WO2013042747A1 - Corps fritté d'oxyde, procédé pour produire celui-ci, et film conducteur transparent d'oxyde - Google Patents

Corps fritté d'oxyde, procédé pour produire celui-ci, et film conducteur transparent d'oxyde Download PDF

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WO2013042747A1
WO2013042747A1 PCT/JP2012/074111 JP2012074111W WO2013042747A1 WO 2013042747 A1 WO2013042747 A1 WO 2013042747A1 JP 2012074111 W JP2012074111 W JP 2012074111W WO 2013042747 A1 WO2013042747 A1 WO 2013042747A1
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oxide
transparent conductive
conductive film
sintered body
film
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PCT/JP2012/074111
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Japanese (ja)
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桑原　正和
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住友金属鉱山株式会社
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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Definitions

  • the present invention relates to an oxide transparent conductive film used for a display element such as a touch panel, electronic paper, a solar cell, and an optical device such as a light emitting diode (LED) or an organic electroluminescence (EL), and the oxide transparent conductive film.
  • the present invention relates to an oxide sintered body for obtaining a film and a method for producing the same.
  • the oxide transparent conductive film has high conductivity and high transmittance particularly in the visible light region, display elements such as touch panels and electronic paper, solar cells, and transparent electrodes in optical devices such as LEDs and organic EL, etc. It is widely used as a material. In addition, it is also used for heat ray reflective films, antistatic films, and antifogging transparent heating elements for automobile windows.
  • indium oxide (In 2 O 3 + ⁇ ) oxide film As the oxide transparent conductive film, indium oxide (In 2 O 3 + ⁇ ) oxide film, zinc oxide (ZnO + ⁇ ) oxide film, and tin oxide (SnO 2 + ⁇ ) oxide film are widely used.
  • indium oxide-based oxide films are most often used.
  • indium oxide films containing tin oxide as a dopant are called ITO (Indium Tin Oxide) films, and particularly low resistance films. It is mainly used because it can be easily obtained.
  • a sputtering method is used as a main means for manufacturing these transparent oxide conductive films.
  • Sputtering is an effective technique when film formation of low vapor pressure materials and precise film thickness control are required, and its operation is very simple, so it is widely used industrially. ing.
  • a substrate on which a transparent conductive film is formed is used as an anode
  • a sputtering target is used as a cathode
  • glow discharge is generated between them
  • argon plasma is generated.
  • a film is formed by causing argon cations in the plasma to collide with the sputtering target of the cathode and depositing particles of the target component which are blown off by this on the substrate.
  • Sputtering methods are classified into a direct current sputtering method using direct current discharge and a high frequency sputtering method using high frequency discharge.
  • the high-frequency sputtering method has an advantage that stable deposition can be performed not only on a conductive target but also on a high-resistance target or a target in which a conductive material and a high-resistance material are mixed, but the deposition rate is low and the apparatus cost is low. Has disadvantages such as high price.
  • the direct current sputtering method is generally used industrially because it is inexpensive and has a simple film formation operation and is excellent in high-speed film formation. It is necessary to use sex targets.
  • the high-resistance substance is charged by irradiation with argon ions, and arcing occurs during film formation.
  • a conductive target that does not include is required.
  • the DC magnetron sputtering method has an advantage that the deposition rate is high by placing a magnet on the back side of the target and confining ⁇ electrons in the vicinity of the target by applying a magnetic field.
  • an oxide transparent conductive film such as ITO is formed by DC magnetron sputtering, a sufficiently low resistance film cannot be obtained unless the temperature of the substrate is raised. This is because the higher the substrate temperature at the time of film formation, the better the crystallinity of the film and the doping of the additive components, and the lower the resistance value of the resulting film.
  • Japanese Patent Laid-Open No. 2005-290458 discloses a technique relating to a cerium-containing indium oxide-based sputtering target material (In—Ce—O) and a transparent conductive film obtained using this sputtering target. It is disclosed. This transparent conductive film is assumed to be used in an amorphous state. However, when the substrate temperature is set to 200 ° C. or higher, or the substrate is heated at a temperature of 200 ° C. to 250 ° C., the film may be crystallized. It is shown.
