TW200923973A - Indium oxide transparent conductive film and manufacturing method thereof - Google Patents

Abstract

This invention provides a transparent conductive film, using indium oxide target having a sintered oxide to form an amorphous film, wherein the sintered oxide contains indium oxide and tin, and also contains barium; wherein the content of tin and barium is such that when y represents a molar ratio of tin with respect to 1 mole of indium, and x represents a molar ratio of barium with respect to 1 mole of indium, the value of y is not reach the value of (-2.9x10<SP>-2</SP>Ln(x)-6.7x10<SP>-2</SP>).

Description

200923973 _ VI. Description of the Invention: [Technical Field] The present invention relates to a film which can be formed into an amorphous film which can be easily crystallized by weak acid I, and further Crystallization

The film of I is a transparent conductive film having low resistance and high transmittance and a method for producing the same. [Prior Art] Indium oxide-tin oxide (composite oxide of In2〇3-Sn〇2, hereinafter referred to as "ΙΤ0") film is widely used as a transparent conductive film because of its high visible light transmittance and high conductivity. In the liquid crystal display device or the glass, the heat-preventing film, the infrared-ray reflective film, and the like are prevented from being dew condensation, but there is a problem in that it is difficult to form an amorphous film. On the other hand, an indium oxide-zinc oxide (ITO) transparent conductive film is well known as an amorphous film. However, this film is inferior in transparency to the ΙΤ0 film and has a yellow state problem. Therefore, the applicant of the present invention has previously proposed to add a ruthenium to ΙΤ0 as a transparent conductive film, and to form a transparent transparent conductive film under predetermined conditions (see Patent Document 1). The problem. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-135649 (Application No.). SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In view of the above problems, the present invention provides a film which can be formed into an amorphous film which can be easily patterned by weak acid etching and further crystallized easily. Further, the film which is further crystallized is a transparent conductive film having low resistance and high transmittance, and a method for producing the same. [Means for Solving the Problem] 320646 200923973 'Shu Ming is the result of various reviews to solve the above problems. It is known that the indium oxide-based transparent conductive film which is added is a low-resistance and excellent transparency. It can be easily patterned by weak acid etching, and further, it can be easily changed, and the application is made first (Japanese Patent Application No. 2007-095783). In this case, the crystallization temperature was 1 Torr. In the following composition range, the formation of an amorphous film is an extremely difficult condition, and the present invention is intended to solve related problems. f. The first aspect of the present invention is a transparent conductive film in which a sputtering target of a material oxide sintered body is formed into an amorphous film, and the oxide sintered body contains an oxide port and tin and contains germanium. The conductive film is characterized by containing oxidized steel and tin and containing yttrium, * and (d) Mohs y = y = for the indium 1 耳 钡 莫 对于 对于 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟_2.9 .1〇Ln(x) 6. The value of 7xl〇2) 'The crystallization temperature by annealing is C or more. ^In the invention of the first aspect of the sample, the indium-based transparent conductive film containing the tin-containing composition of the formula i is relatively easy to form an amorphous film, and the engraving of the weakly acidic surrogate become possible. The second aspect of the present invention is a transparent conductive film characterized by forming a film under the condition that the partial pressure of water is h 0xl "4Pa β or less than 1. Οχιό-% in the transparent conductive film according to the first aspect. membrane. In the second aspect, the film is formed by partial pressure of the specified water, and it is easier to form a film into an amorphous film by using a film of the amorphous type, and the weakly acidic (four) agent is used. (4) It is possible. The third aspect of the present invention is in the transparent film of the first or second aspect of the present invention. The above-mentioned amorphous film contains a transparent conductive film characterized by hydrogen. In the third aspect, the film is formed by a partial pressure of water, and the gas is taken in a state of being bonded to the film, and the film is relatively easily formed into an amorphous film and the weakly acidic etchant is used. Etching is possible. The fourth aspect of the present invention is the transparent conductive film described in any one of the first to third aspects, and the transparent conductive film characterized by annealing to form a crystallized film. In the fourth aspect, after the film formation is an amorphous film, it can be easily crystallized by annealing, and the weak acidity can be imparted. The +5 aspect of the present invention is in the transparent conductive month of the fourth state, and the annealing is performed at 100 to 300 t: the transparent conductive characteristic is characterized by the fourth aspect, which is crystallized at a lower temperature. Membrane. The electro-membrane pattern is a transparent conductive film characterized by the conductivity of the transparent conductive film after permeation, electricity, and annealing described in the fourth or fifth aspect. In the relevant aspect, the resistivity after annealing is very low.

卞 is a low resistance film of 5. GxlG 4Q . _"', electric PJ The seventh aspect of the present invention is a transparent conductive film 1 prepared by sputtering a target of an oxide sintered body, the gas, clothing &amp; method, using tin and containing yttrium, the transparent conductive film Two = with indium oxide and at the same time containing yttrium, and relative to yttrium 3 with a slit of indium and tin for indium 1 Mo, the molar ratio of tin to y: phase i 〇 W6. - non-deficient ((9) The partial pressure is l.〇xlo, a or more, 1〇χΐρ '成臊蚪', and the water is 3 or less at the time of film formation. 320646 200923973 In the seventh aspect, 'by the specified partial pressure of water The film contains an indium oxide-based transparent conductive film having a ruthenium composition, and is relatively easy to form a non-曰B-type film, and etching with a weakly acidic etchant is possible. The eighth aspect of the present invention is based on In the method of the first embodiment, the transparent conductive film characterized by annealing at a crystallization temperature of 1 〇〇 C or more is described in the coating method. Due to the crystallization temperature of 100DC or more

