WO2011145665A1 - 酸化亜鉛焼結体タブレットおよびその製造方法 - Google Patents
酸化亜鉛焼結体タブレットおよびその製造方法 Download PDFInfo
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- WO2011145665A1 WO2011145665A1 PCT/JP2011/061461 JP2011061461W WO2011145665A1 WO 2011145665 A1 WO2011145665 A1 WO 2011145665A1 JP 2011061461 W JP2011061461 W JP 2011061461W WO 2011145665 A1 WO2011145665 A1 WO 2011145665A1
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- zinc oxide
- sintered body
- tablet
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- orientation
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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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
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- C04B35/453—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 based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions
- the present invention relates to a zinc oxide sintered tablet used as an evaporation source when an oxide transparent conductive film is manufactured by a vacuum vapor deposition method, and a manufacturing method for obtaining the zinc oxide sintered tablet.
- the oxide transparent conductive film has high conductivity and high transmittance in the visible light region. For this reason, the oxide transparent conductive film is used not only for electrodes of solar cells, liquid crystal display elements, and other various light receiving elements, but also by utilizing reflection and absorption characteristics at wavelengths in the near infrared region, It is also used as a heat-reflective film for window glass of buildings, various antistatic films, and as a transparent heating element for anti-fogging such as a freezer showcase.
- the oxide transparent conductive film includes zinc oxide (ZnO) containing aluminum or gallium as a dopant, tin oxide (SnO 2 ) containing antimony or fluorine as a dopant, indium oxide (In 2 O 3 ) containing tin as a dopant, and the like. It's being used.
- an indium oxide film containing tin as a dopant is also referred to as an ITO (Indium Tin Oxide) film, and is widely used because a transparent conductive film having a particularly low resistance can be easily obtained.
- a vacuum evaporation method in which an evaporation source is heated in a vacuum and an evaporated raw material is deposited on a substrate, and a substance constituting the target is made by colliding argon ions with the target.
- a sputtering method for knocking out and depositing on an opposing substrate and a method for applying a coating liquid for forming a transparent conductive layer are used.
- the vacuum deposition method and the sputtering method are effective means when using a material having a low vapor pressure or when precise film thickness control is required, and the operation is very simple. It is widely used industrially.
- the vacuum deposition method is usually performed by heating a solid (or liquid) as an evaporation source in a vacuum at a pressure of about 10 ⁇ 3 Pa to 10 ⁇ 2 Pa and decomposing it once into gas molecules and atoms. This is a method of condensing again as a thin film on the substrate surface.
- a heating method of the evaporation source a resistance heating method (RH method) and an electron beam heating method (EB method, electron beam evaporation method) are generally used, but there are a heating method using a laser beam and a high frequency induction heating method.
- flash vapor deposition arc plasma vapor deposition, reactive vapor deposition, and the like are also known, and these are also included in vacuum vapor deposition.
- vacuum deposition methods those accompanied by ionization of the evaporated material and reaction gas, such as the high density plasma assisted deposition (HEPE) method, are collectively referred to as an ion plating method.
- HEPE high density plasma assisted deposition
- ITO films In the production of ITO films, ion plating methods such as electron beam vapor deposition and high-density plasma assist vapor deposition, and other vacuum vapor deposition methods are widely used in addition to the commonly used sputtering method.
- an evaporation source in the vapor deposition method an ITO tablet (also referred to as an ITO pellet) made of an ITO sintered body is used.
- a zinc oxide transparent conductive film made of zinc oxide or zinc oxide containing aluminum, gallium or the like as a dopant has a very low price of zinc, which is the main raw material, and has a high light transmittance and resistance to light. Because of its excellent plasma properties, it is widely used as an electrode for thin film silicon solar cells. Moreover, since the forbidden band width of zinc oxide is as wide as about 3.4 eV and exciton energy is high, its application to light emitting diodes has been actively reported in recent years. Furthermore, application to transparent thin film transistors is also expected.
- the reason why a boron group element such as aluminum or gallium, which is an element having a higher valence than zinc, is included is to reduce the specific resistance (electric resistivity) of the film. This is because it can.
- Sputtering methods are mainly used in the production of zinc oxide transparent conductive films.
- a zinc oxide sintered body target is used as a raw material, but various crystal orientation zinc oxide sintered body targets have been proposed so far in order to obtain a film having excellent uniformity.
- Patent Document 1 a zinc oxide sintered body target having (002) crystal orientation larger than (101) crystal orientation is disclosed in Patent Document 2, and (101) Zinc oxide sintered body target having large (101) crystal orientation in Patent Document 2.