  • JP 2004-43851 A discloses that an oxide transparent conductive film having high conductivity and high transmittance in the visible light region is formed by heating the substrate at a temperature of 200 ° C. or higher to form a crystallinity.
  • An indium oxide film (In—W—O) containing tungsten is disclosed.
  • JP-A-9-209134 and JP-A-9-161542 a transparent conductive film having a higher resistance than that of ITO is obtained by a direct current sputtering method. Therefore, a low-resistance metal element such as titanium, iridium, and cobalt is added to ITO.
  • a resistive sputtering target is disclosed. When these sputtering targets are used, a transparent conductive film is obtained even when the substrate temperature is set to room temperature by direct current magnetron sputtering.
  • the present invention provides an oxide transparent conductive film having sufficient crystallinity, which has high conductivity and high transmittance in the visible light region, and such characteristics. It is an object of the present invention to provide an oxide sintered body capable of depositing an oxide transparent conductive film comprising a film by a direct current sputtering method using a transparent resin substrate.
  • the oxide sintered body of the present invention is an oxide sintered body containing indium oxide as a main component and containing tin oxide and cobalt oxide, and an atomic ratio of Sn to In: Sn / In is 0.019 to 0 .102, and the atomic ratio of each component to the sum of In, Sn, and Co: In / (In + Sn + Co) is 0.771 to 0.967, Sn / (In + Sn + Co) is 0.016 to 0.091, Co / (In + Sn + Co) is 0.015 to 0.15, and its relative density is 98% or more. Furthermore, in the oxide sintered body of the present invention, the specific resistance is preferably 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • an oxide transparent conductive film having the following characteristics can be obtained even by film formation at a low substrate temperature of 150 ° C. or lower.
  • Such an oxide sintered body uses indium oxide powder, tin oxide powder, and cobalt oxide powder having an average particle size of 0.05 ⁇ m or more and less than 1.0 ⁇ m as raw material powder. , Water and a water-soluble binder were blended, and the resulting slurry was pulverized, stirred for 10 hours or more, dried and granulated, and the resulting granulated powder was packed into a mold and pressure-molded to obtain The molded body can be obtained by sintering at 1450 ° C. to 1600 ° C. for 12 hours to 25 hours in an oxygen atmosphere.
  • the oxide transparent conductive film of the present invention is a transparent conductive film containing indium oxide as a main component and containing tin oxide and cobalt oxide, and the atomic ratio of Sn to In: Sn / In is 0.019 to 0 .102, and the atomic ratio of each component to the sum of In, Sn, and Co: In / (In + Sn + Co) is 0.771 to 0.967, Sn / (In + Sn + Co) is 0.016 to 0.091, Co / (In + Sn + Co) is 0.015 to 0.15, and the specific resistance is 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • the oxide transparent conductive film of the present invention when the film thickness is 15 nm to 40 nm, it is preferable that the average transmittance of a single film at a wavelength of 400 nm to 800 nm is 98% or more. Moreover, even if it is a case where it exposes to the environment of temperature 95 degreeC and humidity 95% for 1000 hours, it is preferable that the resistance change rate will be 1.2 or less.
  • the specific resistance is 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • a highly crystalline transparent oxide conductive film having a low resistance and a high transmittance such that the average transmittance of a single film at a visible wavelength of 400 nm to 800 nm is 98% or more can be obtained. That is, even when a transparent resin substrate is used as a substrate during film formation, a crystalline oxide transparent conductive film having low resistance and high transmittance can be formed.
  • the oxide sintered body of the present invention has a high relative density and low resistance, even when used as a sputtering target in the formation of an oxide transparent conductive film by a direct current sputtering method, arcing during film formation is performed. , And the generation of nodules and particles due to this can be prevented.