The g曰曰i film is comparatively easy to form a film into an amorphous film, and etching with a weakly acidic etchant is possible. The ninth aspect of the present invention is based on the method of coating a transparent conductive film according to the seventh or eighth aspect. After the film is formed into an amorphous film, the film is characterized by annealing. In the ninth aspect of the related art, the film is formed into an amorphous film, and then it is easily crystallized by retreat, thereby imparting weak acid resistance. The first Q'% of the month of the month In the method of fabricating a transparent conductive film according to the ninth aspect, the above-mentioned annealing is performed by a gentleman 1 nt, a tear, a human flesh, and a mouth-to-day system at 100 to 3 〇〇.制造 制造 仃 之 。 。 。 。 。 。 。 。 。 。 。 。 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 相关 结晶 相关 结晶In the manufacturing method as described above, the method of manufacturing a transparent conductive film characterized by a resistivity of a transparent V-electrode film of a group of volts and volts is 5 cnm. 'The resistivity after annealing is very low, and it can be a low-resistance film with a resistance of 5.00x10 Ω.cm or less.",, electric 320646 6 200923973 - [Effect of the invention] According to the present invention In the case where a film having a predetermined range of a film of tin and antimony added to indium oxide and having a predetermined crystallization temperature is formed, the film can be relatively easily formed into an amorphous film, and after film formation, It can be easily patterned by a weak acid etchant, and can be easily crystallized, and further, the crystallized film can exhibit the effect of a transparent conductive film having low electrical resistance and high transmittance. The sputtering target for a transparent conductive film used in the indium oxide-based transparent conductive film of the present invention is mainly composed of indium oxide, and is an oxide sintered body containing tin and containing cerium, or as an oxide, or as a composite. O. Moss or more and less than 0. 10 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 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 It is better to form the key dryness in the range of the ear. When the amount of addition is less than this content, there is no obvious additive effect, and when added in a larger amount, the resistance of the transparent conductive film formed tends to become higher. And with a yellower condition Further, the content of ruthenium in the transparent conductive film formed by the above-mentioned sag #巴 is the same as the content of the sputtering target used. Further, the content of tin is desirably used.约至0. 3摩尔, preferably 0. 005 to 0. 3 moles of the range of sputtering 萆 成 film formation is better. If within this range, properly controlled The density and mobility of the carrier electrons of the Tibetan leather can maintain the conductivity in a good range. Moreover, if the amount exceeding this range is added, the carrier electrons of the sputtering target are lowered by 7 320646 200923973 - the mobility is lowered' At the same time, the conductivity is shifted to the direction of deterioration, which is not preferable. Further, the content of tin in the transparent conductive film formed by the sputtering target is the same as the content of the sputtering target used. The indium oxide is transparent. The composition of the conductive film can be analyzed by ICP after the single film is completely dissolved. Further, when the film itself becomes a component structure, the section of the portion is cut out by FIB (Focused Ion Beam) as needed, and it is also possible to use the SEM (Scanning Electron / microscope: Elemental analysis instruments such as scanning electron microscopes or TEMs (transmission electron microscopes) (EDS (energy dispersion method) or WDS, [Auger electron spectroscopy analysis, etc.] related sputtering targets due to It has a resistance value that can be sputtered by DC Magnetron Sputtering. Although there is a relatively inexpensive DC magnetron sputtering for sputtering, it is of course possible to use a high-frequency magnetron plating device. Such a transparent conductive film is formed by sputtering a target, and an amorphous indium oxide system having the same composition can be formed by forming a film under the conditions of water partial pressure of I, 1·〇xl〇_4Pa or more under 1. OxlOla. Here, in order to make the above partial pressure of water into a predetermined range, it is possible to introduce an ambient gas (generally argon gas) in the film forming chamber at the time of film formation, and it is necessary to use a gas containing oxygen as needed. l (T4Pa pressure) and simultaneously introduce water vapor through a mass flow controller, etc., when the vacuum is less than 1 (T4Pa and high vacuum, make the ambient gas ι/1〇) The pressure of 〇 to 1/10 is better. In addition, under the condition that the degree of vacuum is about 1〇_4 to l〇_3pa and the degree of vacuum is very poor, the main component of the remaining gas is water. Also 8 320646 200923973 - ie Since the degree of vacuum reached is almost equivalent to the partial pressure of water, water vapor is not particularly introduced, and a desired partial pressure state of water can be obtained. The indium oxide-based transparent conductive film of the present invention is regulated by In the amount of film formation, the film formation is carried out in a state of an amorphous state by a temperature condition at room temperature or higher at a crystallization temperature, that is, a crystallization temperature lower than 100 ° C. Further, such a film is amorphous. The film is an advantage of being etched with an etchant which can be weakly acidic. Here, in the present specification, since etching is included, in the patterning step, a predetermined pattern can be obtained. The resistivity of the transparent conductive film is in accordance with The content varies depending on the content, but the specific resistance is 1. 0x1 (Γ4 to 1. 0x1 (Γ3Ω. cm. Further, the crystallization temperature of the film formed varies depending on the content of the ruthenium, and the content is increased. The crystallization temperature is increased, but it can be crystallized by annealing at a temperature of 100 ° C to 300 ° C. Since these temperature fields are users of conventional semiconductor manufacturing steps, such steps can also be used. It is crystallized in the temperature range. In this temperature range, crystallization is preferably carried out at 1 oo ° c to k 300 ° C, preferably 15 Torr to 250 ton: crystallization is preferably carried out at 200 ° 匚 to 250 ° C. Crystallization is optimal. Here, the annealing is performed at a desired temperature and for a certain period of time in the atmosphere, in an ambient gas, or in a vacuum. The so-called certain time is usually from a few minutes to a few hours, but in the industry, if the effect is the same, a short time is better. Here, in the transparent conductive film of the present invention, the composition range using the sputtering target is the molar ratio y with respect to the tin of the indium 1 mole, and the molar ratio with respect to the indium 1 moir is expressed as X. -2. 9xl(T2Ln(x)-6. 7χ1(Γ2) value, by 9 320646 200923973 h OxlOla the following conditions l〇〇 °C or so, can be obtained due to water partial pressure is l.〇xl〇 -4Pa or more, film formation, increase the film formation temperature, and set it on the crystal film. l^u 疋 3 3 film formation is amorphous, and the composition of the film in the film should be more crystallization temperature as described above. The film formation temperature is low, and the composition with less tin content, the lower the crystallization temperature, and the more the amount of tin or antimony, the higher the crystallization temperature, and the water is divided by 1. 〇xl〇-4Pa or more, h 0xl0-】Pa under the conditions of film formation and water: minutes = film formation phase comparison 'crystals of each composition to (10). C or so. Therefore, relative to indium tin (n) x) The composition range of the value of 6.7xl〇), the crystallization temperature at the time of film formation of u&gt;arPa is not up to the shoe, in particular, the film formation condition of the amorphous film is obtained by the partial pressure of L〇x10, above, &quot;xl〇_ipa film formation conditions can be made non-parallel..., for example, crystallizing around the boot: water production: when the partial pressure ratio is lower than h, the above-mentioned crusted -%) =, = effect of the sage, on the other hand, the partial pressure of water is higher than the upper limit (1 · 0 and the time of the knot, the condition of the moon is made amorphous), but the core I is annealed. 2 'The specific resistance (resistivity) of the film is not reduced, and most of the crystallization is poor under the resistance of 5.^ Ω·_. And the molar ratio of 'in relation to indium> Moir + Moer γ 旲 ' with respect to x is not (~2. 9χ1〇Λη(χ)-6. 7χ1(Γ2)

