TW200927972A - Method for making indium oxide tranparent conductive film - Google Patents

Abstract

This invention provides a method for making a transparent conductive film, which is formed by using a sputtering target having a sintered oxide which contains indium oxide, and optional tin, and an additive element, and the amorphous film is formed under a condition that the water partial pressure being 1. 0x10<SP>-5</SP>Pa or less.

Description

200927972 VI. Description of the Invention: [Technical Field] The present invention relates to a film having a uniform amorphous film which can be easily patterned by weak acid etching = patterning A method of producing a transparent conductive film which is crystallized and becomes a low electric resistance and high transmittance after crystallization. [Prior Art] Since indium oxide-tin oxide (composite oxide of In2〇3_Sn〇2, the following, © _"ITG") film is light-transmissive (four) high and highly conductive, it is widely used for liquid crystal display« It is known as a transparent conductive film, or a heat-radiating film for preventing binding condensation, an infrared reflecting film, etc., but it is difficult to form an amorphous film. As an amorphous film, an indium oxide-oxygen (10) transparent conductive film is known. Further, the present invention has previously proposed a method for producing an amorphous transparent conductive film which is formed by adding a shixi as a transparent conductive film to a film of ιτ〇 and forming a film according to a predetermined condition (refer to Patent U). Further, the applicant of the present invention has found that an indium oxide-based transparent conductive film to which ruthenium is added is an amorphous film having low resistance and excellent transparency, and can be filled by weak acid etching and more easily crystallized. The application has been filed previously (Japan's special wish 2007-095783). For the grinding of such an amorphous film by sputtering, the general method is to introduce the argon gas (Ar) as an inert gas into the vacuum reached by the full management while controlling The resistivity and the osmotic pressure of the osmotic pressure of the ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ When a non-uniform film having such a streak is patterned by wet etching using a weak acid such as oxalic acid, etching residue is generated to cause a problem of a decrease in yield. There is also the problem of inconsistent crystallization temperature due to annealing in the annealing. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-135649 (Patent Application) [Description of the Invention] In view of the above circumstances, an object of the present invention is to provide a method for producing a transparent conductive film. The entire film is a uniform amorphous film and can be easily patterned by weak acid etching, and can be easily crystallized, and becomes a low-resistance and two-transmissive transparent conductive film after the formation. .