  • oxide sintered body (2) manufacturing method of oxide sintered body, (3) film formation of transparent conductive film, and (4) transparent conductive film.
  • Oxide sintered body As a result of intensive studies on indium oxide-based oxide sintered bodies, the inventors have added a cobalt oxide in addition to indium oxide and tin oxide, and these The composition ratio of each metal component of indium (In), tin (Sn), and cobalt (Co) constituting the oxide is regulated within a predetermined range, and an oxide sintered body is manufactured under predetermined manufacturing conditions. By doing so, it becomes possible to increase the density of the obtained oxide sintered body and to make the sintered body texture dense, and b) to use the oxide sintered body of the present invention as a sputtering target.
  • the present invention has obtained the knowledge that it has low resistance and high transmittance and has excellent stability with little resistance change even in a high temperature and high humidity environment (temperature 95 ° C., humidity 95%, 1000 h). Has been completed.
  • the content of tin oxide is regulated so as to be within a range of 0.019 to 0.102 in terms of Sn / In atomic ratio of Sn. If the tin oxide content is less than 0.019 Sn / In, the relative density of the sintered body will not be 98% or more, and the specific resistance of the sintered body will be 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less. It will not become. Further, in the transparent conductive film formed using such a sintered body having a small content of tin oxide, the average transmittance of the film does not become 98% or more, and the specific resistance of the film is also 5 ⁇ 10 ⁇ 3.
  • the resistance change rate in a high temperature and high humidity environment exceeds 1.2.
  • the content of tin oxide exceeds 0.102 in Sn / In, the oxide transparent conductive film after film formation does not crystallize at a substrate temperature of 150 ° C. or lower, and the average transmission of the obtained film The rate will not be over 98%.
  • the tin oxide content is preferably in the range of 0.040 to 0.102 in terms of Sn / In.
  • the content of indium oxide, tin oxide, and cobalt oxide is 0.771 to the atomic ratio of each metal component to the total of In, Sn, and Co: In / (In + Sn + Co)
  • the regulation is 0.967, Sn / (In + Sn + Co) is 0.016 to 0.091, and Co / (In + Sn + Co) is 0.015 to 0.15.
  • the density of the oxide sintered body is increased, the sintered body structure is densified, the crystallinity is improved, and the crystal orientation is in a certain direction. Can be controlled. Due to the action of this cobalt oxide, it is possible to stably obtain the characteristics of low resistance and high transmittance in the oxide transparent conductive film by regulating the content of tin oxide, and in particular, resistance in a high temperature and high humidity environment. Excellent stability with a change rate of 1.2 or less is brought about.
  • the cobalt oxide content needs to be 0.015 to 0.15 in terms of the atomic ratio of Co to the total of In, Sn and Co: Co / (In + Sn + Co).
  • the content of cobalt oxide is Co / (In + Sn + Co) and less than 0.015, the density of the oxide sintered body is not sufficiently high, and the specific resistance of the sintered body is also high. In this case, although the obtained transparent conductive film has crystallinity, the specific resistance tends to be high, and the stability is not sufficient.
  • the cobalt oxide content is preferably in the range of 0.05 to 0.15 in terms of Co / (In + Sn + Co).
  • the content of indium oxide is 0.771 to 0.967 in In / (In + Sn + Co), and the content of tin oxide is 0.016 to 0.091 in Sn / (In + Sn + Co). Is preferred.
  • the oxide sintered body of the present invention has a relative density from the viewpoint of effectively preventing the arcing generated during sputtering and the causes affecting the film properties such as the generation of nodules and particles resulting therefrom. Needs to be 98% or more, more preferably 99% or more.
  • the specific ratio (volume resistivity) of the oxide sintered body is set to 5 ⁇ 10 5 by regulating the composition ratio of the oxide sintered body as described above and setting the relative density to 98% or more. ⁇ 3 ⁇ ⁇ cm or less, preferably 1.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less. That is, when an oxide sintered body having a lower relative density and a higher specific resistance than the range defined in the present invention is used, the rate of change in resistance under a high temperature environment deteriorates, and the stability of the film deteriorates. The transmittance of the film is lowered and the specific resistance of the film is also increased.