When the value of JO 320646 200923973 is more than or equal to the range, the film is formed into a film having a crystallization temperature of 100 ° C or higher, even if the partial pressure of water is less than 1. Ox 10 4Pa. May 2007-095783), it is not necessary to form a film under the conditions of 1. 0xl0_4Pa or more, 1. Oxl (^Pa or less), but film formation under these conditions, of course, may be non- Next, the method for producing a sputtering target used in the present invention will be described, and the production method is not particularly limited. First, as a sputtering target constituting the present invention The starting materials are generally powders of In2〇3, Sn〇2 and BaC〇3, and Iri2〇3 and BaC〇3 are pre-calcined into BaIn2〇4, in which In2〇3 and Sn〇2 are mixed. It is preferable to use it in order to prevent the occurrence of pores due to gas generated when BaC〇3 is decomposed. It is also possible to use such monomers, compounds, composite oxides, etc. as raw materials, and when using monomers or compounds. The step of forming an oxide is carried out in advance. Mixing at a desired blending ratio The raw material powder and the molding method are not particularly limited, and various wet methods or dry methods known in the art can be used. Examples of the dry method include a cold press (Co Id Press) method or a hot press method. The pressing method is to fill a molding powder into a mixed powder to prepare a molded body, which is then calcined. The hot pressing method is to calcine and sinter the mixed powder in a forming mold. In the wet method, for example, a filter forming method is used. The filter molding method is a filter molding method in which a water-insoluble material obtained by decompressing water from a ceramic raw material slurry to obtain a molded body is obtained. a lower mold for forming having one or more drainage holes, a water-permeable filter placed on the lower mold for molding, and a sealing material for sealing the filter through the upper surface of 320646 200923973 The molding die frame is composed of the lower mold for molding, the molding die frame, the sealing material, and the transition piece, which are separately detachable, so that it is difficult to reduce from the same side of the filter raft [drainage material] Moisture filtration The mold is prepared by mixing (4) the mixed powder, the ion-exchanged water and the organic additive, and the slurry is injected into the filter forming mold, and the water in the slurry is discharged under reduced pressure from the same side of the sieve to produce a After the obtained molded body is dried, the calcination temperature is preferably 1300 to = o °c. The better is to delete 165 (rc, the environment) It is an atmospheric environment, an oxygen environment, a non-oxidizing environment, or a vacuum environment. On the other hand, the case of the rolling method is better at 120 (sintering near rc, which is a non-oxidizing environment or a vacuum environment. After being fired in various ways, the machine for forming and machining is machined to a predetermined size to form a target. [Examples] Hereinafter, the present invention will be described based on examples, but not limited thereto. I (sputter target production examples 1 to 67) A purity of &gt; 99.99% of In2〇3 powder, secret powder, and purity &gt; 99.9% of Bac〇3 powder were prepared. First, the total amount of 2 〇〇g of the in2〇3 powder of BET=27m/g is 58.6 wt% and Ba=1 · 3 m2/g of BaC〇3 powder 4 ..4 wt%, and dried. The state is mixed with a ball mill and placed in the atmosphere as (4). (3) Performing calcination in 3 hours to obtain BalmO4 powder. Secondly, the above-mentioned Ba is a powder, and the powder of 祝 祝 忌 忌 忌 及 及 〗 〗 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 The ratio of 'prepared to about (10), to the ball two ^ Bay: ~. Then, a PVA aqueous solution as a binder was added, and the mixture was cold-pressed to obtain a molded body. In the atmosphere, Fu, ι. Hour, every ◦c: heart: ί vs.: f* body degreasing' Secondly, a sintered body is produced in _2, 凡, 日' in an oxygen environment. The specific calcination conditions are: loot: / h, = liter: to 80 (rc, then 4, c / h ' from _.. warmed to the offer, after the small sputum, with 100 ° C / h cooling conditions, From 160 (rc cooling to room two 丨 processing 5 烧结 sintering system to dry. The density and integrated resistance at this time, for example, in the composition of 32, each is. In the composition of the coffee 22 'different is 6. 96g /cm3, 2·87χ1 (Γ4Ω. cm. (Test Examples A1 to A18) In a 4 inch DC magnetron sputtering device, each of the above-described manufacturing examples 1 to 18 is sprinkled with a substrate temperature of room temperature. Temperature (about 2 〇. 〇), the partial pressure of water is l_〇xl (T4Pa, _ side change oxygen partial pressure between 〇 to 3 〇sccm (equivalent to 0 to 1. 1x10 2pa), while making the test The transparent conductive films of Examples A1 to A18. The sputtering conditions were as follows, and a film having a thickness of 1200 A was produced. The size of the grain was .0 = 4 in, t = 6 mm. Sputtering method: DC magnetron sputtering. Broken and rotating chestnut (rotary pumpH cold beam vacuum pump (cryo pump). The degree of vacuum reached: 5 · 3xl (T6 [Pa].