[Means for Solving the Problem] The inventors of the present invention have obtained the results of intensive studies in order to solve the above problems, and when the amorphous indium oxide-based transparent conductive film is formed by the addition of an additive element, for example, a film surface When the reaction between the water and the oxygen as the reactive gas is not uniform, the present invention can be finally obtained by not obtaining an amorphous state in which the entire film is uniform, and a film having low resistance and excellent transparency. x is also known in the 'sputtering chamber', because the residual gas partial pressure decreases with the exhaust time, and the moisture originating when the substrate such as glass is transported into the vacuum chamber The influence of adsorption gas, etc., so that the environment will change greatly, but the change of 320653 4 200927972 in this environment, especially the residual water will have a great influence on the film formation of the amorphous film as described above, so that it becomes uneven. The reason for success. Further, it has been found that, in particular, in a large-scale sputtering apparatus, "in order to form a film on a large-sized glass substrate, the amount of water carried in transporting the substrate into the vacuum chamber is increased, and the adsorption of water in the substrate becomes In the case of unevenness, uneven reaction or temperature unevenness between the water and the reactive gas occurs, so that unevenness occurs in the residual property. According to the present invention, the present invention can be formed by controlling the partial pressure of water to a low value below a predetermined value, thereby forming a film of an amorphous crucible which is uniform throughout the crucible, thereby being capable of being etched by weak acid. Patterning is easy and uniform, and it is easier to crystallize the film. The first aspect of the present invention is a method for producing a transparent conductive film, which is characterized in that a sputtering target having an oxide sintered body containing a combination of indium oxide and tin as needed while containing an elemental oxide is used. When a film is formed, and a transparent conductive film containing indium oxide and tin is contained at the same time as needed, and an element is added and is amorphous, the partial pressure of water at the time of film formation is made into lxi〇-5pa ( Pascal) below. In the first state, since the partial pressure of water is controlled to be equal to or lower than a predetermined value, tT is formed into a film of an amorphous film in which the entire film is uniform. The second embodiment of the present invention is a method for producing a transparent conductive crucible according to the first aspect, wherein the amorphous conductive film is formed into a crystallized transparent conductive film by annealing treatment. In the second state, after the film is formed into an amorphous film, the crystallization is easily crystallization by annealing, and it is made weak in acidity. 5 320653 200927972 Transparent guide 3:! Party: such as: to the 3rd - state - since _) rotten coffee and touch group (=::tL scratch (four)), two 1 = if used "1", [Effect of the invention] The addition of %" can be used to form an amorphous film. 时 When an eight-knee amorphous transparent conductive film containing water containing indium oxide and tin at the same time is required, The film forming body is all equal to i xi = xi 〇 5pa, and can be used to create a kind of versatility, and can be easily 透明 'transparent conductive effect which can be easily patterned by weak acid etching. Crystallization, After crystallization, it has low resistance and high transmittance. [Embodiment;] 透明 Transparent conductive film used for epoxidized indium-based transparent conductive film and containing added element hypoxic steel as the main body. t : sintered body, added element, as long as it maintains the state &amp; solid bath (_d here, add elements and ί, ΎΤ to limit. etc.:: and two: can be illustrated · · bSiWLi'u, The film formation of the film." Adding the addition of elements, and achieving the amorphous mole above the indium 1 molar content is preferably 0.000 1 mole above not reached 〇1〇320653 200927972 Moer, better for Ο. Just 2 is suitable for the range. If less than this amount, up to two, the dance is more than this amount, then ^, then add The effect is not significant. In addition, the yellow condition will become the increase of the resistance of the transparent conductive enamel and the addition of the charged film; the transparent content of the yin containing #钱(四) will be the same content. ', for the sputtering target used The content of the content of the kick is based on the sputtering target of the 莫 莫 Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo The density and mobility of the G.3 Moer range: The carrier electronic control sheep with proper control of 嶋 maintains good conductivity. In addition, if it is added, it will reduce the sputtering target. The mobility of the carrier electrons is the same as that of the conductivity deterioration. Here, the transparent conductive material formed by the sputtering target described above has the same content in the touch line _. a target having a resistance value capable of being deplated by DC (direct current) magnetron (magnetr〇n) Therefore, it is possible to perform sputtering with a relatively inexpensive DC magnetron ore, and of course, a high-frequency magnetron sputtering device can be used. If such a transparent conductive film is used for a sputtering target, an indium oxide transparent layer having the same composition can be formed. Conductive film. The composition analysis of such a ruthenium oxide-based transparent conductive film can be performed by ICP (inductively coupled plasma) after all the single film is dissolved, and the film itself becomes a component. Etc., if necessary, use a FIB (focused ion beam 'focused ion beam) or the like to cut a section of a similar section 'Using 7 320653 200927972 to SEM (Scanning electron microscope) or TEM (transmissive electron) Elemental analysis device (EDS (energy dispersive spectrometer)) or WDS (wavelength dispersive spectrometer, Auger electron spectroscopy, etc.) Can be specified.氧化 The indium oxide-based transparent conductive film produced by the present invention contains a predetermined amount of a predetermined additive element, and although it varies depending on the content, it is a temperature condition lower than a crystallization temperature at room temperature or higher ( For example, a temperature condition lower than 2 & £ &gt; c is preferably formed at a lower temperature than 15 (TC is a lower temperature condition, more preferably a lower temperature condition than 100 ° C). The film is formed in a state of a crystal shape. Further, such an amorphous film has the advantage of being able to be engraved with a weakly acidic etchant. Here, in the present specification, it is included in the patterning step. And used to obtain the established round case. ❾ , and: the resistivity of the obtained transparent conductive film ((10) state kiss), although due to the type of added elements, the summer heat ^ ^ (^ ~. In the case of the crystallization temperature of the ^ 经 经 经 经 经 经 经 经 经 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶Because of this; ^ 仃敎 processing, can be used in the case, can also be 'in the usual semiconductor In the temperature range of the manufacturing process, == crystallization in the process. In addition, in the fresh C crystallization, the (4) is better, in the 5 〇 200 to 25 (). (: crystallization is best 320653 8 200927972 The additive element for the flb to form an amorphous film may, for example, be Li [Li ' La, Ca, Mg, Y, etc. When such an element is added to form a non-曰曰-shaped film, as in When a film is formed under a predetermined water pressure, it can be prevented from occurring, and the effect of preventing the unevenness of the money can be reduced to the point where the amorphous film can be produced. Here, the annealing treatment refers to heating in a vacuum or an ambient gas at a required temperature for a certain period of time in a vacuum. The time is usually between minutes and hours, but industrial. In the process, as long as the effect is the same, it is generally preferably in a short time. The transparent conductive film crystallized by the annealing treatment is improved in transmittance on the short-wavelength side, for example, 'wavelength 400 to 50 〇 nm. The average transmittance will become above. Again, it will not be as good as in IZ. The O film has a problem that the film has a yellow color. In general, the transmittance on the short-wavelength side is preferably higher. On the other hand, the crystallized transparent conductive film is resistant to etching. Increasingly, so that the weakly acidic engraving agent of the amorphous film can not be rhymed. Therefore, the corrosion resistance, or the device environment in the subsequent step will be improved. Thus, in the present invention Since the content of the added element can be changed, the crystallization temperature after the film formation is set to a desired temperature, and the heat treatment can be performed to avoid the temperature above the crystallization temperature and the amorphous state can be maintained. Further, it may be formed by patterning after film formation, and heat-treating at a temperature equal to or higher than the temperature of the film to change the etching resistance. 320653 9 200927972 Next, the manufacturing method of the reduced-mining rod used in the present invention will be described, but the production method is not particularly limited as long as it is merely an example. First, the raw material constituting the sputtering target of the present invention is generally an oxide of a constituent element, but such a monomer, a compound, a composite oxide or the like may be used as a raw material. When a monomer or a compound is used, a process of preparing an oxide in advance is prepared. ❹

The method of mixing and molding the raw material powders at a desired blending ratio is not particularly limited, and various wet methods or dry methods known in the art can be employed. The dry method and s ' can be exemplified by a cold pressing method or a hot pressing method. In the cold press method, the mixture is filled in a molding die to prepare a molded body, which is calcined. In the hot press method, the mixed powder is calcined in a molding die to be sintered. In the wet method, for example, a filter molding method is preferably used (refer to Japanese Patent Application Laid-Open No. Hei No. 286 GG2). In the filter molding method, a filter molding die is used, which is a mold-forming mold which is obtained by dehydrating and draining water from a ceramic raw material slurry to obtain a water-insoluble material for a molded body. It is formed by a lower mold for molding having one or more water holes, a water-permeable layer (4) placed on the lower mold for molding, and a sealing material for sealing the outer layer (four). Side clamping

