053 c6 89. 0 10. 0 1. 0 0. Oil 0. 112 c7 84. 0 15. 0 1.0 0. 012 0.179 c8 79. 0 20. 0 1. 0 0. 013 0. 253 c9 93. 0 5. 0 2. 0 0. 022 0. 054 clO 88. 0 10. 0 2. 0 0. 023 0. 114 ell 83. 0 15. 0 2. 0 0. 024 0. 181 cl2 78. 0 20.0 2. 0 0. 026 0. 256 cl3 92. 0 5. 0 3. 0 0. 033 0. 054 cl4 87. 0 10. 0 3. 0 0. 034 0.115 cl5 82. 0 15. 0 3. 0 0. 037 0.183 cl6 77. 0 · 20. 0 3. 0 0. 039 -0.260 cl7 90. 0 5. 0 5. 0 0. 056 0. 056 cl8 85. 0 10. 0 5. 0 0. 059 0. 118 cl9 .80· 0 15. 0 5. 0 0. 063 0. 188 c20 75. 0 20. 0 5. 0 0. 067 0 267 c21 85. 0 5. 0 10. 0 0. 118 0. 059 c22 80, 0 10. 0 10. 0 0. 125 0. 125 c23 75. 0 15. 0 10. 0 0. 133 0. 200 C24 70. 0 20. 0 10· 0 0. 143 0. 286 c25 89.992 10. 000 0. 008 0. 00009 0. Ill c26 86.900 13. 000 0.100 0.00115 0. 150 c27 79.900 20. 000 0. 100 0. 00125 0. 250 c28 81,000 18.000 1. 000 0. 01235 0. 222 c29 81.800 18. 000 0. 200 0. 00244 0. 220 c30 84.960 15. 000 0. 040 0. 00047 0. 177 23 320647 20 0926207 (Cooking Case 4 of Qianjin Leather) (Ca-IT0) (addition of lT〇, Ca=0. 02-Sn=0. 1) Preparation purity> 99. 99% of I112O3 powder, Sn〇2 powder And a purity of 99.5% CaC〇3 powder. First, the In2〇3 powder is 73.5% by weight and the CaC〇3 powder is 26.5% by weight. The total amount is prepared to be 200 g, and the mixture is ball milled in a dry state, and is carried out in the atmosphere at 120 (TC). The calcination was carried out for 3 hours to obtain CaIm〇4 powder.

H, then the above-mentioned CaIn2〇4 powder is 4. 8wt%, Iri2〇3 powder is 84. 3wt%, Sn〇2 powder is i〇. 9wt% ratio, the total amount is about 丨.〇kg (each metal The composition of the atom is In=88. Oat%, Sn=10. Oat%, Ca=2. 〇at %) 'In addition to this, the dry material is produced in the same manner as Sr-ITO (Sr=0. 02). . The density at this time was 6.73 g/cm3. A sputtering target having the composition shown in Table 4 below was also produced. 〇 320647 200926207 [Table 4]

Sample No. Composition (at%) vs. I n : 1 mo 1 ratio [mo 1 ] In Sn Ca Ca Sn dl 94. 5 5. 0 0· 5 0. 005 0. 053 d2 89. 5 10. 0 0 5 0. 006 0. 112 d3 84. 5 15. 0 0· 5 0. 006 0. 178 d4 79, 5 20. 0 0· 5 0. 006 0. 252 d5 94. 0 5. 0 1. 0 0. Oil 0. 053 d6 89. 0 10. 0 1_ 0 0. 011 0. 112 d7 84. 0 15. 0 1. 0 0. 012 0. 179 d8 79. 0 20. 0 1.0 0. 013 0. 253 d9 93. 0 5. 0 2. 0 0. 022 0. 054 dlO 88. 0 10. 0 2. 0 0. 023 0. 114 dll 83. 0 15. 0 2. 0 0. 024 0. 181 dl2 78. 0 20. 0 2. 0 0. 026 .0.256 dl3 92. 0 5. 0 3. 0 0. 033 0. 054 dl4 87. 0 10. 0 3. 0 0. 034 0. 115 dl5 82. 0 15. 0 3· 0 0. 037 0. 183 dl6 · 77. 0 20. 0 3. 0 -_ 0 039 0. 260 dl7 90. 0 5. 0 5. 0 0. 056 0. 056 dl8 85. 0 10. 0 5. 0 0. 059 0. 118 dl9 80. 0 15. 0 5. 0 0. 063 0. 188 d20 75. 0 20. 0 5. 0 0. 067 0. 267 d21 85. 0 5. 0 10. 0 0. 118 0. 059 d22 80. 0 10. 0 10. 0 0. 125 0. 125 d23 75. 0 15. 0 10. 0 0.133 0. 200 d24 70. 0 20. 0 10. 0 0. 143 0. 286 d25 94.800 5. 000 0. 200 0.002110 0.052743 d26 86.950 13. 000 0. 050 0.000575 0. 149511 d27 82.900 17. 000 0. 100 0.001206 0.205066 d28 79.900 20. 000 0. 100 0.001252 0.250313 d29 90.900 9. 000 0. 100 0.001100 0·099010 d30 76.000 22.000 2. 000 0.026316 0. 289474 25 320647 200926207 (Sputter target reference production example 1) (Mg-iT〇) (addition of Mg ΙΤ0, Mg=0. 02, Sn=0. 1) & Preparation purity > 99.9W of In2〇3 powder, powder 5重量%。 The magnesium carbonate powder (MgO content of 41. 5wt%). First, the In2〇3 powder is 87.3wt% and the magnesium carbonate powder is 12.7% by weight, the total amount is 2〇〇g, and the ball mill is mixed in a dry state, and is in the atmosphere, at 14 Hey. (: The calcination was carried out for 3 hours, and the MgIm〇4 powder was obtained. Then, the above MgIn2〇4 powder was 4. 6 wt%, the In2〇3 powder was 84 5 wt%, and the Sn〇2 powder was 10.9 wt%, and all were prepared. The amount is approximately 〇kg (the composition of each metal atom is In=88. Oat%, Sn=10. Oat%, Mg=2%) 'In addition to this, with Sr-ITO (Sr=0. 02) The density of the material was 7. 02g/cm3. The same was produced for the sputtered dry material of Mg=0.0.5, Mg=0·12. (Spray target reference manufacturing example 2KY- IT0) 》 (Add Y ΙΤ0, Y=〇· 〇2-Sn=〇. 1) Prepare purity> 99·99% of Iri2〇3 powder, Sn〇2 powder, and purity> 99. 99% of Y2 (C〇3) 3 · 3H2 〇 powder. First, the amount of Im 〇 3 powder is 40. 2wt% and Y2 (C 〇 3) 3 · 3H2 〇 powder is 59. 8wt%, the total amount is prepared to be 200g ' The ΥΙη〇3 powder is 3.6 wt%, and the Ιη2〇3 powder is 85. The ΥΙη〇3 powder is obtained by the method of ball-milling in a dry state, and is calcined in the air at 1200 ° C for 3 hours. 6wt%, Sn〇2 powder is 10. 8wt% ratio 'preparation of all the amount is about 1. 〇kg (each gold 26 320647 200926207 genus The composition of the sub-component is In=88. Oat%, Sn=l 0. Oat%, Y=2. 〇at%), except that 'the system is the same as Sr_ITO (Sr=0.02) to produce a dry material. The density of the film was 7. 02 g / cm 3 . The sputtering target of Y = 0.05 was also produced. (Sputter target reference manufacturing example 3 ΧΒ - ΙΤ 0) (Add Β ΙΤ 0, Β = 0.05, Sn = 0. 1) Preparation of purity >99·99% of Im 〇 3 powder, Sn 〇 2 powder, and pure sound > 99. 99% of β2 〇 3 powder. First, Iri2 〇 3 powder is 87. 5wt %, Sn〇2 powder is 11. 2wt dead and Βζ〇3 powder is 1.3wt% ratio, the total amount is prepared as i.〇kg (the composition of each metal atom is In=85. Oat%, Sn=10. In addition, Oat% and B=5. Oat%) were produced in the same manner as Sr-ITO (Sr=0. 02), and the firing temperature was 1400 ° C. The density at this time was 5 01g/cm3 (Test Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1) Test Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1 were carried out in the following manners. Among the targets produced, the targets of the compositions of the following Table 5 were used, and the dry materials of Test Examples 1 to 14, Reference Examples 1 to 4, and Comparative Example 1 were set in the following manner. The dry materials are respectively placed in a 4 DC DC magnetron sputtering device, the substrate temperature is maintained at room temperature (about 2 〇 ° C), and the oxygen partial pressure is changed between 〇 and 3. Osccm (equivalent to 〇 The transparent conductive films of Test Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1 were obtained to 1 lxi〇-2Pa)'. 27 320647 200926207 [Table 5] Adding element oxygen bonding energy composition (Sn is lO.Oat%) Sr 134 Test Example 10 (Sr=0. 00001) Test Example 1 (Sr=0.01) Test Example 2 (Sr=0 02) Test Example 3 (Sr=0. 05) — Li 151 Test Example Li (Li=0. 00005) — Test Example 4 (Li=0.02) Test Example 5 (Li=0. 05) — La 242 Test Example 12 (La=0. 00008) Test Example 6 (La=0.01) Test Example 7 (La=0. 02) — — Ca 134 — — Test Example 8 (Ca=0. 02) Test Example 9 (Ca=0.05) Test Example 13 (Ca = 0.10) Mg 155 - Reference Example 1 (Mg = 0.02) Reference Example 2 (Mg = 0.05) Reference Example 5 (Mg = 0.12) Y 209 - Reference Example 3 (Y = 0. 02) Reference Example 4 (Y = 0.05) - B 372 - - - Comparative Example 1 (Β = 0.05) - The sputtering conditions were as follows, whereby a film having a thickness of 1200 A was obtained. Thick material size: Φ=4ίη. li=6mm Splash clock method: DC magnetron sputtering device ❹ Exhaust device: rotary pump + freezing vacuum pump reaching vacuum degree: 5. 3xlO_6[Pa]

Ar pressure: 4. OxlO_1 [Pa] Oxygen pressure: 0 to 1. lxl (T2 [Pa] Water pressure: 5. OxlO_6 [Pa] Substrate temperature: room temperature Sputtering power: 130 W (power density is 1.6 W/cm2)

Substrate used: Corning #1737 (glass for liquid crystal display) t=0. 8 mm The resistivity of the film formed by film formation in each oxygen partial pressure, and the resistance after annealing each film at 250 ° C 28 320647 200926207 rate. The results are shown in Figures 1 to 12.