Ar pressure: 4.0xi0-i [Pa]. Oxygen pressure: 〇 to 1. lxl (T2 [Pa]. Water pressure: 1. 〇xl〇-4 [Pa]. 320646 200923973 substrate temperature: room temperature. Sputtering power: 130W (power density 1. 6W / cm2) The substrate was used: C0RNING #1737 (glass for liquid crystal display), t=0. 8 mm. With respect to Test Examples A1 to A18, the relationship between the oxygen partial pressure and the resistivity in film formation at room temperature was obtained at 250°. The relationship between the partial pressure of oxygen after C annealing and the resistivity. Table 1 below shows the molar ratio of 1 mol of In, Ba and Sn relative to each sample, and shows the crystal formation at room temperature. State (a indicates amorphous film, c indicates non-crystallized film) ' _ non-amorphous boat crystallization temperature. Table 1 in the film formation resistivity is the best oxygen content at room temperature film formation The film resistivity in the press. Further, the resistivity after annealing is the resistivity in the optimum oxygen partial pressure at the annealing of 250 ° C. Further, the crystallization temperature shown in Table 1 is obtained as follows. After annealing at 250 °C, the partial pressure of oxygen at the lowest resistivity, film formed at room temperature, at 50 ° C, from 100 ° C to 300 ° C (500 必要 if necessary) to the atmosphere I: Annealing for 1 hour, the film was analyzed by film xRD. Regarding the diffraction ♦ (ha 1 〇peak) of the amorphous film formed at room temperature, the ray was detected because the annealing temperature became high. The initial temperature is determined as the crystallization temperature. Further, the other method for determining the crystallization temperature may be a high temperature film xRD method. Further, in Fig. 1, the test examples A1 to A18 are plotted to • The crystallization temperature is 100 to 300 ° C, and the crystallization temperature is 350 ° C or higher. From the results, the crystallization temperatures of all the samples are 100 ° C to 300 ° C. 14 320646 200923973 [ Table 1] Snapshot numbering manufacturing example &amp; ratio Ba ratio crystal state crystallization bS^(°C) resistivity at film formation (X 1 (ΤΩ. cm) resistivity after annealing (x ΙΟ^Ω · cm) A1 1 0. 05 0.0001 a 150 4.7 3.4 A2 2 0. 05 0.0002 a 150 4.8 3.4 A3 3 0.05 0.0005 a 150 4. 9 3. 5 A4 4 0.05 0.001 a 150 4. 7 3. 6 A5 5 0.05 0.002 a 150 4.7 3.4 A6 6 0.05 0.005 a 150 4.8 3.5 A7 7 0.05 0.01 a 150 5.2 3.6 A8 8 0. 075 0.002 a 150 4.6 2.5 A9 9 0. 075 0.005 a 150 4.8 2.6 A10 10 0.1 0.0001 a 150 4.5 1.9 All 11 0.1 0.0002 a 150 4.5 1.9 A12 12 0.1 0.0005 a 150 4.5 1.9 A13 13 0.1 0.001 a 150 4.5 1.9 A14 14 0.1 0.002 a 150 4.5 1.9 A15 15 0.15 0.0001 a 200 4.7 2.0 A16 16 0. 15 0.0002 a 200 4.7 2.0 A17 17 0.15 0.0005 a 200 4.6 2.0 A18 18 0.2 0.0006 a 250 4.7 2.2 (Test Examples B1 to B18). The sputtering targets of each of the manufacturing examples 1 to 18 were separately mounted on a 4 inch DC magnetron sputtering apparatus, the substrate temperature was room temperature (about 20 ° C), and the partial pressure of water was 1.0 15 320646 200923973 . xl (T3Pa, a transparent conductive film of Test Examples Β1 to Β18 was prepared while varying the oxygen partial pressure between 0 and 3. Osccm (corresponding to 0 to 1.1.0xx0_2Pa). The conditions of the sputtering were as follows. A film having a thickness of 1200 A is produced. The size of the bar: &lt;/&gt; = 4 in, t = 6 mm. Sputtering method: DC magnetron splash button. Exhaust device: rotary pump + refrigerated vacuum pump. , reaching vacuum: 5. 3xlO_6[Pa].