- Patent Document 3 a (110) zinc oxide sintered compact target having a large crystal orientation is proposed.
- this zinc oxide transparent conductive film is being studied for production by vacuum deposition, and various types of zinc oxide sintered tablets as disclosed in Patent Documents 4 to 7 are proposed. Has been.
- Zinc oxide sintered tablets used in this vacuum deposition method have a relative density (ratio of bulk density to theoretical density) of about 50% to 70% from the viewpoint of preventing cracks and cracks during film formation. Is used.
- the zinc oxide sintered body is a material having higher resistance than the ITO sintered body, the relative density is higher than that of a sintered body target having a high relative density of 90% or more as used in the sputtering method.
- the specific resistance value of the sintered body tablet is increased by the lower amount. When the specific resistance value of the sintered tablet increases, uniform sublimation with a plasma beam or an electron beam becomes difficult. At this time, the vapor deposition material scatters in a size of several ⁇ m to 1000 ⁇ m mixed with uniform evaporation gas. A splash phenomenon that collides with the deposited film may occur. This splash phenomenon causes film defects such as pinhole defects. Therefore, realization of a zinc oxide sintered body tablet in which the occurrence of such a splash phenomenon is suppressed is desired.
- Patent Documents 4 to 7 when a zinc oxide sintered body tablet is manufactured, sintering is performed in the atmosphere or a nitrogen gas atmosphere. From the viewpoint of stability, it is described that it is effective to heat-treat the obtained zinc oxide sintered tablet in a reducing atmosphere such as an argon atmosphere or a vacuum in order to improve the conductivity.
- a reducing atmosphere such as an argon atmosphere or a vacuum
- Patent Document 6 discloses that the half-value width of at least one of the diffraction peaks of the (100) plane, (002) plane, and (101) plane in X-ray diffraction analysis is set to 0.110 ° or less and the zinc oxide is sintered. It is possible to suppress the splash phenomenon by making the particle diameters of the crystal grains of the combined tablet uniform.
- Patent Document 7 discloses that the splash phenomenon is reduced by reducing the closed pores in the zinc oxide sintered tablet. Each is described as being capable of being suppressed. However, these technologies are still not enough to suppress the splash phenomenon.
- the present invention suppresses the occurrence of a splash phenomenon when a film is formed by a vacuum evaporation method using a zinc oxide sintered body tablet including a high-resistance tablet in which film formation is generally unstable. It aims at providing the zinc oxide sintered compact tablet from which the zinc oxide transparent conductive film without defects, such as a hole, is obtained stably.
- the inventor has conducted extensive research to solve the above problems, and obtained a compact by uniaxially pressing the granulated powder of zinc oxide produced under special production conditions.
- the knowledge that a splash phenomenon is suppressed was obtained by using a zinc oxide sintered compact tablet obtained by carrying out atmospheric pressure sintering of a body.
- Such a zinc oxide sintered body tablet is characterized in that (103) the crystal orientation is large with respect to the crystal orientation of the uniaxial pressure surface to be the sublimation surface. As described above, by increasing the (103) crystal orientation of the zinc oxide sintered body tablet, it is possible to obtain a remarkable effect that splash is suppressed and film formation stability is improved.
- the zinc oxide sintered body tablet of the present invention is composed of a zinc oxide or zinc oxide sintered body containing a dopant having a hexagonal crystal structure, and is obtained by X-ray diffraction using CuK ⁇ rays.
- the degree of orientation is 0.48 or more.
- the degree of orientation is preferably 0.5 or more, more preferably 0.55 or more, and most preferably 0.6 or more.
- the zinc oxide sintered tablet of the present invention preferably has a specific resistance of 1 ⁇ 10 2 ⁇ ⁇ cm or less. Furthermore, the relative density is preferably 50% or more and 70% or less.
- the zinc oxide sintered body tablet of the present invention presses a granulated powder composed of zinc oxide powder or a mixed powder of zinc oxide and an additive element serving as a dopant, wherein the ratio of donut-shaped secondary particles is 50% or more.
- the molded body obtained by molding is obtained by sintering at a pressure of 800 ° C. to 1300 ° C. at normal pressure.
- the normal pressure sintered body obtained by the above sintering is subjected to a pressure of 1 ⁇ 10 ⁇ 4 Pa or more and 1 ⁇ 10 ⁇ 3 Pa or less at a temperature of 800 ° C. to 1300 ° C. for 1 minute or more. It is preferable to carry out a reduction treatment for holding for 10 minutes or less.