It can be seen from these results that the optimum gas fraction is obtained in either case. In addition, in Test Examples 1 to 9, and Reference Examples 1 to 5, the optimum oxygen partial pressure of 6 to the temperature is 2525 ( The oxygen partial pressure at the time of the TC annealing is the most suitable for the film. Table 6 shows the optimum pressure at room temperature, and the gas knife® pressure at the lowest filming rate after annealing at 250 °C. Therefore, in Test Examples 1 to 9 and Reference Examples 1 to 5, first, after the annealing, the resistivity was the lowest in the oxygen partial pressure at the time of film formation, and the polymerization was carried out at ° ° C and then at 250 ° C. In the case of annealing, the resistivity was the lowest, and in Comparative Example 1 in which the oxygen bonding energy was large, it was found that an amorphous film was obtained at the time of film formation, but in the annealing at 250 ° C, the optimum oxygen was obtained. In addition, in the test examples 10 to 12 in which the amount of addition was too small, it was found that the amorphous film could not be obtained, and the optimum oxygen partial pressure © did not change. In Test Example 13, an amorphous film was obtained at the time of film formation, and in the annealing at 250 ° C, although the optimum oxygen partial pressure was changed 'But no crystallization occurs. In the following Table 6, the optimum oxygen partial pressure change is indicated by '', and the optimum oxygen partial pressure is not changed by X. (Test Example 1) In Test Examples 1 to 13 In Reference Examples 1 to 5 and Comparative Example 1, the transparent conductive film produced by forming the optimum oxygen partial pressure at room temperature was cut into a size of 13 mm square and in a large fluorine environment. (The samples were annealed for 1 hour for these samples in TC. Figures 13 to 19 show the pattern of the film XRD pattern before and after annealing. Further, regarding Test Examples 1 to 4, Reference Examples 1 to 4 and In Comparative Example 1, the crystallinity of the film formation at room temperature and after annealing at 250 ° C was abundance of a 'crystals as c', and the results are shown in Table 6. As a result, it was confirmed that In Test Examples 1 to 9 and Reference Examples 1 to 4 at room temperature film formation, an amorphous film was formed at the time of film formation, but crystallization occurred in annealing at 250 ° C for 1 hour. In Comparative Example 1 in which B having a larger oxygen bonding energy is added, or in Test Example 13 and Reference Example 5 in which the amount of addition is large, even in the case of The film was an amorphous film, but it did not crystallize after annealing at 250 ° C. Further, these were not crystallized after annealing at 300 ° C. Further, in Test Example 10 in which the amount of addition was small In the case of 12, crystallization was also formed during film formation, and it was confirmed that the amorphous film could not be formed. (Test Example 2) The optimum oxygen content of each transparent conductive film after film formation at room temperature was measured. The specific resistance ρ (Ω·cm) at the time of film formation was measured. Further, the resistivity measured for the sample after annealing in Test Example 1 was also measured. These results are shown in Table 6. From the results, it was confirmed In Test Examples 1 to 12, Reference Examples 1 to 4, and Comparative Example 1, the specific resistance was about 1 (Τ4 Ω·cm). However, in Test Example 13 and Reference Example 5, it was found that the specific resistance was 1 (Γ3 Ω · south resistance of CID. (Test Example 3) In Test Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1, The transparent conductive film produced in the optimum oxygen partial pressure at the time of film formation at room temperature of 30 320647 200926207 was cut into a size of 13 mm square, and the transmission spectrum was measured. Further, the film after annealing of Test Example 1 was measured. The transmission spectrum samples were also measured. These results are shown in Figures 20 to 26. In addition, Table 6 shows the average transmission after annealing of each of Test Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1. From these results, it is understood that the transmission spectrum after the film formation and before the annealing can be performed by annealing at 250 ° C for 1 hour to shift the absorption end toward the low wavelength side to improve the color tone. (Test Example 4) In Test Examples 1 to 13, Reference Examples 1 to 5, and Comparative Example 1, the transparent conductive film produced in the optimum oxygen partial pressure film formed at room temperature was cut into 10 x 50 Å, respectively. Size, and use ITO-05NC oxalic acid system, Kanto Chemical Co., Ltd.) (oxalic acid concentration 50g / L) As an etching solution, it was confirmed whether or not etching was possible at a temperature of 30 °C. Further, the 0 samples after the annealing of Test Example 1 were also confirmed in the same manner. These results are shown in Table 6 by etching to "〇" and not etching to "X". From the results, it can be seen that although the amorphous film can be imprinted with a weakly acidic etchant, the crystallized film cannot be engraved. 31 320647 200926207 [Table 6] ο ο ο -ο ο ο ~5~ ΙΟΙ ο X X X ο ο Ιο ο ο ο ο Ι I I I~5~ [x^oi

E 〇〇C0 α>β> ί5 (pss ^Joe) [α^β] -3⁄43⁄4^ [Eo.s_olx] one~ ss • s oz oz 07 °-0 6·® ζ_,,ρ Ύζ s ' • Adultery β1-· ε·ε 8·α ΤΓ SI 'ι ss is

i US 1-3⁄4 4 Εραϋ s> s s s os s · inch 5 6 Γ sh·' ^'£, μ·'" 5 Vc ΜΜ 6 call [ί 2 o

O

O o o o

O o o ιο ιο1 Μ Μ Ν οι 3⁄4^ i i soo soo 宙0Ό

UOO ci §.0 soo

S0.0goo 500 sro g1§ln Ι§1ΌS5 ioopo ioi UOOOOO -3⁄4^ o.l 0~ os 0~ s

OZ

OS

s s0.Z cm Q.S 0n ulol I 800.0 1.0 I cs om 0.0- o<n 0.0- 0.0- cm

I 0ΌΙ- 0.0- ΟΌΙ 0.0^ ΟΌΙ om Qg 0.07 o.g 00001 000.CH 00001 cl

OS

OS 0-8 0.88 0S8 0.68

OS 0.88 008 OS 0S8 o.g og 1 0.5 0 08 Is S6.S 66i s s s Π □ «0 «0 32 ls1 m2 μβι hl Π us 5.?w

SO=JS §.?w so=n soo=n 5Ό=TMΊ SOHel SO="o soneo g.0=8 i=rl zo.o=A 2-0=82 gonws Sts l5,0=go 800000 =3 i=n 5§ontw sf杳咿砵I τ j_ 71 - u 0- ® w 32 320647 200926207 ' (Transparent conductive film containing the composition of Sr) The composition shown in the first table manufactured using the above is used. Dry material, respectively, these targets are installed in a 4 DC DC magnetron sputtering device, the substrate temperature is maintained at room temperature (about 20 ° C), and the oxygen partial pressure is changed between 〇 to 3. Osccm (equivalent A transparent conductive film of each composition was obtained at 0 to 1. lxl (T2Pa). The sputtering conditions were as described, whereby a film having a thickness of 1200 A was obtained. Light material size: φ = 4 ίη · t = 6 mm sputtering method : DC magnetron sputtering device ® exhaust gas arrangement: rotary pump + freezing vacuum pump to reach vacuum: 5. 3x10 - 5 [Pa]

Ar pressure ·· 4. OxlOjPa] Oxygen pressure: 0 to 1.1x10-2 [Pa] Water pressure: 5. 0xl0_5 [Pa] Substrate temperature: room temperature, money plating power: 130W (power density is 1.6W/cm2) ❹ Use Substrate: Corning #1737 (glass for liquid crystal display) t=0.8 mm Here, the optimum oxygen partial pressure of film formation at room temperature is different from the partial pressure of oxygen at 25 (the lowest resistivity after TC annealing). The sample is mostly, but the optimum oxygen partial pressure is not changed due to the difference in composition. In the following Table 7, it is shown that the optimum oxygen partial pressure change is 〇, and the optimum oxygen partial pressure is not changed. The transparent conductive films produced by the optimum oxygen partial pressure of each composition at room temperature were cut into 13 mm squares, and these samples were subjected to 1 hour in 25 (TC) in an atmospheric environment. Annealing, for 33 320647 200926207 at room temperature film formation and after annealing at 250 ° C, the amorphous phase is a, the crystal is c, and the results are shown in Table 7. The crystallization temperature 'is shown in Table 7. The crystallization temperature of the Fellow is after film formation at 100 ° C The temperature at which the crystallization is formed cannot be an amorphous film in the film formation at 1 〇〇 ° C, and is set to be less than 10 ° C. ❹ Further, each transparent conductive film formed into a film is measured in a chamber. The optimum oxygen partial pressure at the time of film formation is the resistivity ρ (Ω _ cm) of the sample which is annealed and crystallized, and these results are shown in Table 7. In addition, the optimum oxygen which will be formed at room temperature is formed. The transparent conductive film produced in the partial pressure was divided into 13 mm squares, and the transmission spectrum was measured on the annealed film. The average transmittance after annealing is shown in Table 7. In addition, film formation at room temperature was performed. The most suitable oxygen content is pressed and the crystallization of the transparent conductive film is cut into the dynamic "ΤΙ Γ 5〇 == Ν (oxalic acid system 'Kanto Chemical (stock)) (5) (four) heart temperature step side rate (4) is set to ❿ ' In addition, it can be crystallized in ▲ i _C. From the results, it can be seen that "in the case of addition film, it is an amorphous film, and when the element is Sr is expected to be in the case of less than loot: crystallization is fine. Range, system two = ^ 3, in the annealing y (mole) 'located in Sr vs. ',,, tin to 1 mol of indium The ear ratio (-4.1xl〇-2Ln(x)-9, 2xl〇-2 indium molar ratio X is above the value and is (-2.9χ1〇^η(Χ) 320647 200926207 -6.7x10—〇 In addition, in this range, especially in the tin to 1 molar indium molar ratio y (mole) is expressed in Sr to 1 mol of indium molar ratio X (- 8. 2 xl (T2Ln(x)-l. 9x101 or more, when the annealing temperature is less than 200 °C, it cannot be crystallized, so it is preferable to consider it at 200° when considering the film forming process. The range of crystallization in the annealing above C. Further, in the above range, it is more preferable that when the molar ratio y of tin to 1 mol of indium is 0.15 m or more and 0.2 m or less, the specific resistance after annealing at 250 ° C It is 3. 0 χ 10_4 Ω · cm or less.