  • (2-1) Raw material powder As a raw material of the oxide sintered body according to the present invention, indium oxide powder, tin oxide powder and cobalt oxide powder can be used. It is necessary to be 0.05 ⁇ m or more and less than 1.0 ⁇ m. Preferably, the average particle size of these powders is in the range of 0.1 ⁇ m or more and less than 0.8 ⁇ m.
  • the average particle size is less than 0.05 ⁇ m, the powder aggregates and it becomes difficult to mix uniformly.
  • the thickness is 1.0 ⁇ m or more, the resulting oxide sintered body cannot have a relative density of 98% or more. For this reason, arcing generated during sputtering occurs, and the characteristics of the film deteriorate due to generation of nodules and particles resulting from the arcing.
  • the mixing ratio of these powders may be determined according to the composition ratio of the target oxide sintered body, that is, the atomic ratio of each metal component. Specifically, the atomic ratio of Sn to In: Sn / In is set to 0.019 to 0.102, and the atomic ratio of each component to the total of In, Sn, and Co: In / (In + Sn + Co) is Preparation may be made so that 0.771 to 0.967, Sn / (In + Sn + Co) is 0.016 to 0.091, and Co / (In + Sn + Co) is 0.015 to 0.15.
  • a water-soluble binder is added to these raw material powders in an amount of 0.5 to 1.5% by mass, and is further placed in a resin pot together with water. Grind and mix.
  • the water-soluble binder is not limited as long as it is a known binder that disappears or vaporizes by heating, and for example, polyvinyl alcohol (PVA), polyvinyl butyral, methyl cellulose, and the like can be used.
  • a ball mill and a bead mill can be used for this process.
  • a ball mill in terms of cost
  • a bead mill from the viewpoint of work efficiency because the ball mill takes much time to grind.
  • the balls and beads for example, those made of hard zirconia (ZrO 2 ) are preferably used.
  • the grindability changes depending on the ball diameter or bead diameter, it is preferable to use a ball having a diameter of about ⁇ 2 mm to ⁇ 6 mm and a bead of about ⁇ 0.2 mm to ⁇ 0.7 mm.
  • the wet pulverization and mixing conditions are preferably 50 to 70 rpm and a pulverization / mixing time of 15 to 28 hours.
  • the number of rotations is preferably 1300 rpm to 1700 rpm, and the pulverization / mixing time is preferably 3 hours to 6 hours.
  • the time for pulverization and mixing is insufficient, the sintered body density finally obtained decreases.
  • zirconia is mixed as an impurity, and the density of the sintered body similarly decreases.
  • a slurry containing raw material powder having an average particle size of 0.5 ⁇ m or less is obtained.
  • the average particle diameter is preferably in the range of 0.1 ⁇ m to 0.5 ⁇ m.
  • the viscosity of the slurry is preferably 30 mPa ⁇ s to 600 mPa ⁇ s.
  • the slurry containing the raw material powder obtained in the above step is spray dried to obtain granulated powder.
  • a spherical granulated powder by using a spray dryer.
  • the drying temperature during spray drying is preferably in the range of 120 ° C to 200 ° C. Further, it is preferable to appropriately adjust the drying speed according to the amount of exhaust air so that spherical granulated powder can be obtained according to the apparatus.
  • a spray dryer it is preferable to use a spray dryer using a disk having excellent mass productivity.
  • the particle size of the granulated powder is desirably 40 ⁇ m to 100 ⁇ m in terms of average particle size.
  • the granulated powder obtained through the spray drying step is filled in a rubber mold and is subjected to a pressure of 250 MPa to 350 MPa, more preferably 280 MPa to 320 MPa, using a cold isostatic press (CIP). Molding is performed at a pressure of. At this time, CIP may be performed after preforming by uniaxial pressing.