In the second step, the lower mold for molding, the molding die frame, the sealing material, and the filter can be separately decomposed in a group I to discharge (4) from the κ 采, only from the side of the transition device = = water in the poly The filter molding die, the slurry prepared by the water and the organic additive, and the filter molding die, only the filter body is produced from the filter 320653 10 200927972. The obtained ceramic molded body is dried and degreased, and then satin-fired. . - The calcination temperature of the person formed by cold pressing or wet molding is preferably ί300 • to 1650 ° C, more preferably 1500 to 1650 ° C ' and the environment is atmospheric environment, oxygen environment, non-oxidation Environment, or vacuum environment. On the other hand, in the case of 'hot pressing method', it is preferably 12 〇〇. (: It is sintered nearby, and its environment is a non-oxidizing environment or a vacuum environment, etc. In addition, after calcining the crucible according to each method, a machining process for forming into a predetermined size is performed to prepare a target. [Examples] Hereinafter, the present invention will be described based on examples, but the present invention is not limited by the examples. (Sp-iTO) (Sr-iTO) (Sr-added ITO, Sr) =0. 02, Sn=0. 1) Prepare purity &gt;99. 99% of In2〇3 powder, Sn〇2 powder, and purity>99.9% of ❹SrC〇3 powder. First, press In2〇 3 powder 65. 3 wt% and SrC〇3 powder 34.7 wt% ratio prepared a total amount of 200g, ball milled (1) 311 mill) in a dry state, 12 在 in the atmosphere (pre-calcined for 3 hours under TC) , srin2〇4 powder was prepared. Then, according to the above-mentioned SrIn2〇4 powder 2.2% by weight, In2〇3 powder 86.6% by weight, and Sn〇2 powder 11.2% by weight, the total amount is about 10kg (each The composition of the metal atom is In=88. Oat. %, sn=i〇. 〇at. %, Sr=2. 0 'The ball is mixed by ball milling. Thereafter, pvA (polyvinyl alcohol) water is added as the liquid Binder The mixture was dried, dried, and subjected to cold pressing to obtain a molded body of 320653 11 200927972. This molded body was 60 in the Datong Shi β bottle, and the fat was removed at a temperature of TC/hour. Next, under an oxygen atmosphere, the sintered body is produced at a temperature of 15 般, and the calcination conditions, specifically, from the chamber 'to the dish to 8 〇〇 C, are 200 〇 C / hour. Overflow, from 800 ° C to 1550 ° C for 400 C / small day to keep warming, after 8 hours, from 155 &gt; c to room temperature to be cooled at 10 CTC / hour conditions. After that, the sintered body was processed to obtain a target. The density at this time was 7. 〇 5 g / cm 3 . In the same manner, Sr = 0.0001, Sr = 0. (Π, Sr = 0.05. (Sputter target production example 2) (Li-ITO) (ITO with Li added, Li=0.02, Sn=0. 1) Quasi-injury purity> 99. 99% of Im〇3 powder, Sn〇2 powder And purity> 99.9% of Li2C〇3 〇 First, according to the ratio of I112O3 powder 79.0% by weight and U2CO3 powder 21. 0% by weight, prepare a total amount of 200g, and perform ball milling mixing in a dry state. Pre-calcined at 10 ° C for 3 hours in helium to obtain LiIn 〇2 powder. Next, in addition to the above LiIn〇2 powder 2.2% by weight, in2〇3 powder 86.8 wt% and SnCh powder 11.0 wt% ratio to prepare a total amount of about 丨.0kg (; each metal The composition of the atom was 'In=88. Oat. %, Sn = 10. Oat. %, Li = 2. 0 at. %), and the rest was dried in the same manner as Sr-ITO (Sr=0. 02). However, the calcination temperature was 1450 °C. Further, the density at this time was 6.85 g/cm3. (Spray target production example 3) (La-IT0) (IT0, La=0.02, Sn=〇. 1 added with La) Preparation of purity &gt;99. 99% of Iri2〇3 powder, Sn〇2 powder, And purity &gt;99. 99% 320653 200927972 of La2(C〇3)3 · 8H2O powder. First, according to the ratio of In2〇3 powder 31.6 wt% and La2(C〇3)3·8H2〇 powder 68.4 wt%, prepare a total amount of 200 g, and perform ball milling in a dry state, in the atmosphere. Pre-calcined at 1200 ° C for 3 hours to prepare LalnOs powder. Then, in addition to the above-mentioned LaIn〇3 powder 4.3% by weight, 1112〇3 powder 85. 0 reset % and Sn〇2 powder 10·7 reset % ratio preparation total amount about 1. 〇kg (each The composition of the metal atom was made in the same manner as Sr-ITO (Sr = 0.22) except that In = 88. Oat_%, Sn = 10. Oat. %, La = 2. 0 at. %). ® The density at this time is 7. 04g/cm3. (Sputter target production example 4) (Ca-IT0) (Addition of Ca ΙΤ0, Ca=0. 02, Sn=0. 1) Preparation of purity &gt;99. 99% of I112O3 powder, Sn〇2 powder, and purity &gt;99. 5% CaC〇3 powder. First, according to the ratio of 1 〇 3 powder 73.5 wt% and CaC 〇 3 powder 26.5 wt%, prepare a total amount of 200 g, ball mill mixing in a dry state, pre-calcination at 1200 ° C in a large gas After 3 hours, CaIn2〇4 powder was obtained. Okg( Each metal atom group is prepared in a ratio of 4.8 wt%, In2〇3 powder 84.3 wt%, and Sn〇2 powder 10.9 wt%. The target was prepared in the same manner as in the case of Sr-ITO (Sr=0. 02) except that, in the case of In = 88. Oat. %, Sn = l〇. Oat. %, Ca = 2. 0 at.%). The density at this time was 6.73 g/cm3. (Spray target production example 5) (Mg-IT0) (IT0, Mg=0. 02, Sn=0. 1 added with Mg) Preparation purity &gt;99. 99% of Im〇3 powder, Sn〇2 powder, And magnesium carbonate hydride 13 320653 200927972 magnesium powder (MgO content 41.5 wt%). First, according to the ratio of In2〇3 powder 87.3% by weight and magnesium hydroxide powder 12.7% by weight, prepare a total amount of 200g, perform ball milling in a dry state, and preheat in the atmosphere at 1400 ° C. After calcination for 3 hours, MgIn2〇4 powder was obtained. Okg( Each metal atom is prepared, in addition to the above-mentioned MgIn2〇4 powder, 4.6% by weight, In2〇3 powder, 84.5 % by weight, and Sn 〇 2 powder, 10.9% by weight. The composition was prepared in the same manner as in the case of Sr-ITO (Sr=0. 02) except that In=88. Oat.%, Sn=10. Oat.%, Mg=2. 0 at.%). ® The density at this time is 7. 02g/cm3. In the same manner, a sputtering target of Mg = 0.05 and Mg = 0.12 was produced. (sputter target production example 6) (Y-IT0) (addition of Υ ΙΤ 0, Υ = 0.22, Sn = 0.1) Preparation of purity Y > 99. 99% of In 2 〇 3 powder, Sn 〇 2 powder, And purity &gt;99. 99% of Y2(C〇3)3 · 3H2〇 powder·. First, according to the ratio of In2〇3 powder 40.2% by weight and Y2(C〇3)3 · 3H2〇 powder 59.8 wt%, a total amount of 200 g is prepared, and ball milling is carried out in a dry state in the atmosphere. Pre-calcined at 1200 ° C for 3 hours to prepare Yin 〇 3 powder. Next, a total of 1.0 kg was prepared in addition to the above-mentioned YIin〇3 powder 3.6 wt%, Im〇3 powder 85.6 wt%, and Sn〇2 powder 10.8 wt% (the composition of each metal atom is, In=88) The target was prepared in the same manner as in the case of Sr-ITO (Sr=0. 02) except for Oat. %, Sn = l 0. Oat. %, Y = 2. Oat. %). The density at this time is 7. 02g/cm3. In the same manner, a sputtering target of Y = 0.05 was produced. (Examples 1 to 13, Comparative Examples 1 to 5) 14 320653 200927972 实施 实施 Examples 1 to 13 and Comparative Examples 1 to 5 were carried out as follows. Among the targets manufactured by the above-mentioned method, the targets of the following compositions were used to form the targets of Examples 1 to 13 and Comparative Examples 1 to 5, and the DC magnetron sputtering was carried out separately. The plating apparatus and the substrate temperature is set to room temperature (about 2 〇 ° C) 'The oxygen partial pressure is changed between 0 and 3. 0sccm (equivalent to 〇炱丨.1&quot;&quot;10 21^), The transparent conductive films of Examples 1 to 13 and Comparative Examples 1 to 5 were obtained. [Table 1] Add Element