35 320647 200926207 [Table 7] Sample No. The ratio of In : lmol [mol] The optimum oxygen permeability after annealing at the crystalline crystallization temperature after annealing. The average transmittance after annealing is Sr Sn [〇 /χ] [a/c] rc] [Ω · cm] [A/sec] [%] al 0. 005 0.053 XC <100 2.8 X 92.2 a2 0.006 0.112 XC <100 1.9 X 90.1 a3 0. 006 0.178 〇a 150 1.8 3.6 91.2 a4 0. 006 0. 252 〇a 200 2.3 2.4 86.8 a5 0.011 0.053 X c <100 3.2 X 93.1 a6 0. Oil 0.112 〇a 100 2.1 5.7 96.9 a7 0.012 0.179 〇a 150 1.8 3.6 95.2 A8 0.013 0.253 〇a 200 2.4 2.4 90.0 a9 0. 022 0.054 X c <100 4.8 X 91.4 alO 0.023 0.114 〇a 150 2.6 5.8 93.5 all 0.024 0.181 〇a 200 2.2 3.7 94.2 al2 0.026 0.256 〇a 250 2.8 2.5 90.3 al3 0.033 0.054 〇a 100 5 9.9 90.1 al4 0.034 0.115 〇a 200 3.2 6.1 92.9 al5 0.037 0.183 〇a 250 2.7 4.0 93.1 al6 0.039 0. 260 〇a 300 3.4 2.4 88.4 al7 0.056 0.056 〇a 200 8.1 9.5 87.4 al8 0.059 0.118 〇 a 300 6.3 5.9 91.1 al9 0.063 0.188 〇a 300< 6.5 4.1 88.8 a2 0 0.067 0.267 〇a 300< 7.8 2.5 84.1 a21 0.118 0.059 〇a 300< 15.2 11.0 84.2 a22 0.125 0.125 〇a 300 < 13.1 7.2 84.3 a23 0.133 0. 200 〇a 300< 10.5 5.3 83.6 a24 0.143 0.286 〇a 300< 13.0 2.7 83.1 a25 0. 000011 0,111112 X c <100 1.8 X 97.5 a26 0.000589 0. 176574 X c <100 1.8 X 96.4 a27 0.001221 0. 219780 〇a 150 2.1 3.0 93.8 a28 0.012195 0.207317 〇a 200 2.2 3.2 94.3 a29 0.001112 0.111235 X c <100 1.9 X 91.0 a30 0.026316 0. 289474 〇a 300 4.6 1.6 88.7

36 320647 200926207 (Transparent Conductive Film Containing Li. Composition) Using the dry materials of the composition shown in Table 2 manufactured above, these dry materials were respectively placed in a 4-pair DC magnetron sputtering apparatus. The temperature was maintained at room temperature (about 20 ° C), and the partial pressure of oxygen (equivalent to 0 to 1.1 < 1 () - 2 ? 3) was changed between 〇 and SCCm to obtain each composition. Transparent conductive film. The ore-containing conditions are as follows. Thus, a film having a thickness of 1200 A can be obtained. Material size: φ=4ίη. t=6mm Splashing method: DC magnetron splashing device Θ Exhaust device: rotating system + cold vacuum pump reaching vacuum degree: 5. 3xlO_5[Pa]

Ar pressure: 4. Oxl〇-1 [Pa] Oxygen pressure: 〇 to 1. lx10_2 [Pa] Water pressure: 5. 0x10 - 5 [Pa] Substrate temperature: · Room temperature sputtering power: 130W (power density is 1.6 W/cm2) Ο Substrate: Corning #1737 (glass for liquid crystal display) t=0. 8mm Here, the optimum oxygen partial pressure at room temperature and the lowest resistivity after annealing at 25〇〇c The partial pressure of oxygen in the membrane is mostly different, but the optimum partial pressure of oxygen is not changed due to the difference in composition. In the following Table 8, it is shown that the change in the optimum oxygen partial pressure is 〇, and the change in the optimum oxygen partial pressure is X. Further, the transparent conductive films produced by forming the optimum oxygen partial pressure of each composition at room temperature were cut into a size of 13 mm square, and the samples were subjected to 'at 250 ° C in the atmosphere> Annealing for an hour, for the crystal state of 37 320647 200926207 at room temperature and after annealing at 250 ° C, amorphous is a, and crystal is c, and these results are shown in Table 8. Further, the crystallization temperatures of the respective compositions were measured and shown in Table 8. The crystallization temperature is a temperature at which crystallization occurs after film formation at 100 ° C, and it is not possible to form an amorphous film in the film formation at 1 〇〇 ° C, and is set to less than 10 〇 (TC. Further, measurement The resistivity Ρ (Ω · cm) of the sample which was crystallized by forming the film by the optimum oxygen partial pressure at the time of film formation at room temperature, and the results are shown in Table 8. Further, the transparent conductive film produced in the optimum oxygen partial pressure film formed at room temperature was cut into a size of 13 mm square, and the transmission spectrum was measured on the annealed film. The average transmittance after annealing was expressed in the table. In addition, the transparent conductive crucible which was annealed and crystallized in the optimum oxygen partial pressure formed at room temperature was cut into a size of 1〇χ5〇 leg, and ΙΤΟ-05Ν was used. The oxalic acid system (manufactured by Kanto Chemical Co., Ltd.) (oxalic acid concentration: 50 g/L) was used as an etching solution, and the etching rate ❹ (A/sec) in the temperature of 3 {Γ(:) was measured. The results are shown in Table 8. These results are shown in Figure 28. In the figure, it will be less than (10). And (10) to the singer can be crystallized, and the others are ^. From the results, it can be known that when the additive element is Li, when it is less than 1 〇 (rc when filming) It is made into an amorphous film, and then it is etched in 3G "C: the composition range of crystallization is made of tin to 1 mole of 莫 耳 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫The range of 1. 6x10 Ln(x)-5. 9xl(rl) expressed by Mobbi is above (1). (1) 320647 38 200926207 ' -5. The range below 7x10'. In addition, in this range , especially in the tin to 1 molar indium molar ratio y (mole) is expressed in Li to 1 mole of indium molar ratio X (-7. 0 xlO-2Ln (x)-1.6xlO_1 In the above range, when the annealing temperature is less than 200 ° C, crystallization cannot be performed. Therefore, when the film formation process is considered, it is preferable to crystallization in the annealing at 200 ° C or higher. 015以下。 In the above range, more preferably, the tin to 1 molar indium molar ratio y is 0. 28 m or less, and Li to 1 mol of indium molar ratio of X is 0. 015 or less At the time of annealing at 250 ° C The electric resistance is 3. 0x10 - 4 Ω · cm or less. ❹ 39 320647 200926207 [Table 8] Sample No. The ratio of In · lmol [mol] The optimum crystallization temperature at the time of film formation at the crystalline crystallization temperature Average Transmittance after Annealing Rate Li Sn [〇/χ] [a/c] [°C] [Ω · cm] [A/sec] [%] bl 0.005 0.053 XC <100 2.7 X 92.1 b2 0.006 0.112 XC <100 1.8 X 90.1 b3 0.006 0.178 XC <100 1.8 X 91.2 b4 0.006 0.252 〇a 200 1.9 2.4 86.8 b5 0.011 0.053 X c <100 3.6 X 93.1 b6 0.011 0.112 X c <100 2.7 X 96.9 b7 0.012 0.179 〇a 200 2.2 3.4 95.2 b8 0.013 0. 253 〇a 250 2.4 2.4 90.0 b9 0,022 0.054 〇a 100 5.6 8.2 91.4 blO 0.023 0.114 〇a 200 4.6 6.1 93.5 bll 0.024 0.181 〇a 250 4.2 3.6 94.2 bl2 0.026 0.256 〇 a 300 4.9 2.5 90.3 M3 0.033 0.054 〇a 150 7.2 8.2 90.1 bl4 0.034 0.115 〇a 200 5.8 5.7 92.9 bl5 0. 037 0.183 〇a 250 6.2 3.7 93.1 bl6 0.039 0.260 〇a 300< 6.6 2.5 88.4 bl7 0. 056 0.056 〇 a 250 9.4 8.4 87.4 bl8 0. 059 0.118 〇a 300 8.8 5.6 91.1 Bl9 0. 063 0.188 〇a 300 < 7.0 3.8 88.8 b20 0.067 0.267 〇a 300< 9.8 2.6 84.1 b21 0.118 0.059 〇a 300 < 16.3 9.7 84.2 b22 0.125 0.125 〇a 300 < 14.2 8.6 84.3 b23 0.133 0.200 〇a 300<12.5 6』 83.6 b24 0.143 0.286 〇a 300< 15.6 2.8 83.1 b25 0.000056 0.111117 X c <100 1.9 X 95.6 b26 0.002415 0.205314 X c <100 2.0 X 91.8 b27 0.001112 0.111235 X c <100 1.8 X 91.5 b28 0.001178 0.176678 X c <100 1.9 X 92.1 b29 0.012195 0.207317 〇a 200 2.2 3.0 90.3 b30 0.025000 0.225000 〇a 250 4.6 2.8 88.3

40 320647 200926207 (Transparent Conductive Film Containing La Composition) Using the above-described targets having the compositions shown in Table 3, these targets were respectively mounted on a 4 DC DC magnetron sputtering apparatus to adjust the substrate temperature. The transparent conductive film of each composition was obtained while maintaining the oxygen partial pressure (corresponding to 0 to 1. lxlO_2Pa) between 0 and 3.0 cmc. The sputtering conditions were as follows, whereby a film having a thickness of 1200 A was obtained. Dimensions of leather material ·· Φ=4ίη. t=6mm Sputtering method: DC magnetron sputtering device ® Exhaust device: rotary pump + freezing vacuum pump Reach vacuum: 5.3xl (T5[Pa]