  • CIP cold isostatic press
  • the maximum pressure holding time during molding is preferably 1 to 10 minutes.
  • the gas generated by decomposing the water-soluble binder is discharged out of the furnace together with oxygen, thus promoting binder removal.
  • a high-strength and high-density sintered body can be obtained.
  • the oxygen concentration can be up to 100% by volume (pure oxygen atmosphere), but about 30% by volume is sufficient from the viewpoint of cost.
  • the heating temperature during binder removal is preferably 200 ° C. to 800 ° C., and the heating time is preferably 30 hours or more.
  • the heating temperature is less than 200 ° C.
  • the binder remains without volatilization, leading to a decrease in the density of the sintered body.
  • the temperature exceeds 800 ° C.
  • shrinkage of the molded body starts during the binder removal step, so that the binder remains inside the sintered body, causing a problem of density reduction.
  • the heating time is less than 30 hours, the binder may not be sufficiently decomposed.
  • the rate of temperature rise is preferably 0.1 ° C./min to 1.5 ° C./min, and 0.3 ° C./min to 1.0 ° C./min. More preferably, minutes.
  • the compact is sintered by firing at a temperature of 1450 ° C. to 1600 ° C. for 10 hours to 25 hours under atmospheric pressure.
  • the firing temperature is preferably 1450 ° C. to 1600 ° C., more preferably 1470 ° C. to 1570 ° C.
  • the liquid phase sintering can proceed sufficiently to increase the density of the sintered body, and further, the indium oxide can be prevented from melting and sintered in a desired shape.
  • the body can be easily manufactured.
  • the holding time at the above baking temperature is preferably 10 hours to 25 hours, and more preferably 15 hours to 20 hours. Within this range, a high-quality indium oxide-based oxide sintered body can be obtained while realizing a reduction in sintering time (reduction in power consumption) and high productivity.
  • the rate of temperature rise is preferably 0.1 ° C./min to 1.5 ° C./min, preferably 0.3 ° C./min. More preferably, it is set to ⁇ 1.0 ° C./min. Further, after holding at the firing temperature for a predetermined time, it is preferable to cool to near room temperature at a cooling rate in the range of 0.2 ° C./min to 1.2 ° C./min.
  • the sputtering method for film formation using the oxide sintered body of the present invention as a sputtering target is not limited at all, and any known means can be used. However, from the viewpoint of mass productivity, it is preferable to adopt a means using a direct current sputtering method, particularly a direct current magnetron sputtering apparatus. Since the relative density of the sputtering target of the present invention is as high as 98% or more, the occurrence of arcing and nodules is suppressed even when the direct current sputtering method is used.
  • a film having high crystallinity can be obtained even when the substrate temperature during sputtering is 150 ° C. or lower.
  • a film is formed on a resin substrate such as a transparent plastic substrate, a high transmittance can be obtained.
  • the conditions for forming the oxide sintered body of the present invention as a sputtering target are not particularly limited except for the substrate temperature, and can be formed under normal conditions.
  • a target-substrate distance 35 mm to 120 mm
  • ultimate vacuum 1 ⁇ 10 ⁇ 3 Pa or less
  • introduced gas 0% to 10% O 2 gas.
  • the substrate temperature may be lower than 150 ° C. by not heating from room temperature, or the substrate may be cooled and held at a predetermined temperature lower than 150 ° C. as necessary.
  • the transparent conductive film of the present invention is a transparent conductive film containing indium oxide as a main component and containing tin oxide and cobalt oxide, and an atomic ratio of Sn to In: Sn / In is 0.019 to 0.102, and the atomic ratio of each component to the sum of In, Sn, and Co: In / (In + Sn + Co) is 0.771 to 0.967, and Sn / (In + Sn + Co) is 0 .016 to 0.091, Co / (In + Sn + Co) is 0.015 to 0.15, and the specific resistance is 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • the specific resistance of the transparent conductive film is preferably 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • the composition of the transparent conductive film may depend on the film formation conditions, it can usually be the same as the composition of the oxide sintered body used as the film formation material by appropriate setting. That is, by determining the composition of the oxide sintered body based on the composition of the transparent conductive film, a transparent conductive film having a desired composition can be obtained by film formation.