Sr

Li

La

Ca

Mg

Y Comparative Example 1 (Sr=0.〇〇〇Ql^--Comparative Example 2 Composition Comparative Example 3, (La=0.0000?^^- Example 1 (Sr=0.01) Example 2 (Sr=0_02) Implementation Example 3 (Sr = 0.05) - Example 4 (Li = 0.02) Example 5 (Li = 0.05) - Example 6 (La = 0.01) Example 7 (La = 0.22) - - - - Example 8 (Ca = 0.02) Example 9 (Ca = 0.05) Comparative Example 4 (Ca = 0.10) - Example 10 (Mg = 0.02) Example 11 (Mg = 0.05) Comparative Example 5 (Mg = 0.12) Example 12 (Y = 0.02) Example 13 (Y = 0.05) A sputtering condition was as follows to prepare a film having a thickness of 1200 A. Dry size: C4 忖, t=6mm Miscellaneous exhaust device PUmP)+m(e3T°PUmP) Arrival straightness: 5,3xl (nPa) Red (argon) Force: 4 on 1〇-1 [called 15 320653 200927972 Oxygen pressure: 0 to 1. 0x10-2 [Pa] Water pressure: 5. OxlO_6 [Pa] Substrate temperature: room temperature. Sputtering power: 130 W (watt) (power density 1. 6 W/cm2) * Using substrate: Corning #1737 ( Glass for liquid crystal display) ΐ=0· 8 mm The resistivity of the film formed under the partial pressure of oxygen and the resistivity after annealing each film at 250 ° C were measured. The results are as shown in Fig. 1 to As shown in the figure, it is known from the results that in any case, there is an optimum partial pressure of oxygen. Further, it is known in Examples 1 to 13 that the optimum oxygen partial pressure at room temperature is annealed at 250 ° C. The partial pressures of oxygen at the time of film formation with the lowest post-resistance are different from each other. Table 2 shows the optimum partial pressure of oxygen at room temperature and the partial pressure of oxygen at the time of film formation with the lowest resistivity after annealing at 250 °C. In Examples 1 to 13, it can be seen that the film is formed by annealing at 250 ° C and then forming a film at a partial pressure of oxygen at the lowest resistivity q, and then annealing at 250 ° C. On the other hand, in Comparative Examples 1 to 3 in which the amount of addition was too small, it was found that the amorphous film was not obtained and the optimum partial pressure of oxygen did not change. Further, a comparative example in which the amount of addition was excessive 4 and 5, it can be seen that although an amorphous film can be obtained during film formation, the optimum oxygen partial pressure will be changed during annealing at 250 ° C without crystallization. In Table 6 below, there will be an optimum oxygen partial pressure. The changer is represented by 〇, and the changer without the optimum oxygen partial pressure is represented by X. 16 320653 200927972 (Test Example 1) In Examples 1 to 13 and Comparative Examples 1 to 5, the transparent conductive films produced by the optimum oxygen partial pressure at room temperature were cut into 13 mm, respectively. The size of the sample was treated in the atmosphere for 25 hours in the atmosphere. Further, in Examples 1 to 13 and Comparative Examples 1 to 5, in the case of the film formation of the chamber/dish and the crystal state after the annealing treatment of 250 C, the amorphous film was designated as a, and the crystallized film was recorded. And etc. are shown in Table 2. In the case of Examples 1 to 13 which were formed into a film at a temperature, it was confirmed that the film was amorphous, but it was 2 赃! The hourly annealing treatment will crystallize. In another case, the non-sickness at the time of film formation was crystallized in Comparative Examples 4 and 5 in which the amount of addition was large. Further, in the cases of Si: 3〇〇tT^, in the examples 1 to 3, it was confirmed that the film formation of the comparative film having a small amount of addition was formed at the time of film formation. "The optimum oxygen resistivity Ρ (Ω,) of the room temperature conversion of the amorphous yttrium (test example 2) can not be achieved. In addition, the test 2 of the test example 1 was also measured. _ The resistivity of the 。 。 将 。 。 。 。 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻 电阻High resistance of cffl. 320653 17 200927972 (Test Example 3) In Examples 1 to 13 and Comparative Examples 1 to 5, the transparent conductive films produced by the optimum oxygen partial pressure at room temperature film formation were respectively cut into 13 mm. See the square size 'and measure the transmission spectrum. 'And' the transmission spectrum of the film after the annealing treatment of Test Example 1 was also measured. Further, each of Examples 1 to 13 and Comparative Examples 1 to 5 was used. The average transmittance after the annealing treatment is shown in Table 2. From the results, it is understood that the transmission spectrum before the post-annealing treatment is an annealing treatment at 250 ° C for 1 hour, and the absorption end is shifted to a low level. The fact that the wavelength side is such that the color tone is improved. (Test Example 4) From Examples 1 to 13 and Comparative Example 1 In the case of 5, the transparent conductive film produced by the optimum oxygen content at the time of film formation at room temperature is cut into the size of 1 〇 咖 咖, using ITG-〇 5N (oxalic acid system, Kanto Chemical Co., Ltd. 50 g / liter) As an etchant, at the temperature of 3 〇t, it is confirmed whether it is at or after the aging. Further, after the annealing treatment of the test example i, the enthalpy is confirmed in the same manner. For example, the etcher can also be marked with "X", which is shown in Table 2. The result is that amorphous, but crystallized film 320653 18 200927972 [Table 2]