- the granulated powder composed of the doughnut-shaped secondary particles is prepared by using the raw material powder of the zinc oxide powder or the mixed powder as a slurry, and the slurry at a temperature of 80 ° C. to 100 ° C. It is obtained by adjusting the ratio of secondary particles to 50% or more and spray drying.
- a part of the granulated powder is preferably calcined at a temperature of 800 ° C. to 1300 ° C. for 10 to 30 hours.
- the granulated powder after calcination and the uncalcined granulated powder are preferably mixed and used.
- the zinc oxide sintered tablet of the present invention When used for film formation by vacuum deposition, the occurrence of a splash phenomenon is suppressed, film formation by stable discharge becomes possible, and causes film defects during film formation.
- the production of the transparent conductive film by the vacuum deposition method is significantly improved, such as the generation of the damaged material is prevented and the removal work of the damaged material becomes unnecessary.
- the zinc oxide based sintered tablet of the present invention has a feature that (103) crystal orientation is large with respect to crystal orientation on a uniaxial pressure surface serving as a sublimation surface.
- the peak integrated intensities of the (103) plane and (110) plane by X-ray diffraction using CuK ⁇ rays are I (103) and I (110) , I (103) / (I (103) + I (110) If the degree of orientation of the uniaxial pressure surface represented by) is 0.48 or more, splash during film formation is suppressed.
- the degree of orientation of the uniaxial pressure surface is less than 0.48.
- the degree of orientation of the uniaxial pressure surface is 0.48 or more, preferably 0.5 or more, more preferably 0.55 or more, particularly preferably 0.6 or more. It has become.
- the specific resistance of the sintered body is relatively low, which is more advantageous for suppressing splash.
- the zinc oxide sintered compact tablet for vacuum evaporation in which the splash was suppressed is realizable by using the surface which has such a high orientation degree for a sublimation surface.
- the vacuum deposition here widely includes an electron beam deposition method, an ion plating method such as a high density plasma assisted deposition method, and other vacuum deposition methods.
- the zinc oxide-based sintered tablet of the present invention having a large (103) crystal orientation is characterized by improved film-forming stability even when the specific resistance is high.
- the large crystal orientation is also effective in improving the stability of film formation in a low-resistance tablet. That is, this invention is not restricted to the zinc oxide sintered compact tablet comprised only from a zinc oxide, It can apply also to the zinc oxide sintered compact tablet comprised from the zinc oxide containing various dopants.
- boron, aluminum, gallium Boron group elements such as indium, titanium group elements such as titanium, zirconium and hafnium, chromium group elements such as molybdenum and tungsten, vanadium group elements such as vanadium, niobium and tantalum, lanthanoids such as cerium, praseodymium and gadolinium, and One or more elements selected from yttrium, tin, ruthenium, magnesium, iridium, and bismuth may be added.
- the addition amount of these dopants is 50 atomic percent or less with respect to all elements other than oxygen, but is preferably 3 atomic percent to 10 atomic percent from the viewpoint of reducing resistance.
- the obtained zinc oxide sintered tablet may be subjected to a reduction treatment after sintering at normal pressure.
- the sintered compact tablet which consists only of zinc oxide Preferably it is 99.9% or more of purity, More preferably, it is preferable that it is 99.99% or more of purity. However, the inevitable impurities are allowed to exist within the above purity range.
- the relative density (bulk relative to the theoretical density) is prevented from the viewpoint of preventing the occurrence of cracks and cracks during film formation.
- the density ratio is 50% to 70%.
- the theoretical density of zinc oxide used when calculating the relative density is 5.78 g / cm 3 .
- the firing conditions in the calcining and / or sintering process may be regulated in the manufacturing process of the zinc oxide sintered body tablet described later.
- the zinc oxide sintered body tablet of the present invention does not contain the above-mentioned dopant, its specific resistance depends on the density, but is about 1.0 ⁇ 10 5 ⁇ ⁇ cm to 1.0 ⁇ 10 9 ⁇ ⁇ cm. It becomes. Even in such a high resistance, the zinc oxide sintered tablet of the present invention has a high (103) crystal orientation on the sublimation surface, so that the uniformity of sublimation is improved and a splash phenomenon occurs. It becomes difficult to do.
- the zinc oxide-based sintered tablet of the present invention has a specific resistance of 1 ⁇ 10 2 ⁇ ⁇ cm or less in order to maintain stable discharge. Preferably, it is 10 ⁇ ⁇ cm or less.