Ar pressure: 4 · OxlO_I [Pa]. Oxygen pressure: 0 to 1. lxl (T2 [Pa]. Water pressure: 1.0xl03 [Pa]. Substrate temperature: room temperature. Sputtering power: 130 W (power density 1. 6 W/cm2). Substrate: C0RNING #1737 (glass for liquid crystal display), t=0. 8mra For the test examples B1 to B18, the relationship between the oxygen partial pressure k at room temperature and the resistivity and the oxygen partial pressure and resistivity after annealing at 250 ° C were obtained. In the following Table 2, the molar ratio of Ba and Sn in the case of 1 mol of In for each sample is shown in a crystalline state at room temperature (a is regarded as an amorphous film, When c is used as the crystallization film), the crystallization temperature of the amorphous film is also exhibited. Further, the crystallization temperature, the resistivity at the time of film formation, and the resistivity after annealing are as described above. Further, in Fig. 2 The test examples B1 to B18 were marked with a crystallization temperature of 100 to 300 ° C and a crystallization temperature of 350 16 320646 200923973 ° ° C with ▲. As a result, it was found that the crystallization temperature of all the samples was 100 ° C to 300 ° C. [Table 2] Sample No. Production Example Sn Ratio of Ba to Crystallization State Crystallization Temperature rc) Resistivity at Film Formation (χΙΟ^Ω · cm) Resistivity after annealing (χΙΟ^Ω cm) B1 1 0. 05 0.0001 a 200 4.7 3.5 B2 2 0.05 0.0002 a 200 4.8 3.5 B3 3 0.05 0.0005 a 200 4.9 3.5 B4 4 0.05 0.001 a 200 4.9 3.4 B5 5 0. 05 0.002 a 200 4.9 3.5 B6 6 0. 05 0.005 a 200 5.0 3.6 B7 7 0.05 0.01 a 200 5.4 3.6 B8 8 0.075 0.002 a 200 4.8 2.6 B9 9 0.075 0.005 a 200 4.9 2.7 B10 10 0.1 0.0001 a 200 4.5 2.1 B11 11 0.1 0.0002 a 200 4.5 2.0 B12 12 0.1 0.0005 a 200 4.6 2.1 B13 13 0.1 0.001 a 200 4.6 2.1 B14 14 0.1 0.002 a 200 4.7 2.1 B15 15 0.15 0.0001 a 250 4.6 2.2 B16 16 0.15 0.0002 a 250 4.7 2. 0 B17 17 0.15 0.0005 a 250 4.7 2.2 B18 18 0.2 0. 0006 a 300 4.9 2.4 17 320646 200923973 . (Reference test examples Cl to C67). The sputtering targets of each of the manufacturing examples 1 to 67 are respectively mounted on a 4 inch DC magnetron sputtering apparatus, the substrate temperature is room temperature (about 20 ° C), and the partial pressure of water is 1.Ox 10 - 5 Pa. While changing the oxygen partial pressure between 0 and 3. Osccm (equivalent to 0 to 1. 1. 0xl0_2Pa), a transparent conductive film of Reference Examples C1 to C67 was prepared. — The conditions of the sputtering are as follows, and a film having a thickness of 1200 A is obtained. Geba size: 0 = 4in, t = 6mm 〇, sputtering method: DC magnetron sputtering. Exhaust device: rotary pump + refrigerated vacuum pump. The degree of vacuum reached: 5. 3xlO_6 [Pa].