  • the transparent conductive film of the present invention when the film thickness is 15 nm to 40 nm and the transmittance is measured with a spectrophotometer or spectroscopic ellipsometry using visible light of 400 nm to 800 nm, the average transmittance is a single film. Is 98% or more.
  • the substrate is formed without heating, it becomes a crystalline transparent conductive film having high crystallinity.
  • the transparent conductive film of the present invention is mainly oriented in the (222) plane and has a very high crystallinity.
  • the resistance change rate is within 1.2, preferably 1.0 or less. Such characteristics are particularly effective when a product to which the transparent conductive film is applied is used outdoors in a high temperature environment, or when an in-vehicle electronic device is applied.
  • Example 1 As raw material powders, indium oxide (In 2 O 3 ) powder (purity 99.9%, average particle size of about 0.9 ⁇ m), tin oxide (SnO 2 ) powder (purity 99.9%, average particle size of about 0.9 ⁇ m) ), And cobalt oxide (CoO) powder (purity 99.9%, average particle size of about 0.8 ⁇ m).
  • indium oxide (In 2 O 3 ) powder purity 99.9%, average particle size of about 0.9 ⁇ m
  • tin oxide (SnO 2 ) powder purity 99.9%, average particle size of about 0.9 ⁇ m
  • CoO cobalt oxide
  • this compact was placed in a sintering furnace (manufactured by Marusho Denki Co., Ltd.), and oxygen was circulated at a rate of 100 L / min per 1 m 3 of the furnace volume, thereby maintaining the oxygen concentration at 30% or more.
  • the state was heated to 700 ° C., and the binder removal treatment was performed for 34 hours. Thereafter, firing was performed for 20 hours by setting the atmosphere in the furnace to an air atmosphere and a maximum temperature of 1550 ° C. to obtain a sintered body.
  • the above sintered body was ground to produce an indium oxide sputtering target having a diameter of 4 inches (101.6 mm) and a thickness of 5 mm.
  • an ICP emission spectrometer ICPS8100, manufactured by Shimadzu Corporation
  • the composition range and sintering temperature of the raw material powder of Example 1 are shown in Table 1.
  • the relative density and specific resistance of the sintered body were measured for the obtained indium oxide-based sputtering target.
  • the specific resistance of the oxide sintered body was measured using a four-point probe resistivity meter Loresta EP (Dia Instruments, MCP-T360 type). As a result, the specific resistance of the sputtering target of Example 1 was 4.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the obtained sputtering target was metal-bonded to an oxygen-free copper backing plate, set in a magnetron sputtering apparatus (made by Tokki Co., Ltd.) using a DC power source, sputtered under the following conditions, and a transparent conductive film having a film thickness of 25 nm. A membrane was obtained.
  • a glass substrate was used, and the film was formed without heating the substrate.
  • Crystallinity of transparent conductive film The crystallinity of the obtained transparent conductive oxide film was confirmed using a multipurpose X-ray diffractometer (Spectres, Inc., X'Pert-PRO MPD). When a diffraction peak on the (222) plane was observed, a crystalline film was obtained, and when no diffraction peak was observed, it was determined that the film was not crystallized. As a result, it was confirmed that the transparent conductive film of Example 1 had high crystallinity.
  • Transmissivity of transparent conductive film With respect to the obtained transparent conductive oxide film, the transmittance of light having a wavelength of 400 nm to 800 nm was measured using a spectrophotometer (manufactured by JASCO Corporation, UbestV-570iRM / DS). A transmittance peak was observed at a wavelength of 500 nm to 600 nm. The average transmittance at wavelengths of 400 nm to 800 nm was 98.2%.