Ar pressure: 4. OxlOlPa] Oxygen pressure: 0 to 1. lxlO_2 [Pa] Water pressure: 5. Oxl (T5 [Pa] substrate temperature: room temperature sputtering power: 130 WC power density is 1.6 W/cm 2 ) p : Corning #1737 (glass for liquid crystal display) t=0. 8mm Here, the optimum oxygen partial pressure at room temperature film formation is different from the oxygen partial pressure at the time of film formation after annealing at 250 ° C. The sample is mostly, but the optimum oxygen partial pressure is not changed due to the difference in composition. In the following Table 9, it is shown that the change in the optimum oxygen partial pressure is 〇, and the change in the optimum oxygen partial pressure is X. Further, the transparent conductive films produced by forming the optimum oxygen partial pressure of each composition at room temperature were cut into a size of 13 mm square, and the samples were subjected to an atmosphere at 250 ° C in an atmospheric environment. Annealing for an hour, for 41 320647 200926207 film formation at room temperature and after crystallization at 250t annealing, the crystal is a 'crystal crystallization' and these results are shown in Table 9. Further, the crystallization temperature of each composition was measured and shown in Table 9. The crystallization temperature is 10 (the temperature at which crystallization occurs after TC film formation, and it cannot be an amorphous film at the time of film formation at 1 〇〇 ° C, and is set to less than 1 〇〇 < 3 (:. The electric resistivity Ρ (Ω · cm) of the sample which was crystallized by the optimum oxygen partial pressure film formation at the time of film formation at room temperature was measured, and the results were expressed. Further, in Table 9, the transparent conductive film produced in the optimum oxygen partial pressure film formed at room temperature was cut into a size of 13 mm square, and the transmission spectrum was measured on the annealed film. The rate is shown in Table 9. In addition, the transparent conductive film which was produced by annealing in the optimum oxygen partial pressure at room temperature was cut into a size of 1 〇 x 5 〇 mm and used. ITO-05N (Grass. Acid, Kanto Chemical Co., Ltd. oxalic acid concentration: 50 g/L) was used as an etching solution, and the etching rate (A/© sec) at a temperature of 3 〇 was measured. The results are shown in Table 9. The results are reversed as shown in Figure 29. In the figure, an amorphous film can be formed at less than 10 (TC film formation temperature, Those who can be crystallized from 1〇〇 to 3〇〇ΐ are drums as Lu, and others are Α. From the results, it can be known that when the additive element is La, it is less than l〇〇t : When film formation, it becomes an amorphous film, and then it is annealed at 1 〇〇 to 中, and the composition range of crystallization is the molar ratio y of indium to tin in the range of La to 1 mol. The molar ratio of indium to X is expressed by the value of (-6. 7χ10-2 Ln(x)-2· 2xlG ^ and is equal to or less than the value of (1). 3xl (rlLn(1)_7·7χ1(Γΐ) 42 320647 200926207. In this range, especially in the tin to 1 molar indium molar ratio y (mole) is expressed in La to 1 molar indium molar ratio X (-8. 7 xl (T2Ln ( x)-2. ΟχΗΓ1) In the above range, when the annealing temperature is less than 200 °C, it cannot be crystallized. Therefore, when considering the film forming process, it is preferable to apply it in annealing at 200 °C or higher. Further, in the above range, it is more preferable that when the molar ratio of tin to 1 mol of indium molar ratio y (mole) is 0.23 mol or less, the ratio after annealing at 250 ° C The resistance is 3. 0χ10_4 Ω · cm or less. 〇43 320647 200926207 [Table 9] Sample No. Ratio of In : lmol [mol] Optimum oxygen partial pressure film formation Crystallization crystallization temperature After annealing, average resistance after annealing Transmittance La Sn [〇/x] [a/c] f°C] [Ω · cm] [A/sec] [%] cl 0.005 0.053 XC <100 2.7 X 93.2 c2 0.006 0.112 XC <100 1.9 X 98.2 c3 0.006 0.178 〇a 150 1.8 3.4 93.4 c4 0. 006 0.252 〇a 200 3.8 1.9 94.2 c5 0.011 0.053 X c <100 2.8 X 92. 6 c6 0.011 0.112 〇a 100 2.0 4.8 98.3 c7 0.012 0.179 〇a 150 1.9 3.5 92.5 c8 0.013 0.253 〇a 250 4.0 1.8 93.2 c9 0. 022 0. 054 〇a 100 3.0 7.6 92.1 clO 0.023 0.114 〇a 150 2.0 4.9 98.8 ell 0. 024 0.181 〇a 200 2.1 3.6 94.2 cl2 0.026 0.256 〇a 250 4.2 1.8 91.2 cl3 0.033 0. 054 〇a 150 3.1 7.4 91.9 cl4 0.034 0.115 〇a 200 2.2 5.1 94.1 cl 5 0.037 0.183 〇a 250 2.3 3.5 93.6 cl 6 0.039 0. 260 〇a 300 5.9 1.9. 87.6 cl 7 0.056 0.056 〇a 250 6.4 7.3 90.2 cl 8 0.059 0.118 〇a 300 8.6 4.9 87.3 cl 9 0.063 0.188 〇a 300< 7.1 3.6 85.2 c20 0.067 0.267 〇a 300 < 9.9 2.0 83.9 c21 0.118 0.059 〇a 300 < 9.5 8.4 82.5 c22 0.125 0.125 〇a 300 < 14.5 6.2 84.6 c23 0.133 0. 200 〇a 300 < 13.0 4.4 84.6 c24 0.143 0.286 〇a 300< 16.1 2.2 82.3 c25 0. 00009 0.111 X c <100 1.9 X 98.2 c26 0.00115 0.150 X c <100 1.8 X 96.5 c27 0. 00125 0.250 〇a 150 4.0 1.9 93.5 c28 0 01235 0.222 〇a 200 2.3 2.9 94.6 c29 0. 00244 0.220 〇a 150 2.4 2.0 94,8 c30 0. 00047 0.177 X c <100 2.6 X 94.2

44 320647 200926207 (Transparent conductive film containing Ca) The sputtering conditions are as described in r, whereby a film having a thickness of i200A can be obtained. Dry material size: 4=40. Hall Sputtering method: DC magnetron sputtering device Exhaust device: Rotary pump + cold bead vacuum pump Reaching degree of vacuum: 5. 3xl〇_5[Pa]

Ar pressure: 4. OxlOlPa] Oxygen pressure: 0 to 1. lxl〇_2 [Pa]

I Water pressure: 5. 0xl (T5[Pa] Substrate temperature: room temperature sputtering power: 130W (power density is 1.6W/cni2) Use substrate. Kang content #1737 (glass for liquid crystal display) >^0. 8 coffee using the above-mentioned target having the composition shown in Table 4, respectively, these 绮 installed in the 4 (four) DG 杂 杂 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 A transparent conductive film of each composition was obtained by changing the partial pressure of oxygen (phase to ll.lxlG Pa). Post-electricity = enthalpy: the optimum oxygen partial pressure of the warm film, and annealing at 25 〇t but Not because of the composition of the sample, the most suitable = change table: the most suitable oxygen partial pressure butterfly 2 =:: = film see the most suitable oxygen partial pressure cut in the manufacturing city in the 2 ah in the sample of these hours into the ί = 320647 45 200926207 In the state of film formation at room temperature and after annealing at 250 C, the amorphous phase is a, and the crystal is c, and these results are shown in Table 1. Further, 'the crystallization temperature of each component is measured' It is shown in Table 1Q. The crystallization temperature is the temperature at which crystallization occurs after film formation at 10 0 C, and it cannot be an amorphous film in the film formation of 1 〇〇. In addition, the resistivity ρ (Ω · of the sample which was crystallized after the film formation of each of the transparent conductive films at room temperature was measured by the optimum oxygen partial pressure at room temperature was measured. Cm) These results are shown in Table 1. In addition, the transparent conductive film produced by forming the optimum oxygen partial pressure at room temperature is cut into a size of 13 mm square, and the film is annealed. The transmission spectrum was measured. The average transmittance after annealing is shown in Table 1 ❾ sec). As a result, as shown in Table 10, the transparent conductive film which was annealed and formed by annealing at the optimum oxygen partial pressure at room temperature was cut into a size of 5 ' and used ITG- 〇5M (oxalic acid system, manufactured by Kanto Chemical Co., Ltd.) (oxalic acid concentrated and 5 g/L) as the residual liquid 'measured by the button rate in temperature (a/ These results are shown in Figure 30. Temperature Can form an amorphous film, and in the pancreas, and at 100 to

In the figure, it will crystallize in less than 1 〇 〇 °c] to 300T:

The value of Ln(x)-9. 3xl〇-2) is 'annealing at 100 to 300 ° C after less than 100 t: ' when the additive element is Ca' is tin to 1 mol of indium. Mohr ratio J is expressed in the range of _4·1x10 2 and is (~2. 5xlO_1Ln(x)_5. 7xl0-1) 46 320647 200926207. In addition, in the range , especially in the tin to 1 molar indium molar ratio y (mole) is expressed in Ca to 1 molar indium molar ratio X (-8. 7 xl (T2Ln (x)-2. In the range of OxltT1) or more, when the annealing temperature is less than 200 ° C, crystallization cannot be performed. Therefore, when the film formation process is considered, the range of crystallization in annealing at 200 ° C or higher is preferable. Further, in the above range, it is more preferable that when the molar ratio of tin to 1 mol of indium is 〇 (mole) is less than 28 mTorr, the specific resistance after annealing at 250 ° C is 3 0χ1(Γ4Ω·cm or less. 47 320647 200926207 [Table 10] Sample No. Ratio of In : lmol [mol] Optimum Oxygen Partial Pressure Forming Crystallization Crystallization Temperature Annealing After Annealing After Annealing average Transmittance Ca Sn [〇/x] [a/c] rc] [Ω · cm] [A/sec] [%] dl 0.005 0.053 X c <100 2.8 X 94.6 d2 0.006 0.112 X c <100 1.9 X 95.4 d3 0.006 0.178 〇a 150 1.9 3.7 94.5 d4 0.006 0.252 〇a 200 2.2 1.9 92.9 d5 0.011 0.053 X c <100 3.2 X 91.3 d6 0.011 0.112 〇a 100 2.2 5.4 95.2 d7 0.012 0.179 〇a 150 2.0 3.8 92.1 d8 0.013 0.253 〇a 250 2.6 1.9 90.0 d9 0.022 0.054 X c <100 4.8 X 91.7 dlO 0-023 0.114 〇a 150 3.0 5.5 96.2 dll 0.024 0.181 〇a 200 2.3 4.0 93.4 dl2 0.026 0.256 〇a 300 2.9 1.9 88.4 dl3 0.033 0 054 〇a 100 5.3 8.7 90.2 dl4 0. 034 0.115 〇a 150 3.8 5.6 88.4 dl5 0.037 0.183 〇a 250 2.9 3.9 90.1 dl6 0.039 0.260 〇a „ 300 < 4.1 2.0 85.6 dl7 0.056 0.056 〇a 200 9.9 8.8 81.9 dl8 0.059 0.118 〇a 250 6.4 5.4 95.1 dl9 0.063 0.188 〇a 300< 6.8 4.1 89.0 d20 0.067 0.267 〇a 300 < 8.5 2.1 83.9 d21 0.118 0.059 〇a 300 < 19.5 9.9 83,2 d22 0.125 0.125 〇a 300< 17.8 6.2 89.9 d23 0.133 0.200 〇a 300< 16.3 4.9 83.8 d24 0.143 0.286 〇a 300< 18.6 2.2 84.5 d25 0.002110 0. 052743 X c <100 2.7 X 93.8 d26 0.000575 0.149511 X c <100 1.9 X 94.1 d27 0.001206 0.205066 〇a 150 2.0 2.8 90.2 d28 0.001252 0.250313 〇a 150 2.1 1.9 93.1 d29 0.001100 0.099010 X c <100 2.1 X 90.3 d30 0.026316 0. 289474 〇a 300 32. 2.1 88.2

48 320647 200926207 In this way, by adding the addition of the yuan boast, -± _ ', to obtain a specific effect 'only the different kinds of sage, can obtain the specific effect of quasi-calling, plus Sr, Li, La, Ca elements of the yifu p阁—, 禆赤A is not detached, and is surrounded by less than 100. When the ruthenium is formed into a film, it is a non-daily film, and after annealing in 1 〇〇曰 π λα λ 丄 main 300 c, the composition range of the crystallization of the koji is called,,,,,, The indium molar ratio y (mole) of the ear is located above the q 7 value expressed by the additive element pair 1 莫, -9 (-9. secret 2Ln(x)-21xlUtr molar ratio x and is (-2· 5χ1〇,χ) -5. 7x10) The range below the value. The result is shown in Figure 31. In the figure, among all the elements, an amorphous film can be formed at a film formation temperature of less than 10 ° C, and it can be set to # in the range of 1 〇〇 to 3 〇〇, except for this. The outside is ▲. In addition, the sample number is represented only by the number after the letter is removed. (Test Example 14) In the same manner as in Production Example 1, a target of Sr = 0.0001 was produced, and this was used as a target of Test Example 15, and this was mounted on a 4 DC DC magnetron sputtering sputtering apparatus. The transparent conductive film of Test Example 14 was obtained by maintaining the substrate temperature at room temperature (about 20 ° C) and changing the oxygen partial pressure (corresponding to 0 to 1. lxl0 to 2 Pa) between 〇 and 3.0. The sputtering conditions were as follows, whereby a film having a thickness of 1200 A was obtained. Dry material size: φ=4ίη· t=6mm Sputtering method: DC magnetron plating device Exhaust device: Rotary pump + freezing vacuum pump Reach vacuum: 5.3xl (T6[Pa]