Ar pressure: 4. Oxl (r) [Pa]. Oxygen pressure: 0 to 1. lxl (T2 [Pa]. Water pressure: 1. 0xl (T5 [Pa]. Substrate temperature: room temperature. Sputtering power: 130W (Power density: 1.6 W/cm2). Substrate used: C0RNING #1737 (glass for liquid crystal display), t=0. 8 mm For reference test examples C1 to C67, the oxygen partial pressure in the film formation at room temperature was determined. The relationship between the resistivity and the partial pressure of oxygen after annealing at 250 ° C. The following Tables 3 and 4 show the difference between Ba and Sn for 1 mol of In with respect to each sample. The ear ratio is not crystallized at room temperature (a is used as an amorphous film and c is used as a crystallized film), and the crystallization temperature of the amorphous film is also exhibited. The resistivity at the time of film formation and the resistivity after annealing are as described above. 18 320646 200923973 = 2 The dry form is obtained, and the resistivity of the film after film formation is obtained at room temperature (about muscle) long partial pressure. The water is paid by the same pressure, and the pressure is determined by the relationship between ^Minimum resistance of oxygen Waste as the best oxygen in the film formation = pressure ': the best oxygen star between the two, the difference between the two, to call the difference, to ▲ is almost the same. Indium Branch for the indium 1 tin The material y is expressed by X as the value of (~2.9xl(T2Ln〇〇-6.7x) with respect to 1伯', and (_2 nun-iT , , v=〇n士(Χ)—4·6Χ10, the value below, except for the eight-segment life ^ 'After-formed amorphous type Qingcheng low f resistance filming oxygen:: coating = after 2 Γ臈 subsequent resistance filming Oxygen partial pressure is not the same, partial pressure is not the same. Also ^ the best oxygen partial pressure and the lowest oxygen resistance at room temperature i in the composition range 'is not formed by the film at the time of film formation : Γ 佳 good oxygen partial pressure 'better is the crystallization resistance after annealing; change: = resist oxygen partial pressure film formation, after annealing the film of electricity J 4 / to go relative to the marriage 1 Mo tin Mohby y, relative to the indium material, the mail X wire (_2. 9 navigation) - 6. 7x, dry day, the crystallization temperature is smaller than the loot range. Eight # as the first picture and the second As shown in the figure, it is known that when the S of water is in the indium film, it is relative to the tin of indium 1 When the molar ratio of Mobi y, 10-WW 7 is expressed as X in the range of less than (-2.9x • xl〇), the crystallization temperature is as high as 150. 〇320646 19 200923973, above, easy film formation It is an amorphous film. [Table 3] Sample No. Production Example Sn Ratio of Ba to Crystallization State Crystallization Temperature rc) Resistivity at Film Formation (X 1 (ΤΩ · cm) Resistivity after Annealing (χ10'4Ω · cm) C19 19 0 0.1 a &gt; 450 19.2 21.4 C20 20 0.025 0.07 a 400 12.7 14.3 C21 21 0.025 0.1 a &gt;450 15.3 17.5 C1 1 0.05 0.0001 c &lt;100 4. 6 3.3 C2 2 0.05 0.0002 c &lt;100 4. 7 3.4 C3 3 0. 05 0. 0005 c &lt;100 4.8 3.4 C4 4 0. 05 0. 001 c &lt;100 4. 7 3.5 C5 5 0.05 0.002 c &lt;100 4. 2 3.0 C6 6 0.05 0.005 c &lt 100 4.2 3.1 C7 7 0.05 0. 01 c &lt; 100 4.3 3.4 C22 22 0.05 0. 02 a 150 5.2 4.9 C23 23 0.05 0. 03 a 200 7.5 6.2 C24 24 0.05 0. 05 a 400 8.2 9.2 C8 8 0.075 0 002 c &lt;100 3.3 2.1 C9 9 0.075 0.005 c &lt;100 3.4 2.1 C25 25 0.075 0. 01 a 100 4.2 3. 1 C26 26 0.075 0. 02 a 150 5.1 3.5 C27 27 0. 075 0. 03 a 250 6.7 5. 1 C10 10 0.1 0. 0001 c &lt;100 4.4 1.8 C11 11 0.1 0.0002 c &lt;100 4.4 1.8 20 320646 200923973 C12 12 0.1 0.0005 C &lt;100 4.4 1.8 Γ13 13 0.1 0.001 c &lt;100 4.4 1.8 C14 14 0.1 0.002 c &lt;100 4.5 1.8 C28 28 0.1 0.005 a 100 4. 5 1.8 C29 29 0.1 0.01 a 150 4. 7 2.3 C30 30 0.1 0.02 a 200 5. 6 2.7 C31 31 0.1 0.03 a 250 6. 1 4. 6 C32 32 0.1 0.05 a 400 8. 6 10.0 C33 33 0.1 0.1 a &gt;450 14.2 15.3 C15 15 0.15 0.0001 c &lt;100 4. 7 1.8 C16 16 0.15 0.0002 c &lt;100 4. 7 1.8 C17 17 0.15 0.0005 c &lt;100 4. 8 1.8 C34 34 0.15 0.001 a 150 4. 6 1.8 C35 35 0.15 0.002 a 150 4. 6 .1.8 C36 36 0.15 0. 005 a 150 4.8 1.8 ί. 21 320646 200923973 , [Table 4] Sample No. Manufacturing Example Sn is crystallized in a crystal state than Ba Temperature rc) Resistivity at film formation (χ10&quot;4Ω · cm) Resistivity after annealing (χ10'4Ω · cm) C37 37 0.15 0.01 a 200 5. 0 2.1 C38 38 0. 15 0.02 a 250 6.0 2.6 C30 30 0. 15 0.03 a 350 7. 0 5.9 C40 40 0.15 0. 05 a &gt;450 8.6 8.1 C18 18 0.2 0.00006 a &lt;100 4.9 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. 9 1.9 C46 46 0.2 0.005 a 200 5. 2 1.9 C47 47 0.2 0.01 a 200 5. 9 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 &gt;450 10.3 9.8 C51 51 0.22 0. 00005 a 100 4. 9 2.0 C52 52 0.22 0. 033 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 22 320646 200923973

(Test Examples A68 to A73). The production example (10) to the target of the sintered body having the composition shown below is prepared in the same manner as in the following Tables V.. On the 4 inch DC magnetron plating device, each board is equipped with a temperature of room temperature (about scratch), the water is divided into two Pa, and the oxygen partial pressure is changed to 3. A transparent conductive film of Test Examples A68 to A73 was prepared between 〇SCCm (corresponding to 0 to 1.0x10 Pa). The conditions for the splattering are as follows, and a film having a thickness of 丽a is obtained. Geba size. 0 = 4in, t = 6mm. Sputtering method: DC magnetron sputtering. 23 320646 200923973 , Exhaust device: rotary pump + refrigerated vacuum pump. The degree of vacuum reached: 5. 3xlO_6 [Pa].