Can you carry out mi [〇] 〇〇〇〇〇〇〇〇〇〇〇〇〇 XXX 平均 退 退 退 退 退 退 退 退 2 9 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 7.8 97.5 95.6 98.2 89.9 79.9 Crystallinity after annealing (250 〇〇[a or c] υ ο O o 〇u υ υ ϋ uo O ϋ O o CO CO Crystallization when forming a [a or c] αι nt A CO ea CO to CEl AC〇a ea· CO ooo cd 03 Resistivity of annealed fabric [χΙΟ^Ω · cm] CD Csj CO CO CD 0〇od o csi S 〇CO a&gt; 03 CO CO a&gt; CO c&lt; i oo aa 03 17.8 14.6 Resistivity at 勰 [χΙΟ^Ω · cm] LA 呀·Csl IA ΓΟ CO 卜 CO irS O iri CO LA 09 in 卜. CD ΙΛ in CD 〇» 卜* O) 守CO cva CO 14.3 10.5 Variation of optimum gas partial pressure [Ο] 〇〇〇〇〇〇〇〇〇〇〇〇〇XXX 〇〇 Relative to In 1 ratio [mol] 0.011 0.023 0.059 0.023 0.059 0-011 0.023 0.023 0.063 0.023 1 0.063 0.023 0.059 0.000011 0.000056 0.000089 0.125 0.154 base [atX] . Add element ο O c4 s O s . °· O csi 5 0 01 O LT) 〇 oi s 0.001 0.005 0.008 10.0 12.0 a 10.0 10.0 10.0 10,0 10.0 e 10,0 10.0 10.0 10.0 1 10.0 10.0 10.0 10.000 10.000 10.000 10.0 10.0 νΞ 89.0 88.0 85.0 88.0 o 89.0 CD Ss 88.0 Muscle 0 88.0 丨80.0 88.0 85.0 89.999 89.995 89.998 80.0 O Adding element * J3 JS δ β &gt;&gt;&gt;1 2 e Swab name Sr=0.01 Sr=a〇2 Sr=0.05 Li=0.02 Li=0.05 La =0.01 La=0.02 1 Ca=0.02 ! Ca=0.05 Mg=0.02 Mg=0.05 Y=0.02 Y=0.05 Sr=0.00001 Li=0.00005 La=0.00008 ca=o. ίο Mg=0.12 Example / Example 1 2 3 4 5 6 Example 7 8 9 10 11 12 13 1 2 mm 3 4 5 19 320653 200927972 (Comparative Example 6) Except that the target of Example 2 was used, and the water was pressed into lxl (T4Pa, the rest was as described above). The film was formed under the same conditions as the sputtering conditions. Thus, the obtained film had a slightly lower resistivity than that of Example 2 and had an etching residue. ▲ In addition, the annealing treatment at 250 ° C for 1 hour was crystallized, but remained. There is a part of the amorphous portion. In addition, the result of this comparison with Example 2 is shown in Table 3. Here, the last name The etching rate refers to the etch rate of the film when ITO-05N (oxalic acid concentration: 50 g/liter) is used for the amorphous film formed at room temperature to etch at a liquid temperature of 30 ° (:). ❹ 20 320653 200927972 [Table 3]

After annealing at 250 °C, the specific transmittance is 2 93.5 90.2 weak acid side 〇X resistivity [χΙΟ^Ω · an] CD CQ 卜 csi optimum helium gas grinding change 〇〇 crystallinity j 1 o C (one Part a) I residue side velocity after meal side [A/sec] oo iT) Ξ· weak acid touch] 〇〇1 resistivity [χΙΟ^Ω ·αη] Cv] LO tfi Crystalline CO CO secret time Moisture 4 5x10^ lxitr1 Phase In 1 molar ratio [mol] 0.023 0.023 Addition element O CM* Composition [at.X] a 10.0 •Ξ 88.0 o 00 oo Add element* Sample name Sr=0.02 Sp^O 02 Example / Peak Example 2 1 tbfe Example 6 200927972 As a result, it is found that when an amorphous film is formed under conditions where the partial pressure of water is not controlled and the degree of vacuum is deteriorated, This may result in uneven etching, uneven etching, or uneven crystallization due to annealing treatment. Moreover, it is apparent that such an effect is also produced when an amorphous film is produced. In addition, as an example of forming a film of an amorphous film, an example in which Ba is added is shown below, but it is easy to estimate that the pressure is not controlled, and the degree of vacuum is deteriorated. When the film is formed into a film, unevenness in etching properties, uneven etching, or uneven crystallization due to annealing treatment may occur. (Sputter target production examples A1 to A60) A powder of &gt;99.99% of 1112〇3 powder, 511〇2 powder, and purity &gt;99.9% of BaC〇3 powder were prepared. First, according to the ratio of BET=27m2/g of In2〇3 powder 58.5 wt% & BET=1. 3m2 ❹ /g of BaC〇3 powder 41.4% by weight, the total amount of preparation 2〇〇§, The mixture was ball milled in a dry state, and pre-calcined in the atmosphere for 11 hours in the atmosphere to obtain BaIn2〇4 powder. The first one was BaIn2〇4 powder, BET=5inV_n2〇3 powder, and Sn. 〇2 powder' is compared with the molar ratio of the molars in Table 4 and Table 5, and the two phase fields are ball milled and mixed. 1 甭~ summer 1.0kg, mixed, dried, and cold tPVA Water money as a binder residue. At 600 ° C in the atmosphere at 60 ° ^ Waiting for the molded body. This molded body, degreased for 10 hours at a temperature of c / hour, followed by 320653 200927972 in an oxygen environment 'at 1600 ° C Calcination was carried out for 8 hours to obtain a sintered body. The calcining condition 'specifically, the temperature was raised from room temperature to 800 ° C at 1 ° C / hour, from 800 ° C to 160 (TC at 400 ° C / After heating for an hour, after 8 hours, the conditions were cooled from 1600 ° C to room temperature at 10 0 C / hr. Thereafter, the sintered body was processed to obtain a dry mass. The resistivity (bu 1 k resistivity) is, for example, the composition of A32, each of which is & 88g/cm3, 2. 81χ10_4Ω cm, and the composition of A22 is 6. g6g/cm3, 2.87 xlO&quot;4Qcm ° 实施 (Examples A1 to A60) The sputtering targets of the respective manufacturing examples A1 to A60 were respectively placed on the DC magneto-gear clock device at 4 o'clock, and the substrate temperature was set to room temperature (about 2 〇 ° C). The transparent conductive film of Examples A1 to A60 was obtained by subjecting the partial pressure of oxygen to a change between 0 and 3.0 sccm (corresponding to 〇1 to 10 2 Pa). The conditions of the sputtering were as follows, and the thickness was obtained. 1200 A film. Light size: Φ = 4 pay 't = 6mm @ . Sputtering method: DC magnetron sputtering exhaust device: rotary pump + cryogenic pump up to vacuum: 5. 3xlO_6 [Pa]