Ar Pressure: 4. 〇xl〇_1[Pa] 320647 49 200926207 Oxygen pressure: 0 to 1. lxl (r2[pa] Water pressure: 1. 0xl (T3[Pa] Substrate temperature: room temperature sputtering power: 130W (Power density: 1.6 W/cm 2 ) Substrate: Corning #1737 (glass for liquid crystal display) t = 0.8 mm (Test Example 15) The same target as Test Example 14 was used, and was the same as Test Examples 1 to 9. The conditions of the production were carried out, and the transparent conductive film of Test Example 15 was obtained. (Test Example 5) The same as Test Examples 1 to 9, Reference Examples 1 to 4 and Comparative Example 1, and Test Example 14 and Test Example 15 were confirmed. Whether there is a change in the optimum oxygen partial pressure before and after annealing, and the same tests as in Test Examples 1 to 4 were carried out. Table 11 shows the results. From the results, it was confirmed that in the composition of Sr = 〇. 0001, When the film formation is carried out under the condition that water is substantially absent, an amorphous film cannot be obtained (measurement φ test example 15), but if the water pressure is increased to 1. 〇xl (T3 [Pa], the water system is hydrogen. Entering into the film, an amorphous film can be obtained, and the optimum partial pressure of oxygen is also changed before and after annealing. This is due to the influence of water. The crystallization temperature of the film rises, especially in a region having a small content. That is, the crystallization temperature of the amorphous film is, for example, in a lower region of 10 CTC, the crystallization temperature can be increased by 50 to 1. 〇〇 ° C or so, as a result, the amorphous film can be easily formed. When the oxygen bonding energy is almost equal to I38kj / mo 1 of 134kJ / mol of Sr, this phenomenon also occurs, so it can be presumed that , this 50 320647 200926207 phenomenon is also the same in L i, La, Ca, Mg, Y of other elements in which the oxygen bonding energy is in a specific range. Because of the relationship with the previous application, the Ba is from the scope of the present application. The following is a reference example to reveal a case of Ba. 〇❹ 51 320647 200926207 [Table 11] ο 可 Can the etching rate be [Ο or Μ 1 ο X Average transmittance after annealing g 97.8 97.1 Crystallinity after annealing (250 ° C) [β or c] 1 ο ο Crystallinity at film formation 1 [a or C] 1 α ο Specific resistance after annealing E 〇ά 1 α > σ > Specific resistance at film formation Ί 1 Ο S The optimum oxygen partial pressure change Ι[0 or χ]Ι ο X ψ ( 5 xuiux Proportion I 0.000111 0.000111 ¢1 Add Yuan 0.010 0.010 & 10.000 10.000 £ 89.990 of .990 Add element (Α Sample name Sr=0.0001 Moisture pressure: 1.〇xlO-3Pa Sr=0.0001 Test Example 14 Test Example 15 52 320647 200926207 (Reference example) (Sputter target reference manufacturing example 1 to 67) Preparation purity > 99. 99% of Iri2〇3 powder, Sn〇2 powder, and purity>99.9% BaC〇3 powder . 〇❹ First, the ratio of the BaC〇3 powder of BET=27 m2/g of 58.6 wt% and BET=1.3 m2/g is 41.4 wt%, and the total amount is 200 g, in a dry state. The mixture was ball milled and calcined in the atmosphere under uoyc for 3 hours to obtain BaIn2〇4 powder. Next, the above BaIn2〇4 powder, BET=5 m2/g of In2〇3 powder, and BET=1.5 m2/g of Sn〇2 powder, and 鼬 and Sn to 1 mol of In correspond to the following Table 12 and Table 13. The proportion of the moles is prepared, and the total amount is prepared to be about 1.0 kg' and ball milled and mixed. Thereafter, a PVA aqueous solution was added as a binder, mixed, dried, and cold pressed to obtain a molded body. In the atmosphere, the molded body was degreased at 600 ° C for 6 hours at a temperature increase rate of Tc/h. Then, in an oxygen atmosphere, the sintered body was obtained by firing at 16 rpm for 8 hours. The sintering conditions, specifically, the temperature rise rate of iGGt/h, the temperature is raised to 8 〇{rc, and the temperature is raised from 4 〇 (the heating rate of rc/h is increased to 16 GG, ° C 'after 8 hours). The cooling condition of (10).c/h is cooled from 1600 C to room temperature. After that, the sintered body is added to obtain a dry material. The second, and the overall resistivity are, for example, in the composition of 32, respectively. 〇.〇/Λ*2.81χ1 (Γ4Ω·(10), in the composition of 22, respectively 6.96 g/cm and 2.87x1〇_4q · [ (Reference Examples A1 to A67) Each reference manufacturing example 1 to 67 (10) was plated The dry material is installed in 4 pairs of 320647 53 200926207 DC magnetron splash; do: # m, and the device 'maintains the substrate temperature at room temperature (about 20. 〇, will set the moisture to the right _, m / x ^ 丨. 0xl0—4pa, and the oxygen partial pressure was changed between 〇 and 3. Osccm (the same as π nn * field, to l lxl 〇 -2pa), and the transparent conductive films of Reference Examples A1 to A67 were obtained. Thus, a film having a thickness of 1200 Å can be obtained. Target size: φ=4ίη. t=6mm Sputtering method: DC magnetron sputtering device Q Exhaust device: Rotary pump + freezing vacuum pump to reach vacuum: 5. 3xlO_6[Pa]

Ar Pressure: 4. 〇xl〇-1[Pa] Oxygen pressure: 0 to 1. lxl〇-2[pa] Water pressure: 1. 〇xl〇-4[pa] Substrate temperature: room temperature sputtering power: 130W (Power Density: 1.6 W/cra2) Substrate: Corning #1737 (glass for liquid crystal display) © For Reference Examples A1 to A67, the relationship between the oxygen partial pressure and the resistivity at room temperature film formation was obtained, and 25 (The relationship between oxygen partial pressure and resistivity after TC annealing. Tables 12 and 13 below show the Ba and % of each sample to 1 molar Ear molar ratio, and room temperature film formation In the case of the crystalline state (amorphous film β is a, the crystallized film is referred to as c)' and the crystallization of the amorphous film is not produced. In the table 12 and the table 13 The rate refers to the resistivity of the film of the optimum oxygen partial pressure at room temperature film formation. Further, the resistivity after annealing is the resistivity of the optimum oxygen partial pressure at the time of annealing at 250 ° C. 320647 54 200926207 In addition, the 12th The crystallization temperature shown in Table 13 and Table 13 is obtained by the following method, that is, a film formed at room temperature under the oxygen partial pressure after annealing at 250 ° C, from 100 ° C to 300 ° C C (450 ° C if necessary) was annealed in the atmosphere at 50 ° C for 1 hour, and analyzed by thin film XRD. For diffraction of amorphous film showing room temperature film formation The halo peak is detected by increasing the annealing temperature, and the initial temperature is determined as the crystallization temperature. For other methods of crystallization temperature, a high temperature thin film XRD method can also be used. In the drawing, reference examples A1 to A67 are shown, wherein the crystallization temperature is 100 to 300 ° C, and the crystallization temperature is 350 ° C or higher. From the results, the crystallization temperature is The range below 300 ° C is the molar ratio of tin to 1 mol of indium y (mole), which is represented by the molar ratio X of indium to 1 mol (-6.9 x 1 (T2Ln ( The value of x)-1.6xlO_1) is not less than the value of (-8. lxl(T3Ln(x) + l. 8xl0_1). 55 320647 200926207 [Table 12]

Sample No. Production example Sn ratio of Ba to crystal state crystallization temperature (°C) Resistivity at the time of film formation (χ10"4 Ω · cm) Resistivity after annealing (χ10'4 Ω · cm) A1 1 0 0.1 a > 500 19. 6 21.4 A2 2 0.025 0.07 a >500 12. 8 14.4 A3 3 0.025 0.1 a >500 16.0 18.2 A4 4 0. 05 0.0001 a 150 4.7 3.4 A5 5 0. 05 0.0002 a 150 4.8 3.4 A6 6 0.05 0.0005 a 150 4.9 3.5 A7 7 0.05 0.001 a 150 4.7 3.6 A8 8 0.05 0.002 a 150 4.7 3.4 A9 9 0.05 0.005 a 150 4.8 3.5 A10 10 0. 05 0.01 a 150 5.2 3.6 All 11 0. 05 0.02 a 200 5.4 4.7 A12 12 0.05 0.03 a 250 6.0 4.9 A13 13 0.05 0.05 a 400 8.2 9.2 A14 14 0. 075 0.002 a 150 4.6 2.5 A15 15 0.075 0.005 a 150 4.8 2.6 A16 16 0.075 0.01 a 200 5.1 2.7 A17 17 0.075 0. 02 a 250 5.3 3.2 A18 18 0.075 0.03 a 300 6.1 4.6 A19 19 0.1 0.0001 a 150 4.5 1.9 A20 20 0.1 0.0002 a 150 4.5 1.9 A21 21 0.1 0. 0005 a 150 4.5 1.9 A22 22 0.1 0.001 a 150 4.5 1.9 A23 23 0.1 0.002 a 150 4.5 1.9 A24 24 0.1 0.005 a 150 4.6 1.9 A25 25 0.1 0.01 a 200 5.0 2.2 A26 26 0.1 0.02 a 300 5.2 2.6 A27 27 0.1 0.03 a 350 6.2 6.0 A28 28 0.1 0.05 a 450 8.0 7.9 A29 29 0.1 0.1 a > 500 14.8 15.7 A30 30 0.15 0.0001 a 200 4.7 2.0 A31 31 0.15 0. 0002 a 200 4.7 2.0 A32 32 0.15 0 0005 a 200 4.6 2.0 A33 33 0.15 0.001 a 200 4.7 1.9 A34 34 0.15 0.002 a 200 4.8 1.9 A35 35 0.15 0.005 a 200 4.8 1.9 56 320647 200926207 [Table 13]