Ar pressure: 4. OxliT1 [Pa]. Oxygen pressure: 0 to 1. 1x10-2 [Pa]. Water pressure: 1. 0xl0_4 [Pa]. Substrate temperature: room temperature. Sputtering power: 130W (power density 1. 6W / cm2). Substrate used: C0RNING #1737 (glass for liquid crystal display), t = 0.8 mm With respect to Test Examples A68 to A73, the relationship between the oxygen partial pressure and the specific resistance at room temperature film formation and annealing at 250 ° C were obtained. The relationship between oxygen partial pressure and resistivity. Table 5 below shows the molar ratio of Ba and Sn with respect to the indium 1 mol of each aspect, and shows the crystalline state of film formation at room temperature (a is regarded as an amorphous film, and c is regarded as At the same time as the crystallized film), the crystallization temperature of the amorphous film is also shown. Further, the crystallization temperature, the resistivity at the time of film formation, and the resistance after annealing are as described above. Further, in Fig. 1, test examples A68 to A73 are labeled with test examples A1 to A18, and the crystallization temperature is 100 to 300 ° C, and the crystallization temperature is 350 by ▲. Above °C. As a result, it was found that the crystallization temperature for all the samples was 100 ° C to 300 24 320646 200923973. [Table 5] Model number Manufacturing example Sn ratio Ba ratio crystal state crystallization temperature rc) Resistivity at the time of film formation (χ10'4 Ω · cm) Resistivity after annealing (χΙΟ^Ω · cm) A68 68 0.025 0.00005 a 100 5.6 4.2 A69 69 0.025 0.001 a 100 5. 7 4.3 A70 70 0.025 0.01 a 200 6.2 4. 9 A71 71 0.05 0.00001 a 150 4. 7 3.3 A72 72 0.15 0.00002 a 200 4.6 2 A73 73 0.2 0.00001 a 250 4.6 2.2 (Test Example B 6 8 to B 7 3). The sputtering targets of each of the manufacturing examples 68 to 73 were separately mounted on a 4 inch DC magnetron sputtering apparatus. The substrate temperature was room temperature (about 20 ° C), and the partial pressure of water was 1.0 x 10 -3 Pa. The varying oxygen partial pressure was between 0 and 3.0 sccm (corresponding to 0 to 1. lxl (T2Pa), and the transparent conductive films of Test Examples B68 to B73 were prepared. The conditions of the sputtering were the same as in Test Example A68. A73 was the same, and a film having a thickness of 1200 A was obtained. About the test Example B 6 8 to B 7 3 'The gas partial pressure and resistivity at room temperature were determined and after annealing at 250 ° C The relationship between the partial pressure of oxygen and the specific resistance. Table 6 below shows the molar ratio of Ba and Sn with respect to 1 mol of In for each sample, showing the crystalline state of film formation at room temperature (in terms of a is used as an amorphous film and c is used as a crystallization film), and the crystallization temperature of the amorphous film 25 320646 200923973 r is also shown. Further, 'crystallization temperature, resistivity at film formation, and resistance after annealing In the second figure, Test Examples B68 to B73 are labeled with Test Examples B1 to B18, and the crystallization temperature is 1. 00 to 300 ° C, ▲ indicates that the crystallization temperature is 350 ° C or higher. As a result, it is found that the crystallization temperature of all the samples is from 100 ° C to 300 ° C. [Table 6] Sample No. Manufacturing Example Sn ratio Ba ratio Crystallization crystallization temperature (°C) Resistivity at film formation (χ10'4Ω · cm) Resistivity after annealing (χ10'4Ω · cm) B68 68 0.025 0.00005 a 150 5.7 4.4 B69 69 0.025 0. 001 a 150 5. 9 4.4 B70 70 0.025 0.02 a 250 6.3 5.0 B71 71 0. 05 0.00001 a 200 4. 7 3.5 B72 72 0.15 0.00002 a 250 4. 5 2.1 B73 73 0.2 0.00001 a 300 4. 9 2.4 (Refer to Test Case C68 to Cx) The sputtering target of each of the manufacturing examples 68 to 73 is mounted on a 4 inch DC magnetron sputtering device, the substrate temperature is room temperature (about 20 ° C), and the partial pressure of water is 1. 0x1 (PPa, while changing the partial pressure of oxygen to 0 to 3. 0seem (equivalent to 0 to 1. lxl (T2Pa), while preparing the transparent conductive film of reference test examples C68 to C73. Conditions of sputtering, system and test In the same manner as in Examples A68 to A73, a film having a thickness of 1200 A was obtained. With respect to Reference Test Examples C68 to C73, the partial pressure of oxygen formed at room temperature was determined. Relationship between the resistivity and oxygen at 250 ° C annealing after the partial pressure with the resistivity. In the following Table 7, the molar ratio of 'B and Sn' with respect to 1 mol of In for each sample shows the crystal state of film formation at room temperature (a is regarded as an amorphous film, and c is used. As the crystallized film, the crystal crystallization temperature of the amorphous film is also shown. Further, the crystallization temperature, the resistivity at the time of film formation, and the resistivity after annealing are all as described above. Further, in Fig. 3, the results of Test Examples C68 to C73 were marked with reference to Test Examples C1 to C67, that is, with respect to the targets of Production Examples 68 to 73, at room temperature (about 20 °C) The relationship between the oxygen partial pressure and the resistivity of the film formed under the partial pressure, and then the optimum oxygen partial pressure is obtained, and the film formed by partial pressure of each oxygen is annealed at 250 ° C. The relationship between the resistivity and the partial pressure of the film forming oxygen, the resistivity after annealing is the lowest resistance of oxygen [gas partial pressure is taken as the optimum oxygen partial pressure at the time of film formation at 250 ° C, and the best oxygen for both is judged. Whether the partial pressure is different, in Fig. 3, # indicates different, and ▲ indicates almost the same. 27 320646 200923973 [Table 7]

(Experiment to confirm the presence of hydrogen). The DC magnetron reduction of 4 inches: the sputtering target of the manufacturing example 13 is separately installed on the mining device, and the substrate temperature is room temperature (about 2 〇. 〇, the partial pressure of water is 〖. 〇 &gt;&lt; M /a (as an example), 5· 〇xl〇-3pa (as an example illusion and &amp; 〇χ 10 Pa (as a comparative example), three examples were prepared, examples, examples were prepared 2 and the transparent conductive film of Comparative Example 1. The conditions of the sputtering were as follows, and a film having a thickness of 1200 A was produced. The size of the bar was 0 = 4 in, t = 6 mm. The method of antimony mining: DC magnetron sputtering. Air entanglement: rotary pump + refrigerated vacuum pump. Reach vacuum: 5. 3xl (T5 [pa].