- a zinc oxide-based sintered tablet having a specific resistance of at least 1 ⁇ 10 2 ⁇ ⁇ cm or less is used, local heating is eliminated and the material is uniformly heated, so that the occurrence of a splash phenomenon is further suppressed.
- the obtained zinc oxide sintered tablet may be subjected to a reduction treatment after sintering at normal pressure.
- the specific resistance is preferably as low as possible.
- the lower limit of the specific resistance is currently 5 ⁇ 10 ⁇ 1 ⁇ ⁇ It is about cm.
- the specific resistance of the zinc oxide sintered body tablet having a relative density of 50% or more and 70% or less is 3 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or less, preferably 5. It can be lowered to 0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm to about 1.0 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the specific resistance is a value measured by using a four-probe method. Specifically, a four-probe resistivity meter Loresta EP (manufactured by Mitsubishi Chemical Analytech Co., Ltd., MCP-T360 type). ).
- [Method for producing zinc oxide sintered tablet] Manufacture of doughnut-shaped secondary particles
- the zinc oxide sintered body tablet having the excellent characteristics as described above is a result of repeated research by the present inventor.
- the granulated powder having a doughnut-shaped secondary particle ratio of 50% or more is obtained as a sintered body material.
- the knowledge that it can be obtained by using the The ratio of the doughnut-shaped secondary particles is preferably 60% or more, more preferably 68% or more, and most preferably 78% or more.
- such a granulated powder containing a large amount of doughnut-shaped secondary particles is not used as a sintered body material because it causes a decrease in density.
- spherical granulated powder is obtained.
- the orientation of the uniaxial pressure surface of the obtained zinc oxide sintered body tablet The degree will be below 0.48.
- the degree of orientation of the uniaxial pressure surface is 0.48 or more, and by setting it to 60% or more, 0.50 or more, and further 68% or more. By doing so, it can be made 0.55 or more, and by making it 78% or more, it can be made 0.60 or more.
- Donut-shaped secondary particles are formed by agglomerating primary particles in a ring shape, and are obtained by adjusting the water evaporation rate in the slurry in the granulation process by a spray dryer.
- the donut-shaped secondary particles herein may be particles having a shape in which the thickness of the annular portion is uniform or a shape in which the thickness of the annular portion is not uniform and a hole penetrating a so-called sphere is formed. .
- a granulated powder having many such particles a (103) zinc oxide sintered body tablet having a large crystal orientation can be obtained.
- the particle size of the doughnut-shaped secondary particles is in the range of 10 ⁇ m to 100 ⁇ m from the viewpoint of uniform sinterability. This particle size can be set within this range by regulating the granulation conditions described later.
- a raw material powder made of zinc oxide powder or a mixed powder of an additive element serving as a dopant and zinc oxide is prepared.
- a thing with an average particle diameter of 1 micrometer or less from a viewpoint of equalization of sinterability.
- the raw material powder having a particle size (D90) of 1.0 ⁇ m or more and 2.0 ⁇ m or less when the cumulative weight by the particle size distribution measurement is 90% the size and density of the obtained sintered body can be further increased. This makes it possible to manufacture stably and with high yield.
- the calcined powder is calcined at a temperature of 800 ° C. to 1300 ° C., preferably 900 ° C. to 1200 ° C. If the calcining temperature is less than 800 ° C., the grain growth of the particles hardly proceeds, so that the effect of calcining cannot be obtained. If the calcining temperature exceeds 1300 ° C., zinc volatilizes and a predetermined zinc oxide composition is obtained.
- the calcination time is 1 hour to 30 hours, preferably 10 hours to 20 hours.
- the amount of the calcined powder used relative to the uncalcined powder is arbitrarily determined according to the desired relative density of the zinc oxide sintered body tablet, but is preferably 30% by mass to 90% by mass.
- the raw material powder may be directly calcined to obtain a calcined powder.
- calcining to obtain a calcined granulated powder is possible after calcining. It is preferable because the powder is less likely to harden.
- the raw material powder is mixed with pure water, an organic binder such as polyvinyl alcohol and methyl cellulose, a polycarboxylic acid ammonium salt, an acrylic amine salt, and the like, and the raw material powder concentration is 50% by mass to 80% by mass.
- the slurry is preferably mixed so as to be about 65 to 75% by mass, preferably about 70% by mass.
- a mixing method is not specifically limited, A well-known technique can be utilized.
- the slurry is sprayed and dried using a spray dryer to obtain a granulated powder.
- the drying temperature is desirably 80 ° C. or higher and 100 ° C. or lower.