Ar (argon) pressure: 4. OxlO_1 [Pa] Oxygen pressure: 0 to 1. lxl (T2 [Pa] Moisture pressure: 5xl (T6 [Pa] substrate temperature: room temperature sputtering power: 130W (power density 1.6W / Cm2) Substrate used: Corning #1737 (glass for liquid crystal display) 320653 23 200927972 t=0.8mm For the examples A1 to A60', the relationship between the partial pressure of oxygen at room temperature and the resistivity was determined, and the measurement was carried out. The etching rate of the amorphous film of the film, the relationship between the electrical resistivity after annealing at 250 ° C and the oxygen at the time of film formation, and the average transmittance of the film, etc., and the following Tables 4 and 5 show In i molar relative to each sample

The molar ratio of Ba and Sn, the crystal state at the time of film formation at room temperature (indicated by a, the crystallized film is indicated by c), and the temperature at which the amorphous film is formed.曰曰 Tables 4 and 5 show the resistivity at the time of film formation, which means the resistivity of the film at the optimum partial pressure of oxygen at the time of film formation at room temperature. The rate of _ is the meaning of the etching rate of the film when ITO-05N (oxalic acid concentration: 5 〇g/liter) and etching at a liquid temperature of 30 ton is used for the amorphous film formed at room temperature. Furthermore, the average transmittance after the wire is the filming of the lowest partial pressure of oxygen after annealing in the 25th generation, and the film of the film is wavelength-to-wavelength: The crystallization temperature shown in the filament 5 of Table 4 was treated as follows: Silkmer. Will pass 250. (: Annealing to form the film with the lowest resistance of oxygen / f at room temperature, from the boot to the boot (if necessary, annealing in the 45th generation atmosphere for 1 hour, and using the film to extract the film, the chamber The diffraction peak of the amorphous film of the warm film (5) pe= 'The radiation can be detected by the increase of the annealing temperature. The temperature of the basin is determined as the crystallization temperature. In addition, the crystallization temperature is determined. The basin phase method can also use the high temperature film XRDa-ray diffraction method. 320653 24 200927972 [Table 4]