Sample No. Manufacturing Example Sn vs. Ba ratio Crystallization crystallization temperature CC) Resistivity at film formation (χ10'4 Ω · cm) Resistivity after annealing (χ10"4 Ω · cm) A36 36 0.15 0.01 a 250 4.9 2.3 A37 37 0.15 0. 02 a 350 5.6 5.5 A38 38 0.15 0.03 a 400 6.4 6.3 A39 39 0.15 0.05 a >500 8.6 8.3 A40 40 0.2 0.00006 a 250 4.7 2.2 A41 41 0.2 0.0001 a 250 4.8 2.0 A42 42 0.2 0. 0002 a 250 4.7 2.0 A43 43 0.2 0. 0005 a 250 4.8 2.1 A44 44 0.2 0.001 a 250 4.8 2.1 A45 45 0.2 0.002 a 250 4.9 2.2 A46 46 0.2 0.005 a 250 5.2 2.2 A47 47 0.2 0.01 a 350 5.4 5.1 A48 48 0.2 0.02 a 350 6.0 6.0 A49 49 0.2 0.03 a 450 6.7 6.6 A50 50 0.2 0.05 a >500 9.0 10.0 A51 51 0.22 0. 00005 a 250 4.7 2.1 A52 52 0.22 0. 0033 a >500 8.3 6.4 A53 53 0. 25 0.0001 a 250 5.5 2.2 A54 54 0. 25 0. 0002 a 350 5.6 5.2 A55 55 0.25 0.0005 a 350 5.7 5.1 A56 56 0.25 0.001 a 350 5.8 5.2 A57 57 0.25 0,002 a 350 5.8 5.2 A58 58 0.25 0. 005 a 350 5.9 5.4 A59 59 0.25 0.01 a 400 6.0 6.0 A60 60 0.3 0. 0001 a 350 6.6 6.0 A61 61 0 .3 0.0002 a 350 6.3 6.0 A62 62 0.3 0.0005 a 350 6.2 5.9 A63 63 0.3 0. 001 a 400 6.2 5.9 A64 64 0.3 0. 002 a 400 6.3 6.1 A65 65 0.3 0.005 a 400 6.3 6.2 A66 66 0.3 0.01 a 450 6.3 6.4 A67 67 0.3 0.02 a >500 7.8 6.9 (Reference Examples B1 to B67) The sputtering targets of each of the reference manufacturing examples 1 to 67 were respectively mounted on a 4 吋 57 320647 200926207 DC magnetron splash device' The temperature was kept at room temperature (about 2 Torr. 〇, the water pressure is set to l.〇xl〇-3Pa, and the oxygen partial pressure (equivalent to 0 to 1. lxl〇-2pa) is changed between 〇 and 3 〇sccln, and the transparency of the reference examples B1 to B67 is obtained. Conductive film. The spatter condition is as follows, whereby a film having a thickness of 2 〇〇A can be obtained. Dry material size: φ=4ίη· t=6mm Sputtering method: DC magnetron sputtering device Exhaust device: Rotary pump + freezing vacuum pump Reaching degree of vacuum: 5. 3xlO_6[Pa]

Ar pressure: 4. OxlOlPa] Oxygen pressure: 〇 to 1. 1x10-2[pa] Water pressure: l. 〇xl〇-3 [Pa] Substrate temperature: room temperature 贱 plating power: .130W (power density is 1.6W /cm2) Substrate: Corning #1737 (glass for liquid crystal display) t=〇.8mm ❹ For Reference Examples B1 to B67, the relationship between the oxygen partial pressure and the resistivity at room temperature film formation is obtained, and The relationship between the partial pressure of oxygen after annealing and the resistivity after 2501. Tables 14 and 15 below show the molar ratio of Ba and Sn to 1 mol of I η for each sample, and the crystal state at room temperature film formation (the amorphous film is denoted as a 'crystallized film is denoted as c ) 'and the crystallization temperature of the amorphous film. The crystallization temperature, the resistivity at the time of film formation, and the resistivity after annealing are as follows. In addition, in the 33rd drawing, reference examples B1 to B67 are drawn, and the knots of 320647 58 200926207 are 100 to 300 ° C, and the crystallization temperature is 35 (the above rc is known from the results, crystallizing The temperature is 30 (the range below rc, which is the molar ratio of tin to y (mole) of indium to 1 mol, which is expressed by the molar ratio X of indium to ym. The range of lxl〇-2Ln(x)-2. 6x1ο-1) is equal to or less than the value of (-7. ΙχΙΟ^ιΚχΗΙ.βχΙίΓ1). Ο ❹ 320647 59 200926207 [Table 14]

Sample No. Production example Sn ratio of Ba to crystal state crystallization temperature (°C) Resistivity at the time of film formation (χ10'4 Ω · cm) Resistivity after annealing (χ10'4 Ω · cm) B1 1 0 0.1 a > 500 20.2 22.3 B2 2 0.025 0.07 a >500 13.0 14.8 B3 3 0.025 0.1 a >500 16.2 18.4 B4 4 0.05 0.0001 a 200 4.7 3.5 B5 5 0.05 0. 0002 a 200 4.8 3.5 B6 6 0. 05 0. 0005 a 200 4.9 3.5 B7 7 0.05 0.001 a 200 4.9 3.4 B8 8 0.05 0.002 a 200 4.9 3.5 B9 9 0.05 0.005 a 200 5.0 3.6 BIO 10 0.05 0.01 a 200 5.4 3.6 Bll 11 0. 05 0.02 a 250 5.5 4.8 B12 12 0. 05 0.03 a 350 6.3 6.2 B13 13 0.05 0.05 a 450 8.6 9.3 B14 14 0.075 0.002 a 200 4.8 2.6 B15 15 0.075 0.005 a 200 4.9 2.7 B16 16 0. 075 0.01 a 250 5.2 2.8 B17 17 0.075 0.02 a 350 5.4 5.2 B18 18 0.075 0.03 a 400 6.2 5.9 B19 19 0.1 0.0001 a 200 4.5 2.1 B20 20 0.1 0.0002 a 200 4.5 2.0 B21 21 0.1 0.0005 a 200 4.6 2.1 B22 22 0.1 0.001 a 200 4.6 2.1 B23 23 0.1 0.002 a 200 4.7 2.1 B24 24 0.1 0.005 a 200 4.8 2.2 B25 25 0.1 0.01 a 250 5.1 2.4 B26 26 0.1 0. 02 a 350 5.6 5. 4 B27 27 0.1 0.03 a 400 6.2 6.0 B28 28 0.1 0.05 a 500 8.4 8.7 B29 29 0.1 0.1 a >500 15.0 16.0 B30 30 0.15 0.0001 a 250 4.6 2.2 B31 31 0.15 0.0002 a 250 4.7 2.0 B32 32 0.15 0: 0005 a 250 4.7 2.2 B33 33 0.15 0.001 a 250 4.7 2.1 B34 34 0.15 0.002 a 250 4.9 2.2 B35 35 0.15 0.005 a 250 5.0 2.3 60 320647 200926207 [Table 15]

Sample No. Production example Sn ratio Ba ratio crystal state crystallization temperature 电阻 Resistivity at film formation (χ10'4 Ω · cm) Resistivity after annealing (χ10_4 Ω · cm) B36 36 0.15 0.01 a 350 5.2 5.1 B37 37 0.15 0.02 a 400 6.1 6.1 B38 38 0.15 0.03 a 450 6.6 6.4 B39 39 0.15 0.05 a >500 8.7 8.9 B40 40 0.2 0.00006 a 300 4.9 2.4 B41 41 0.2 0.0001 a 300 4.7 2.3 M2 42 0.2 0.0002 a 300 4.8 2.1 B43 43 0.2 0 0005 a 300 4.9 2.3 B44 44 0.2 0.001 a 300 4.8 2.3 B45 45 0.2 0.002 a 300 5.0 2.3 B46 46 0.2 0.005 a 350 5.2 5.1 B47 47 0.2 0.01 a 400 5.5 5.1 B48 48 0.2 0.02 a 400 7.3 6.8 B49 49 0.2 0.03 a 500 7.0 6.9 B50 50 0.2 0. 05 a >500 9.3 10.2 B51 51 0.22 0.00005 a 300 4.8 2.3 B52 52 0.22 0. 0033 a >500 8.4 6.5 B53 53 0.25 0.0001 a 350 6.1 5.8 B54 54 0.25 0. 0002 a 350 6.1 5.9 B55 55 0.25 0.0005 a 400 6.2 5.9 B56 56 0.25 0.001 a 400 6.2 6.0 B57 57 0.25 0. 002 a 400 6.2 6.1 B58 58 0.25 0.005 a 400 6.2 5.9 B59 59 0.25 0.01 a 450 6.1 6.1 B60 60 0.3 0 0001 a 400 6.8 6.5 B61 61 0. 3 0. 00 02 a 400 6.7 6.4 B62 62 0.3 0. 0005 a 400 6.7 6.6 B63 63 0.3 0.001 a 450 6.7 6.6 B64 64 0.3 0.002 a 450 6.8 6.4 B65 65 0.3 0.005 a 450 6.9 6.8 B66 66 0.3 0.01 a 500 7.0 7.0 B67 67 0.3 0.02 a >500 8.2 7.5 (Reference Examples C1 to C67) The sputtering targets of each of Reference Manufacturing Examples 1 to 67 were respectively mounted on a 4 吋 61 320647 200926207 » DC magnetron sputtering device to maintain the substrate temperature at The room temperature (about 20 ° C), the water pressure is set to 1. 0xl (T5Pa ' and 0 to 3. 0sccin change the oxygen partial pressure (equivalent to 0 to 1. lxl 〇 -2pa) ' and obtain a reference example A transparent conductive film of C1 to C67. The sputtering conditions were as follows, whereby a film having a thickness of 1200 A was obtained. Target size: Φ=4ίη. t=6mm Splash mode: DC magnetron sputtering device Exhaust device: Rotary pump + Freezer vacuum pump ® Reach vacuum: 5. 3xlO_6[Pa]

Ar Pressure: 4. OxlOlPa] Oxygen pressure: 0 to 1· lxl〇_2 [Pa] Water pressure: 1. OxlO_5 [Pa] Substrate temperature: room temperature sputtering power: 130W (power density is 1.6W/cm2) Substrate. Corning #1737 (glass for liquid crystal display) t = 0. 8nnn ❹ For Reference Examples C1 to C67, the relationship between the oxygen partial pressure and the resistivity at room temperature film formation, and 250 are obtained. (: relationship between oxygen partial pressure after annealing and resistivity. Tables 16 and 17 below show the molar ratio of Ba and Sn to 1 mol of I η for each sample, and film formation at room temperature. The state of the crystal (the amorphous film is denoted by a 'crystallized film denoted as c), and the crystallization temperature of the amorphous film is shown. The crystallization temperature, the resistivity at the time of film formation, and the electric enthalpy after annealing are as follows. The sputtering target of each reference manufacturing example to 67 was used to determine the partial pressure of oxygen at room temperature (about 62 320647 200926207 20 ° C) and the resistivity of the film formed at the partial pressure. The relationship between the optimum oxygen partial pressure and the relationship between the electrical resistivity and the film formation oxygen partial pressure after annealing the film formed at each partial pressure of oxygen at 250 ° C, after annealing The resistivity becomes the lowest partial pressure of oxygen, and is the optimum oxygen partial pressure at the time of film formation at 250 ° C. Based on this, it is judged whether the optimum oxygen partial pressures of the two are different, and the difference is #, and almost the same is ▲, The results are shown in Figure 34. From the results, it can be seen that when tin is 1 molar in indium molar ratio y (moule), For a molar ratio of 1 mol of indium to X (-2. 9xl0_1 Ln(x) - 6.7xl (T2) or more, at (-2. 0xl0_1Ln(x)-4. 6xl0-1) When the value is below the range of y = 0, the film-forming oxygen partial pressure of the amorphous film after film formation becomes low resistance, and the film partial pressure of oxygen which becomes low resistance after annealing is different, or 250 ° C The optimum partial pressure of oxygen is different from the optimum partial pressure of oxygen at room temperature. That is, in these composition ranges, the optimum partial pressure of oxygen is not obtained from the resistivity of the film immediately formed, but the film is crystallized after annealing. It is more desirable to form a film under the oxygen partial pressure of the lowest φ resistance, and the film after annealing has a lower resistivity, which is more desirable. Further, it is known that the molar ratio of tin to 1 mol of indium is y (mole ), in the range of the value of -2. 9xl (T2Ln(x) -6.7xl0_2) expressed by the molar ratio of indium to 1 mol of indium, the crystallization temperature is smaller than 100 ° C On the other hand, referring to Fig. 32 and Fig. 33, it can be seen that even when tin is applied to a specific range to form a film, even if tin is in a molar ratio of 1 mol of indium to y (mole), it is located. One to one In the range of 63 320647 200926207 (-2. 9xl (T2Ln(x)-6. 7χ1(Γ2)), the crystallization temperature is also higher than 150 °C, and it is easy An amorphous film is formed. That is, as shown in Fig. 32 and Fig. 33, when the water pressure is 1. Oxl0_4 Pa or more, film formation is performed, and substantially does not exist as shown in Fig. 34. When the state of the water is less than 1. Oxl 0 - 4 Pa, it is preferable to form a film at a water pressure of 1.0 x x 0_5 Pa or less, and the crystallization temperature of the amorphous film can be increased. In addition, especially in the absence of water in the substantial absence of water, the crystallization temperature is less than 100 ° C, and the molar ratio of tin to 1 mol of indium is y (moule), located in 钡 to 1 mol of indium In the range below the value of (-2. 9x10 - 2 Ln(x) - 6.7xl0_2) expressed by the molar ratio X, even if the crystallization temperature is in a range lower than 100 ° C, the crystallization temperature becomes 100. Above °C, it is more desirable to have a high temperature of 150 ° C, so that an amorphous film can be easily formed. 64 320647 200926207 [Table 16]