  • the specific resistance of the transparent conductive film was calculated from the product of the surface resistance and the film thickness measured with a four-probe resistivity meter Loresta EP (manufactured by Dia Instruments, MCP-T360 type).
  • the film thickness of the transparent conductive film was determined by measuring the level difference between the non-deposited portion and the deposited portion using a contact-type surface roughness meter (manufactured by Tencor).
  • Example 1 was 3.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the resistance change rate was 1.20.
  • Table 2 shows the measurement results of the relative density and specific resistance of the sputtering target of Example 1, the crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • Examples 2 to 8 A sputtering target was obtained in the same manner as in Example 1 except that the composition ratio of each component was changed to the values described in Table 1. About these sputtering targets, when the composition analysis was conducted by ICP emission spectroscopy, it was confirmed that all were the same as the composition ratio of the raw material powder as in Example 1. Moreover, when the composition analysis was conducted on the transparent conductive film formed using these sputtering targets using an ICP emission spectrophotometer, it was found that all of them were the same as the composition ratio of the sputtering target as in Example 1. confirmed.
  • Table 2 shows the measurement results of the relative density and specific resistance of the sputtering targets of Examples 2 to 8, crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • Comparative Examples 1 and 2 A sputtering target was obtained in the same manner as in Example 1 except that the composition ratio of each component was changed to the values described in Table 1.
  • Sn / In and Sn / (In + Sn + Co) are below the range of the present invention, and In / (In + Sn + Co) is above the range of the present invention.
  • Comparative Example 2 is an example in which Sn / In and Sn / (In + Sn + Co) are below the range of the present invention.
  • Table 2 shows the measurement results of the relative density and specific resistance of the sputtering targets of Comparative Examples 1 and 2 and the crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • Comparative Examples 3 to 5 An oxide sintered body was obtained in the same manner as in Example 1 except that the composition ratio of each component was changed to the values described in Table 1. Comparative Example 3 is an example in which Sn / In and Sn / (In + Sn + Co) both exceed the scope of the present invention. Comparative Example 4 is an example in which Sn / In exceeds the range of the present invention and In / (In + Sn + Co) falls below the range of the present invention. Comparative Example 5 is an example in which only Sn / In exceeds the scope of the present invention.
  • Table 2 shows the measurement results of the relative density and specific resistance of the sputtering targets of Comparative Examples 3 to 5, crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • Example 6 An oxide sintered body was obtained in the same manner as in Example 4 except that the firing temperature was 1400 ° C. All of these sputtering targets and transparent conductive films were also confirmed to have the same composition ratio as the raw material powder. Table 2 shows the measurement results of the relative density and specific resistance of the sputtering target of Comparative Example 6, the crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • Comparative Examples 7 and 8 An oxide sintered body was obtained in the same manner as in Example 1 except that the composition ratio of each component was changed to the values described in Table 1.
  • Comparative Example 7 In / (In + Sn + Co) exceeds the range of the present invention, and Co / (In + Sn + Co) falls below the range of the present invention.
  • Comparative Example 8 In / (In + Sn + Co) falls below the range of the present invention, and Co / (In + Sn + Co) exceeds the range of the present invention.
  • Table 2 shows the measurement results of the relative density and specific resistance of the sputtering targets of Comparative Examples 7 and 8, crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • Comparative Examples 9 to 14 oxide sintered bodies were obtained in the same manner as in Examples 1 to 6, respectively, except that at least one raw material powder having an average particle size of 1.0 ⁇ m or more was used. All of these sputtering targets and transparent conductive films were also confirmed to have the same composition ratio as the raw material powder.
  • Table 2 shows the measurement results of the relative density and specific resistance of the sputtering targets of Comparative Examples 9 to 14, crystallinity, transmittance, specific resistance, and resistance change rate of the transparent conductive film.