The resistivity (χ10-4Ωαη) of the sample number Sn when compared with the filming temperature at the crystallization temperature of Ba (χ10-4Ωαη) Residual rate (A/sec) The resistivity after annealing (χ10'4Ωαη) The average transmittance after annealing ( %) A1 0 0.1 a &gt;450〇C 19.0 22.3 21.4 79.3 A2 0.025 0.07 a 400°C 12.5 18.2 14.3 84.2 A3 0.025 0.1 a &gt;450〇C 15.2 19.8 17.5 82.8 A4 0. 05 0.002 c &lt;100°C 4.1 X 3.0 94.3 A5 0.05 0.005 c &lt;100°C 4.1 X 3.1 90.0 A6 0. 05 0.01 c &lt;100°C 4.2 X 3.4 88.6 A7 0.05 0.02 a 150°C 5.0 7.4 4.9 90.9 A8 0. 05 0.03 a 200 °C 7.5 10 6.2 91.2 A9 0.05 0. 05 a 400°C 8.2 13.2 9.2 91.5 A10 0.075 0.002 c &lt;100°C 3.3 X 2.1 92.4 All 0.075 0.005 c <10(TC 3.3 X 2.1 92.5 A12 0.075 0.01 a 100° C 4.2 6.7 3.1 90.0 A13 0.075 0.02 a 150°C 5.1 7.5 3.5 95.5 A14 0.075 0.03 a 250〇C 6.7 8 5.1 91.8 A15 0.1 0. 0001 c &lt;100°C 4.3 X 1.8 95.2 A16 0.1 0. 0002 c &lt; 100 ° C 4.3 X 1.8 95.2 A17 0.1 0.0005 c &lt; 100. 4.3 X 1.8 95.3 A18 0.1 0.001 c 〈loot 4.3 X 1.8 95.2 A19 0.1 0. 002 c &lt;100 ° C 4.3 X 1.8 94.8 A20 0.1 0.005 a 100 ° C 4.3 4.9 1.8 94.0 A21 0.1 0.01 a 150 ° C 4.7 5.4 2.3 92.2 A22 0.1 0.02 a 200 ° C 5.5 6.2 2.7 93.8 A23 0.1 0.03 a 250〇C 6.1 6.7 4.6 92.5 A24 0.1 0.05 a 400°C 8.6 8 10.0 86.7 A25 0.1 0.1 a &gt;450〇C 14.2 10.6 15.3 83.2 A26 0.15 0.0001 c <100°C 4.6 X 1.8 94.5 A27 0.15 0. 0002 c &lt;100°C 4.6 X 1.8 94.5 A28 0.15 0. 0005 c &lt;100. . 4.6 X 1.8 94.6 A29 0.15 0.001 a 150°C 4.6 3.9 1.8 94.5 A30 0.15 0.002 a 150°C 4.6 3.9 1.8 92.3 25 320653 200927972 [Table 5] The resistance of the sample number Sn to Ba when crystallized at a crystallizing temperature Rate (χ10'4Ωαη) #刻率(A/sec: resistivity after annealing (χ10*4Ωαη) Average transmittance after annealing (%) A31 0.15 0.005 a 150°C 4.6 4 1.8 92.1 A32 0.15 0.01 a 200°C 5.0 4.1 2.1 93.2 A33 0.15 0.02 a 250〇C 6.0 4.4 2.6 91.4 A34 0.15 0.03 a 350〇C 6.9 4.7 5.9 91.5 A35 0.15 0.05 a &gt;450〇C 8.6 4.9 8.1 84.7 A36 0.2 0. 00006 c 〈loot 4.8 X 1.9 94.5 A37 0.2 0. 0001 a 150°C 4.8 3.5 1.9 93.4 A38 0.2 0. 0002 a 150°C 4.8 3.5 1.9 93.2 A39 0.2 0. 0005 a 150°C 4.8 3.5 1.9 93.8 A40 0.2 0. 001 a 200 °C 4.8 3.5 1.9 94.4 A41 0.2 0.002 a 200°C 4.8 3.5 1.9 93.6 A42 0.2 0.005 a 200°C 5.2 3.6 1.9 93.4 A43 0.2 0.01 a 200°C 5.8 4 2.4 93.5 A44 0.2 0. 02 a 250〇C 6.7 4.2 3.0 93.0 A45 0.2 0.03 a 400. 8.0 4.5 6.2 92.0 A46 0.2 0.05 a &gt;450〇C .10.1 4.7 9.8 83 .5 A47 0.22 0.00005 a loot: 4.9 3 2.0 94.3 A48 0. 22 0.033 a 400°C 8.1 4.6 6.3 89.6 A49 0. 25 0. 0001 a 250〇C 4.7 2.3 2.1 95.0 A50 0.25 0. 0002 a 250〇C 4.7 2.3 2.1 93.9 A51 0.25 0.0005 a 250〇C 4.7 2.3 2.1 94.9 A52 0. 25 0.001 a 250〇C 4.7 2.3 3.6 93.2 A53 0.3 0.0001 a 300°C 5.3 1.2 4.3 89.0 A54 0.3 0.0002 a 300°C 5.3 1.2 4.3 89.0 A55 0.3 0. 0005 a 300°C 5.3 1.2 4.3 89.0 A56 0.3 0.001 a 300°C 5.3 1.2 4.3 88.9 A57 0.3 0.002 a 300°C 5.4 1.2 4.4 87.8 A58 0.3 0.005 a 350〇C 5.7 1.3 4.7 88.9 A59 0.3 0.01 a 400 °C 6.2 1.7 5.1 95.7 A60 0.3 0.02 a 450〇C 7.8 1.9 6.0 94.5 26 320653 200927972 (Test Example A1) Using the sputtering targets of each of the manufacturing examples A1 to A60 and determining at room temperature (about 2 ° C) The relationship between the oxygen partial pressure and the resistivity of the film formed under the partial pressure to determine the optimum oxygen partial pressure while the film is formed from 250 ° C. The relationship between the resistivity after annealing and the film formation oxygen, and the resistivity after annealing is the lowest resistance oxygen. The partial pressure of gas is the optimum oxygen partial pressure at the time of film formation at 250 ° C to determine whether the optimum oxygen partial pressures of the two are different, and the difference is marked with Lu, and the same is marked with ▲, indicated by Figure 12. From the results, it is known that the molar ratio y of the tin relative to the indium 1 is: when compared with the 锢1 molar, the molar ratio is represented by x (_2. 9xl 〇 -2Ln(x) -6 When the value of 7x10 2) is greater than or equal to the value of (_2. 〇xi〇MLn(x)-4. 6x10—〇 and the range of y=〇 is removed, the amorphous film after film formation becomes low resistance. The film-forming oxygen partial pressure and the film-forming oxygen partial pressure which becomes a low resistance after annealing treatment may become different, or at 25 (the optimum oxygen partial pressure a of rCT and the optimum oxygen partial pressure at the temperature) The fact that the composition range is not the optimum oxygen partial pressure obtained from the resistivity immediately after film formation, but the film which is crystallized after annealing treatment becomes the lowest resistance oxygen. Partial pressure is used for film formation, and the resistivity of the film after annealing is lower, so it is a better practice. Here, most of the samples of the test examples within this range are δ ' At 250. (: The film after the annealing treatment becomes a low-resistance oxygen partial pressure system, the driver is low at room temperature, so it is known that under low oxygen partial pressure The film forming system is better. In the case of Α58 to Α60, the film after annealing at 250T: 27 320653 200927972 becomes a low-resistance oxygen partial pressure system higher than that at room temperature, so it is known that The method of film formation under high oxygen partial pressure is better than the fact that the transparent conductive film of resistance is good. • Also, for samples with high crystallization temperatures such as A2, A9, and A24, I don’t know if Since it is not crystallized even if it is subjected to annealing at 250 ° C, the lowest resistivity at the annealing treatment at 250 ° C is higher than the optimum oxygen partial pressure at room temperature. At the optimum oxygen partial pressure of the warm film, the film is subjected to an annealing treatment at 250 ° C, and the resistance is increased. Because of the temperature, the room temperature is the lowest at the annealing temperature. As a result of the manner in which the film formation is annealed, the lowest resistance is obtained. Further, in the case where the annealing treatment is performed at a crystallization temperature, for example, at 400 ° C, it is of course preferable to The resistivity after annealing is the lowest Oxygen partial pressure is used for film formation. If this case is considered, the molar ratio of 钡 is preferably less than 0.05. The film after annealing at 250 ° C in this test example A1 becomes low electric resistance. The partial pressure of oxygen is presumed to be