Sample No. The production example Sn is crystallized in a crystal state than Ba, and the temperature (°C) is a resistivity at the time of film formation (χ10'4 Ω·cm). The electrical resistivity after annealing (χ10'4 Ω·cm) Cl 1 0 0.1 a &gt ;;;;;;;;;;; 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ;100 4.2 3.4 Cll 11 0.05 0. 02 a 150 5.0 4.9 Cl 2 12 0. 05 0.03 a 200 7.5 6.2 C13 13 0.05 0. 05 a 400 8.2 9.2 C14 14 0.075 0,002 c <100 3.3 2.1 C15 15 0.075 0.005 c <100 3.3 2.1 C16 16 0.075 0. 01 a 100 4.2 3.1 C17 17 0.075 0.02 a 150 5.1 3.5 C18 18 0.075 0. 03 a 250 6.7 5.1 C19 19 0.1 0. 0001 c <100 4.3 1.8 C20 20 0.1 0. 0002 c <100 4.3 1.8 C21 21 0.1 0. 0005 c <100 4.3 1.8 C22 22 0.1 0.001 c <100 4.3 1.8 C23 23 0.1 0.002 c <100 4.3 1.8 C24 24 0.1 0.005 a 100 4.3 1 .8 C25 25 0.1 0.01 a 150 4.7 2.3 C26 26 0.1 0. 02 a 200 5.5 2.7 C27 27 0.1 0. 03 a 250 6.1 4.6 C28 28 0.1 0. 05 a 400 8.6 10.0 C29 29 0.1 0.1 a >450 14.2 15.3 C30 30 0.15 0. 0001 c <100 4.6 1.8 C31 31 0.15 0. 0002 c <100 4.6 1.8 C32 32 0.15 0. 0005 c <100 4.6 1.8 C33 33 0.15 0.001 a 150 4.6 1.8 C34 34 0.15 0.002 a 150 4.6 1.8 C35 35 0.15 0. 005 a 150 4.6 1.8 65 320647 200926207 [表Π]

Sample No. Production example Sn ratio Ba ratio crystal state crystallization temperature CC) Resistivity at film formation (χ10'4 Ω · cm) Resistivity after annealing (χ10"*Ω · cm) C36 36 0.15 0.01 a 200 5.0 2.1 C37 37 0.15 0.02 a 250 6.0 2.6 C38 38 0.15 0.03 a 350 6.9 5.9 C39 39 0.15 0.05 a >450 8.6 8.1 C40 40 0.2 0.00006 c <100 4.8 1.9 C41 41 0.2 0.0001 a 150 4.8 1.9 C42 42 0.2 0.0002 a 150 4.8 1.9 C43 43 0.2 0. 0005 a 150 4.8 1.9 C44 44 0.2 0.001 a 200 4.8 1.9 C45 45 0.2 0.002 a 200 4.8 1.9 C46 46 0.2 0.005 a 200 5.2 1.9 C47 47 0.2 0.01 a 200 5.8 2.4 C48 48 0.2 0.02 a 250 6.7 3.0 C49 49 0.2 0. 03 a 400 8.0 6.2 C50 50 0.2 0.05 a > 450 10.1 9.8 C51 51 0. 22 0.00005 a 100 4.9 2.0 C52 52 0.22 0. 0033 a 400 8.1 6.3 C53 53 0.25 0.0001 a 250 4.7 2.1 C54 54 0.25 0.0002 a 250 4.7 2.1 C55 55 0.25 0. 0005 a 250 4.7 2.1 C56 56 0.25 0.001 a 250 4.7 3.6 C57 57 0.25 0.002 a 300 5.7 5.1 C58 58 0. 25 0.005 a 300 5.7 5.3 C59 59 0.25 0.01 a 300 6.0 5.9 C60 60 0.3 0.0001 a 300 5.3 4.3 C61 61 0.3 0 .0002 a 300 5.3 4.3 C62 62 0.3 0.0005 a 300 5.3 4.3 C63 63 0.3 0.001 a 300 5.3 4.3 C64 64 0.3 0.002 a 300 5.4 4.4 C65 65 0.3 0.005 a 350 5.7 4.7 C66 66 0.3 0.01 a 400 6.2 5.1 C67 67 0.3 0.02 a 450 7.8 6.0 (Presence confirmation test of hydrogen) The sputtering target of Reference Example 13 was separately mounted on a 4 吋 DC magnetic 66 320647 200926207 controlled ore device ' _ Keep the substrate temperature at room temperature (about 2 〇 °C), and the water pressure is set to 1. 〇xl (T2Pa (as reference test example D, 5. 〇xl〇-3Pa (as reference test example 2), 5. 0x10 5Pa (as reference test example 3) Under the conditions, the transparent conductive films of Reference Test Examples 1 to 3 were obtained. The sputtering conditions are as follows. Thus, a film having a thickness of 1200 A can be obtained.萆Ba material size: φ=4ίη. t=6mm Sputtering method: DC magnetron sputtering device Exhaust device: Rotary pump + cold bead vacuum pump ❾ Reach vacuum: 5. 3xl (T5[Pa]

Ar pressure: 4. OxlOlPa] Oxygen pressure: 0 [Pa] Water pressure: 1. ΟχΠΓ2, 5. 0χ1 (Γ3, 5. Oxl〇-5[pa:] Substrate temperature: room temperature sputtering power: 130W (power density 1.6W/, cm2) Using a substrate · Corning #1737 (glass for liquid crystal display) t=〇❹ The crystal state of the sample formed under each condition was analyzed by thin film XRD, and it was confirmed that the reference test example was used. It is amorphous in 1, 2, and is crystallization in Reference Test Example 3. '

Further, for the presence of hydrogen in each film, a time-of-flight secondary ion mass spectrometry (TRIF IV manufactured by TOF-SIMS ULVAC PHI Co., Ltd.) 'samples of reference test examples 1 to 3' was used as follows. The measurement conditions were compared and the detected (H+ ion number) / (total ion number) was confirmed. [Measurement conditions] Primary ion: Au+ 320647 67 200926207 Accelerating voltage: 30 kV Scanning conditions: Grating scanning No. 18 indicates the tof-SIMS analysis result of the film-formed sample (counting value of mineral ions) / (total ion count) Value). Here, in the sample of Reference Test Example 3 in which the water-forming pressure at the time of film formation is 5.0. 0xl0-5Pa in the absence of water, the H+ ion is detected, but this can be judged as the base value. . That is, in a recent study, it has been proposed to detect a H+ ion in an indium oxide film formed under a partial pressure lower than that of Reference Example 3 (jpn·j. Appi. Phys., v 〇1. 46' No. 28' 2007, pp. L685-L687), it can be inferred that the detected hydrogen ions enter the film from a small amount of moisture adhering to the substrate at the time of film formation. Therefore, in the invention of the present application, the water pressure in an environment in which water is substantially absent is (H+ ion number) / (total ion) of a film formed in an environment of 〇xl〇-5pa or less 7. 75χ1〇-4 is the reference value, and the (Η+ion number)/(total ion number) added by this value is used as the hydrogen ion contained in the film. Therefore, when the (11+ ion count value) 〆 (the total ion count value) of Reference Test Examples 1 to 3 is compared, it is known that the value is increased as the water pressure at the time of film formation increases. As shown in Reference Test Examples 2 and 2, it was confirmed that the moisture formed in the film can be changed by controlling the water pressure at the time of enthalpy, and the hydrogen entering the film can be presumed to be The hydrogen bond is formed by a dangling bond (unbonded bond) of an atom in the film, and has an effect of inhibiting crystallization of the film. The above measurement results indicate that the additive element is Ba, but even if 320647 68 200926207 is another additive element having an oxygen bonding energy in the range of 100 to 350 kj/mol, 'by controlling the water pressure at the time of film formation, The amount of hydrogen formed by the ingress of moisture into the membrane is altered. [Table 18] Water pressure at the time of film formation [Pa] H+ ion number/total ion number measurement result (measurement result) - (reference value) Reference test example 1 1. Oxl 0'2 9. 18x10] 1.43xl0'4 Reference test Example 2 5. OxlO'3 8. 98xl0'4 1.23X10·4 " Reference test example 3. 5. Oxl〇·5 7. 75x10-4 0. o〇xi〇-° ❹ [Simplified description] 1st Figures (a) to (c) are graphs showing the relationship between the oxygen partial pressure and the specific resistance of Test Examples 1 to 3 of the present invention. Fig. 2 (a) and (b) are graphs showing the relationship between the oxygen partial pressure and the specific resistance of Test Examples 4 to 5 of the present invention. Fig. 3 (a) and (b) are graphs showing the relationship between the oxygen partial pressure and the specific resistance of Test Examples 6 to 7 of the present invention. Fig. 4 (a) and (b) are graphs showing the relationship between the oxygen partial pressure and the specific resistance of Test Examples 8 to 9 of the present invention. Fig. 5 (a) and (b) are views showing the relationship between the oxygen partial pressure and the specific resistance of Reference Examples 丨 to 2 of the present invention. Fig. 6 (a) and (b) are graphs showing the relationship between the oxygen partial pressure and the specific resistance of Reference Examples 3 to 4 of the present invention. Fig. 7 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of the comparative example of the present invention. 320647 69 200926207 shows the oxygen partial house of Test Example 10 of the present invention and resistivity