  • the sputtering target of Comparative Examples 1 and 2 with a small Sn content does not have a relative density of 98% or more, and the specific resistance exceeds 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • the transparent conductive film obtained by using the film had insufficient transmittance, specific resistance, and resistance change rate.
  • Comparative Examples 3 to 5 having a high Sn content it was understood that the transparent conductive film had poor crystallinity and the effect of promoting crystallization by adding cobalt oxide was reduced.
  • Comparative Examples 1, 2, 6, 7, and 9 to 14 in which the relative density of the sputtering target is less than 98% are compared with those in Examples 1 to 9 during arcing and Many nodules were observed, confirming deterioration of film properties and reduction of production efficiency.
  • the oxide sintered body of the present invention requires high transmittance such as a transparent conductive film for solar cells, a transparent conductive film for touch panels, a transparent conductive film for liquid crystal display devices such as a flat panel display, and an organic EL transparent conductive film.
  • a transparent conductive film for solar cells a transparent conductive film for solar cells
  • a transparent conductive film for touch panels a transparent conductive film for liquid crystal display devices
  • an organic EL transparent conductive film organic EL transparent conductive film.
  • it is suitable as a sputtering target for obtaining a transparent conductive film in a film touch panel application for which a transparent plastic film substrate is required by a direct current sputtering method.

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Abstract

[Problème] Produire un film conducteur transparent cristallin ayant un facteur de transmission élevé d'au moins 98 % dans les longueurs d'onde visibles (400 à 800 nm) et une résistance spécifique de pas plus de 5×10-3 Ω·cm, même après une formation de film à une température de substrat basse de pas plus de 150 °C. [Solution] Le film conducteur transparent est obtenu au moyen de la formation de film, la cible de pulvérisation étant un corps fritté d'oxyde tel que Sn/In soit de 0,019 à 0,102, In/(In+Sn+Co) soit de 0,771 à 0,967, Sn/(In+Sn+Co) soit de 0,016 à 0,091, Co/(In+Sn+Co) soit de 0,015 à 0,15, la densité relative soit d'au moins 98 %, et la résistance spécifique soit de pas plus de 5×10-3 Ω·cm.
PCT/JP2012/074111 2011-09-22 2012-09-20 Corps fritté d'oxyde, procédé pour produire celui-ci, et film conducteur transparent d'oxyde WO2013042747A1 (fr)

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Citations (3)

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JPH09161542A (ja) * 1995-12-07 1997-06-20 Idemitsu Kosan Co Ltd 透明導電積層体およびこれを用いたタッチパネル
JPH10269843A (ja) * 1998-04-13 1998-10-09 Tosoh Corp 導電性金属酸化物焼結体及びその用途
JPH11322413A (ja) * 1998-02-16 1999-11-24 Japan Energy Corp 光透過膜、高抵抗透明導電膜、光透過膜形成用スパッタリングタ―ゲット及び高抵抗透明導電膜の製造方法

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JPH09161542A (ja) * 1995-12-07 1997-06-20 Idemitsu Kosan Co Ltd 透明導電積層体およびこれを用いたタッチパネル
JPH11322413A (ja) * 1998-02-16 1999-11-24 Japan Energy Corp 光透過膜、高抵抗透明導電膜、光透過膜形成用スパッタリングタ―ゲット及び高抵抗透明導電膜の製造方法
JPH10269843A (ja) * 1998-04-13 1998-10-09 Tosoh Corp 導電性金属酸化物焼結体及びその用途

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EDITED BY JAPAN SOCIETY FOR THE PROMOTION OF SCIENCE: "The 166th Committee on Photonic and Electronic Oxide", TOMEI DODENMAKU NO GIJUTSU, 1ST EDITION, OHMSHA, LTD., 30 March 1999 (1999-03-30), pages 196 - 201 *
JOLANTA STANKIEWICZ: "Magnetic behavior of sputtered Co-doped indium-tin oxide films", PHYSICAL REVIEW B, vol. 75, no. 23, 2007, pages 235308-1 - 235308-6, XP003030958 *

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