Ar pressure: lOxlOlPa]. Oxygen pressure: 〇 [pa]. Water pressure: 1. Oxio-2, 5. Oxio-3, 5. 〇xl〇-5 [Pa]. 28 320646 200923973 , substrate temperature: room temperature. Sputtering power: 130W (power density 1. 6W / cm2). Use substrate: C0RNING #1737 (glass for liquid crystal display), t=0·8 ram Here, 'the crystal shape of the sample formed by film formation in each condition was analyzed by film xRD, and it was broken in Example 1 and Example 2. An amorphous film was formed, and crystallization was formed in Comparative Example 1. Further, regarding the presence of hydrogen in each film, the time-of-flight secondary ion f mass spectrometry (T0F-SIMS, TRIFT IV manufactured by ULVAC PHI Co., Ltd.) was used, and the samples of Example 1 and Comparative Example 1 were represented by the following The measurement condition 'confirmed (H+ ion number) / (all ion number) was confirmed. [Measurement conditions] Primary ion: Au +

Acceleration voltage: 30KV Scanning conditions: raster-scan (2〇〇χ2〇〇# m) In Table 8, 'is the analyzed sample T0F_SIMS analysis of the knot i (H+ ion number) / ( All ion numbers). Here, the partial pressure of water at the time of film formation is 5.0·0x1 (in the sample of Reference Test Example 3 in which T5Pa is actually formed in an environment where water does not exist, the detected yttrium ion can be judged as the background. That is, in the recent study, it was reported that the indium oxide film was formed by a partial pressure film formed by a partial pressure lower than the water pressure of Reference Example 3 (JPn. J. Appl. Phys. Vol. 46, No. 28). , 2007 ρρ. L685-L687), it is presumed that the hydrogen ions to be detected are attached to the substrate with a small amount of water attached to the substrate during film formation. Therefore, in the present invention, the water is substantially in the absence of water. The pressure is 5. 0x10 - 5Pa or less in the environment of film formation 29 320646 200923973, the subsequent sample (H + ion number) / (all ions number) of 7. 75 χ 1 (Γ 4 as the reference value, compared to this increase (Η The number of ions + (the total number of ions) was taken as the hydrogen ion contained in the film. Thus, in Comparative Example 2 and Comparative Example 1, the count of V + ions (count of all ions) was observed. When the water pressure becomes large, it also becomes larger. Therefore, as in the methods of Examples 1 and 2, the water pressure at the time of film formation is controlled. The amount of hydrogen changed can be confirmed by taking hydrogen into the film. Further, the hydrogen taken into the film is hydrogen terminated by a dangling bond (unbonded bond) with an atom in the film. There is an effect of hindering the crystallization of the film. [Table 8] Water pressure at the time of film formation [pa] Number of r ions / total ion number measurement result (measurement result) 1 (reference value) Example 1 l. OxlO'2 9.18x1 ( Γ4 1.43xl0_4 Example 2 5. OxlO'3 8. 98x10'4 1.23x10-4 Comparative Example 1 5. Oxl Ο '5 7. 75x10-4 0.00x10'° [Simplified Schematic] FIG. 1 shows the present invention The crystallization temperature diagrams of Test Examples A1 to A18 and A68 to A 7 3 . Fig. 2 shows the crystallization temperature diagrams of Test Examples B1 to B18 and B68 to B 7 3 of the present invention. Fig. 3 shows the present invention. Refer to the results of test examples C1 to C73. [Main component symbol description] No 30 320646

Claims (1)

200923973 ·. VII. The scope of the patent application: 1. A transparent conductive film is made by using an oxide film to form an amorphous film, and the sputum is used to make money. The emulsion sintered body contains cerium oxide 3 and cerium, and the transparent conductive film has the characteristics of 'the same, the right and the right molybdenum, the inch is 3, the emulsified indium and tin have the same enthalpy' and (4) in the indium 1 The tin material of the material ": the molar ratio of the ingot to the indium 1 molar is 'ιλ-2Τ. Ν χ is not a failure (-2 9χ 〇Ln(x)-6· 7χ1〇-2) The value is 曰. 100 ° C or more. The daily temperature of the human, mouth is 2. The transparent conductive film containing one of the W brothers is transparent as in the patent application scope, wherein the amorphous film I patent The transparent conductive film of the second aspect, wherein the amorphous film 5. The transparent conductive film of the above-mentioned Patent Application No. 4 to 4, which is known as a film which is crystallized by annealing after being formed into a pancreas. For example, the scope of the patent application is carried out in the range of 5 (10) to _t; wherein the annealing is in the transparent conductive film of item 5 of the 7th item, wherein the month after the annealing is - The resistivity of the film is below 5.0x10, 饳. • The transparent conductive film of item 6 of the profit range, wherein the resistivity of the K film after the annealing is below 5. Gxl (r) coffee. The method 'is to use an oxide sintered body to form an amorphous film'. The oxide sintered body contains indium oxide 320646 31 200923973 and tin and contains 钡'. The transparent conductive layer (4) is characterized by containing tin and containing yttrium, and Mohr ratio 7 relative to indium 1 molar tin: phase 2 is inferior to the molar ratio of indium 1 molar to 0 (4 9 x lO Ln (x) - 6. 7 x 10 2) When the amorphous film is formed at the time of film formation, the partial pressure of the water of the film formation day is 1.0xl{r4Pa or more, 1〇xi (rpa below), and 10. The manufacture of the transparent conductive film of the ninth application patent scope The crystallization temperature of the amorphous film by annealing is (10) t or more. 1. The transparent conductive manufacturing method of the ninth patent of the patent application, which is formed into an amorphous film by annealing. It is a film which is crystallized." • In the manufacturing method of the transparent conductive film of claim 10, after the amorphous film is formed, The film is a crystallized film. The method for producing a transparent conductive film according to the eleventh item of Patent 1 is performed by annealing and crystallization is carried out from 丨(10) to fine c. The method for producing a transparent conductive film 2 is carried out by crystallization from the ruthenium to the 縦C. The method for producing a transflective film of the 13th item of the t-fan (4), the resistivity of the j 16 m conductive film is 5n (four) The manufacturing method of the transmissive electric film of the fourth item is the resistivity of the transparent conductive film after the intermediate annealing is 5. (4). 320646