Fig. 11 is a graph showing the relationship between the oxygen partial pressure of Test Example 13 and the resistivity of Fig. 8 of the present invention. A diagram of the relationship between them. Fig. 12 is a view showing the relationship between the oxygen partial pressures of Reference Example 5 of the present invention. Fig. 13 (a) to (c) are views showing a film XRD pattern before and after annealing of Test Examples 丨 to 3 of the present invention. Fig. 14 (a) and (b) are views showing the film XRD pattern before and after annealing of Test Examples 4 to 5 of the present invention. Fig. 15 (a) and (b) are views showing a film XRD pattern before and after annealing φ of Test Examples 6 to 7 of the present invention. Fig. 16 (a) and (b) are views showing a film XRD pattern before and after annealing of Test Examples 8 to g of the present invention. Fig. 17 (a) and (b) are views showing a film XRD pattern before and after annealing of Reference Examples 1 to 2 of the present invention. Fig. 18 (a) and (b) are views showing a film XRD pattern before and after annealing of Reference Examples 3 to 4 of the present invention. Fig. 19 is a view showing a film XRD pattern before and after annealing of Comparative Example 1 of the present invention. 70 320647 200926207 Fig. 20 (a) to (c) are views showing transmission spectra before and after annealing of Test Examples 1 to 3 of the present invention. Fig. 21 (a) and (b) are views showing transmission spectra before and after annealing of Test Examples 4 to 5 of the present invention. Fig. 22 (a) and (b) are views showing transmission spectra before and after annealing of Test Examples 6 to 7 of the present invention. Fig. 23 (a) and (b) are views showing transmission spectra before and after annealing of Test Examples 8 to 9 of the present invention. Fig. 24 (a) and (b) are views showing transmission spectra before and after annealing of Reference Examples 1 to 2 of the present invention. Fig. 25 (a) and (b) are views showing transmission spectra before and after annealing of Reference Examples 3 to 4 of the present invention. Fig. 26 is a view showing the transmission spectrum before and after annealing of Comparative Example 1 of the present invention. Fig. 27 is a view showing the results of the Sr-containing transparent conductive film of the present invention. Fig. 28 is a view showing the results of the Li-containing transparent conductive film of the present invention. Fig. 29 is a view showing the results of the La-containing transparent conductive film of the present invention. Fig. 30 is a view showing the results of the Ca-containing transparent conductive film of the present invention. Fig. 31 is a view showing the results of the Sr, Li, La, Ca transparent conductive film of the present invention. Fig. 32 is a graph showing the crystallization temperatures of Reference Examples A1 to A67 of the present invention. Fig. 33 is a graph showing the crystallization temperatures of Reference Examples B1 to B67 of the present invention. 71 320647 200926207 Figure 34 is a graph showing the crystallization temperatures of Reference Examples C1 to C67 of the present invention. [Main component symbol description] None. 〇 ❹ 72 320647

Claims (1)

200926207 VII. Patent application scope: 1. A transparent conductive film which is formed by using a sputtering target having an oxide sintered body, the oxide sintering system containing indium oxide and the necessary tin, and 1 mole The indium contains 0.0001 moles or more and less than 0. 10 moles of oxygen bonding energy in the range of 100 to 350 kJ / mol of the addition of elements (except Ba (钡), Mg (town), Y (Ji)), It is characterized by containing indium oxide and the necessary tin, and contains the aforementioned additive elements. 2. The transparent conductive film of claim 1, wherein the aforementioned additive element is selected from the group consisting of Sr, Li, La, and Ca (J bow). At least one of them. 3. The transparent conductive film of claim 1 is formed by using a sputter target having 0 to 0.3 m of tin in 1 m of indium. q. The transparent conductive film of claim 2, wherein a film of a sputtering target containing 0 to 0.3 m of tin is used. 5. The transparent conductive film of claim 2, wherein the molar ratio y of tin to 1 mol of indium is represented by the molar ratio X of indium added by the aforementioned additive element to 1 mol ( -9.3xlO_2Ln(x)-2. The value of lx 10' is not less than the value of (-2. 5xlO_1Ln(x)-5.TxltT1). 6. The transparent conductive film of claim 3, Wherein, tin to 1 73 320647 200926207 Mohr indium molar ratio y, is expressed by the molar ratio x of the aforementioned additive element to 1 mol face (-9. 3x10-2Ln(x)-2 The range of lx ΗΓ1) is equal to or less than the value of (_2· 5x1 〇_1Ln(x)-5. 7x1ο-1) 7. Ο 8. 9. ❹ 10. If the scope of patent application is 4 a transparent conductive film in which the molar ratio y of indium to tin of j-mole is expressed by the molar ratio X of the above-mentioned additive element to 1 mol of steel (-9.3 x 1 (T2Ln(x)-2) a range of lx 1 〇 ' or more and a value below (-2.5 乂 10 9 11 (^) - 5.7 乂 10-1). The transparent conductive film of claim 2, wherein the aforementioned addition 70 Sr, Sr, tin to 1 molar indium molar ratio y , is located above the value of Sr to 1 mol of indium molar ratio x (_4. lxl〇-2Ln(x) 9.2 parent 1〇) and is (_2 9><1〇9 11( A range of the following: The transparent conductive film of the third aspect of the patent application, wherein the addition of the bismuth is Sr, and the tin is 1 ohm of indium. Moerby y, which is located above the value of (-4. lxl〇-2Ln(X) -9.2x10 2) expressed by 讣 to 1 molar of indium, and is (_2. 9xl〇- lLn(x) 6·7χΐ(Γΐ) The range below the value of the transparent conductive film of the fourth aspect of the patent application, wherein the additive element is Sr, tin to 1 molar indium molar ratio y, It is located above the value of (_4. lxl〇-2Ln(x)~9.2xio2) expressed by the molar ratio x of the pair of 1 moles and is equal to or less than the value of (_2 9χ1〇'η(χ)_6 320647 74 200926207. A transparent conductive film according to item 2 of the patent scope of the invention, wherein the aforementioned additive element is a molar ratio y of Ll 'tin to 1 mol of indium, which is located at a ratio of Li to 1 mol. The molar ratio of indium to x is greater than the value of (-1.6χ1〇Λη(χ) 5· 9x10 ) and is ( _2 5 χΐ〇 χ χ — 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. 12. The value of (-UxliTLnOO 5. 9x10 ) expressed by Li ❹ Ο to 1 mol of indium molar ratio X is (1). (1) A range below one value. 13. The transparent conductive film of item 4 of the sf patent scope, wherein the aforementioned addition = prime is a molar ratio y of U'tin to 1 mol of indium, which is located in the indium of Li = 1 mol. The range of (1).6xiG_lLn(1).9x10) is greater than or equal to the value of (_2. 5χΐ〇, (1)-. 14) The transparent conductive film of item 2 of the second patent, wherein the aforementioned position f ' '/ + La35 to 1 mol of indium molar ratio y, which is expressed by the molar ratio X of I S S (-6.7xl (T2Ln〇i .2x10) and above (1) 3χ1 ( Γΐΐη(1)_7 is a range of the following values: The transparent conductive film of the third item of the present invention, wherein the molar force y of the aforementioned inotropic force to Zengxi to 1 mol of indium is located in the indium of L 2 2 i = The ear is expressed by X (~6.7xlir2Ln(x)) and is (-3.3XlrLn(xM.7x10, 320647 75 200926207 -»). 16. Transparent conductive film as in claim 4 Wherein, the aforementioned addition of halogen is U, and the molar ratio y of tin to 1 mol of indium is represented by a molar ratio of La to 1 mol of indium (-6. 7xl (r2Ln(x) ) 2·2x1ο ) The value is equal to or greater than the value of (_3.) 17. The transparent conductive film of claim 2, wherein the addition of ❹70 is Ca, and the molar ratio of tin to 1 mol of indium is y, It is located above the value of (_4.lxl〇_2Ln(x) 9· 3x10 ) expressed by Ca to 1 莫, and is less than or equal to (_2. 5χ1〇iLncymo-i). 18. The transparent conductive film of claim 3, wherein the added halogen is a molar ratio y of Ca'tin to 1 mol of indium, and is located in the indium of Ca to 1 mol. The range of (_4.1χ1οΛη(χ) -9. 3x10 2) expressed by the molar ratio _x is equal to or less than the range of (_2. 5xl〇-lLn(x)_5·7χΐ(Γΐ). The transparent conductive film of claim 4, wherein the aforementioned added halogen is Ca, and the molar ratio y of tin to 1 mol of indium is in the molar ratio of Ca to 1 mol. The range of i (_41xl0-2Ln(x) 9.3x10) is not less than the value of (_2·5xl〇-iLn(x)_5. 7x1^). 20·If the patent application range is from 19th to 19th a transparent conductive film of any one of which is attached to water 1. 0xl〇 pressure-4Pa above deposition by Shu .〇χ1 square-lpa under the following conditions. 32064776 200 926 207 21. Patent application range of the transparent conductive film of the first 2〇 item, which contains hydrogen-based person. The transparent conductive film according to any one of claims 1 to 19, wherein after the film is formed as an amorphous film, it is crystallized by annealing. 23. The transparent conductive film of claim 2, wherein after the film of the amorphous film is formed, it is crystallized by annealing. 24. The transparent conductive film of claim 21, wherein after the film of the amorphous film is formed, it is crystallized by annealing. 25. The transparent conductive film of claim 22, wherein the crystallization by the annealing is from 100 to 300. 26. The transparent conductive film of claim 23, wherein 'the crystallization of the foregoing annealing is performed in 100 to 300 t: 27. The transparent conductive film of claim 24, The crystallization by the annealing is performed at 100 to 300 ° C. The method for producing a transparent conductive film is characterized in that a sputtering target having an oxide sintered body is used to form a film. The bismuth oxide sintering system contains indium oxide and the necessary tin, and the indium of 1 mol contains 〇. 0001 mol or more and is less than 〇. 10 mol oxygen bond is in the range of 100 to 350 kJ/m 〇 1 The addition of elements (except Ba, Mg, γ), thereby obtaining indium oxide and the necessary tin, and containing the former Cheng 夭 丈 兀 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 29 29 29 The scope of the patent is found in the rain, and it is formed by the method of water (4) turning the lead (4). The film is formed under the film. ^心上^❿The following is 320647 77 200926207 30. The manufacturing method of the transparent conductive film of claim 28 The system is amorphous After the film is formed, the crystallized transparent conductive film is formed by annealing. 31. The method for producing a transparent conductive film according to claim 29, which is formed by annealing to form a crystallized film. 32. A method of producing a transparent conductive film according to claim 30, wherein the amorphous film is etched with a weakly acidic etchant, and then tempered by annealing. The method for producing a transparent conductive film according to claim 31, wherein the amorphous film is etched by a weakly acidic money etchant, and then annealed to crystallize the film. The method for producing a transparent conductive film according to any one of items 30 to 34, wherein the crystallization by the annealing is performed at 100 to 300 ° C. ❹ 78 320647