approximately the same as the optimum partial pressure of oxygen formed at 250 ° C. Here, as a film immediately after film formation, the oxygen partial pressure of low resistance is annealed at 250 ° C. The treated film has the same low partial pressure of oxygen as the same, and may be, for example, A4, A6, A35, etc. Further, in these cases, it is presumed that the optimum partial pressure of oxygen at the time of film formation at room temperature is The optimum oxygen partial pressure for film formation at 250 ° C is the same. (Test Example A 2) The transparent conductive film 28 320653 200927972 manufactured by the optimum oxygen partial pressure at room temperature film formation was cut into a size of 10 x 50 mm, respectively. Using ITO-05N (oxalic acid system, manufactured by Kanto Chemical Co., Ltd.) (oxalic acid concentration: 50 g/liter) as an etching solution, the etching rate was measured at a temperature of 30 ° C, and those below 3 A/sec were recorded as "▲". Those who have not reached 4 A/sec for 3 A/sec or more are marked with #, 4 A/sec or more, and the results are shown in Fig. 13. From this result, it is known that the molar ratio y of tin relative to the indium 1 molar is: -2. 9xl 〇-2Ln(x) -6 with respect to the molar ratio of the indium 1 molar. The value of 7x10-2) is greater than or equal to 'the range of 〇22 or less, and is 3 a/sec or more, and particularly, in the range of (5. 9x10 2Ln(x) + 4. 9x1ο-1), Become 4 A / sec or more. Accordingly, the results of the results of the combined test example A1 are shown in the figure. That is, it is known from the results that the molar ratio y of tin relative to indium bismuth is: when compared with the indium 1 molar, the molar ratio is expressed by χ 2 g χ 10-21η (χ) -6.7χ10-)ό^,^ , „ (-2. 〇χΐ〇-lLn(x)^ βχ 〇ΙΟ1) below the value and remove the range of y=0, and in the case of the range below 〇22, The optimum oxygen separation at room temperature and the 25th generation as the retreat temperature will be different, and the rate of the engraving rate will be 3 A/sec or more (10) 、), and the range below the value of χΗ4·9χΐη will become 4 Α / sec. ^ thousand (Test Example A3) For the sample within the preferred range of Figure 14, after annealing, it will become a low-resistance oxygen partial pressure for non-day-day shape _ film, money The resistivity of the transparent conductive film crystallized by the annealing treatment is measured, and those below 3 _-4 Ω cm are denoted by ◎, and those higher than this are denoted by 〇. The results are shown in 320653 29 200927972 Fig. 15 It is known from the results that, for example, the molar ratio of the tin relative to the tin of the 莫 莫 莫 is -0.08 = upper, and the molar ratio relative to the indium of the indium 1 is 〇. The following range, Resistivity Low, it is 3·Oxl (the fact that T4Qcm or less. When it is observed by the result of the combined test example A1, it is understood that the room temperature is formed by the annealing treatment temperature (for example, the optimum oxygen partial pressure at 25 (TC)). The film is then subjected to an annealing treatment to crystallize the film, and the resistivity thereof is also 3. 0x1 〇 _4 Q cm or less. 〇 [Simple description of the drawing] Fig. 1 (a) to (c) Fig. 2 is a view showing the relationship between the oxygen partial pressure and the specific resistance of Examples 1 to 3 of the present invention. Fig. 2 (a) and (b) show the partial pressure of oxygen and the oxygen partial pressure of Examples 4 to 5 of the present invention. Fig. 3 (a) and (b) are diagrams showing the relationship between the oxygen partial pressure and the specific resistance of Examples 6 to 7 of the present invention. 〇 Fig. 4 (a) And (b) is a graph showing the relationship between the oxygen partial pressure and the specific resistance of Examples 8 to 9 of the present invention. Fig. 5 (a) and (b) show the oxygen of Examples 10 to 11 of the present invention. Fig. 6(a) and (b) are diagrams showing the relationship between the partial pressure of oxygen and the specific resistance of Examples 12 to 13 of the present invention. The graph shows the relationship between the oxygen partial pressure and the specific resistance of Comparative Example 1 of the present invention. Fig. 8 is a graph showing the relationship between the oxygen partial pressure of Comparative Example 2 of the present invention and the specific resistance of 30 320653 200927972. Fig. 9 is a view showing the relationship between the partial pressure of oxygen and the specific resistance of Comparative Example 3 of the present invention. Fig. 10 is a view showing the relationship between the partial pressure of oxygen and the specific resistance of Comparative Example 4 of the present invention. Fig. 11 is a graph showing the relationship between the oxygen partial pressure and the specific resistance of Comparative Example 5 of the present invention. Fig. 12 is a view showing the results of Test Example A1 of the present invention. Fig. 13 is a view showing the results of Test Example A2 of the present invention. Fig. 14 is a view showing the results of Test Example A1 and Test Example A2 of the present invention. Fig. 15 is a view showing the results of Test Example A3 of the present invention. [Main component symbol description] None. 〇 31 320653

Claims (1)

200927972 VII. Patent Application Range: 1. A method for producing a transparent conductive film, which is characterized in that a sputtering target having an oxide containing an indium oxide and a tin containing an additive element while containing an indium oxide is used for carrying out When a film is formed into a film and a transparent conductive film containing indium oxide and an additive element and containing an additive element is formed, the partial pressure of water at the time of film formation is set to lxl (T5Pa or less). The method for producing a transparent conductive film according to the first aspect of the invention, wherein, after the amorphous film is formed, a transparent conductive film which is crystallized by annealing is formed. 3. Transparent conductive material according to claim 1 The method for producing a film, wherein the additive element is at least one selected from the group consisting of Ba, Si, Sr, Li, La, Ca, Mg, and Y. 4. The transparent conductive film of claim 2 The manufacturing method, wherein the additive element is at least one selected from the group consisting of Ba, Si, Sr, Li, La, Ca, Mg, and Y. 〇32 320653