- the drying temperature is less than 80 ° C., a sufficiently dried granulated powder cannot be obtained. If the drying is insufficient and the amount of moisture is large, there is a high possibility that the molded body or the tablet will be cracked in the next molding step or sintering step.
- the drying temperature exceeds 100 ° C, the drying of the slurry proceeds rapidly, causing secondary particle breakage and the like, making it difficult to control the secondary particle shape, and generating donut-shaped secondary particles. The ratio of being reduced.
- the amount of exhausted air is preferably 25 m 3 / min or less, and if the amount of exhausted air exceeds 25 m 3 / min, As described above, it is difficult to control the secondary particle shape, and the ratio at which donut-shaped secondary particles are generated is reduced.
- the lower limit also depends on the device and can be applied up to the minimum amount of exhaust air that functions as a device. By satisfying these conditions, it becomes possible to produce a spray dryer granulated powder having a doughnut-shaped secondary particle ratio of 50% or more.
- the doughnut-shaped secondary particle ratio was determined by observing the granulated powder obtained with an electron microscope and measuring the number of doughnut-shaped secondary particles and the total number of secondary particles. It is calculated by using the formula: (number of secondary particles) / (total number of secondary particles).
- the sintered body material powder made of the granulated powder is uniaxially pressed by, for example, a mechanical press method in which pressure is applied in a mold to obtain a molded body.
- a mechanical press method in which pressure is applied in a mold to obtain a molded body.
- a sintered tablet having a desired relative density is obtained. Easy and desirable.
- the amount of calcined powder used as a raw material, the heat treatment temperature of the calcined powder, and the sintering temperature in the subsequent process are made constant, so that the shrinkage rate of each tablet during sintering is substantially reduced. Can be controlled in the same way.
- the dimension of the sintered body tablet can be determined by adjusting the dimension of the compact in press molding.
- a die for press molding has a C-chamfered shape on the inner edge portion, so that when the outer edge portion of the molded body is chamfered, this molded body or this molded body is sintered.
- breakage such as chipping can be prevented, which is preferable.
- the sintered compact tablet which consists of zinc oxide or a zinc oxide containing a dopant is obtained by sintering the said molded object at a normal pressure.
- the sintering temperature at this time is in the range of 800 ° C. to 1300 ° C. In this range, a higher relative density and a lower specific resistance tend to be obtained as the sintering temperature increases. If the sintering temperature is less than 800 ° C., the sintering does not proceed, and the atmospheric pressure sintered body tablet with weak mechanical strength is obtained. In addition, since the sintering shrinkage is not sufficiently advanced, the density and dimensional variations of the sintered tablet increase.
- the sintering temperature exceeds 1300 ° C., zinc volatilizes and deviates from a predetermined zinc oxide composition. From this viewpoint, it is preferable that the sintering temperature is in the range of 900 ° C. to 1100 ° C.
- the rate of temperature increase during sintering the vapor pressure when the added organic component evaporates is taken into account and may be set to 1.0 ° C./min for the purpose of preventing cracking during temperature increase. preferable.
- the firing atmosphere may be any atmosphere in the air, nitrogen gas, argon, or oxygen as long as it is normal pressure.
- the sintering time is arbitrary depending on the firing conditions such as a firing furnace, but may be set to a time during which the compact is sufficiently sintered and not oversintered. Usually, it is 10 hours to 20 hours, preferably 15 hours to 20 hours. When sintering is performed for more than 20 hours, the production cost increases according to the sintering time, and zinc volatilization also occurs.
- the atmospheric pressure sintered body tablet obtained by the sintering may be subjected to a reduction treatment in a vacuum.
- the reduction pressure is 1 ⁇ 10 ⁇ 3 Pa or less
- the reduction temperature is in the range of 800 ° C. to 1300 ° C. Similar to the sintering condition, in this range, as the reduction temperature increases, a higher relative density and a lower specific resistance tend to be obtained.
- the rate of temperature rise to the above reduction temperature is set within the range of 1.0 ° C./min to 10.0 ° C./min.
- the rate of temperature increase is less than 1.0 ° C./min, the productivity is lowered, whereas it exceeds 10.0 ° C./min.
- the sintered body that cannot withstand the thermal shock is cracked, and the yield may be lowered.
- the reduction temperature is less than 800 ° C.
- the reduction does not proceed to the inside of the sintered body tablet, the effect of the reduction treatment cannot be obtained sufficiently, and the conductivity improvement of the sintered body tablet becomes insufficient.
- the effect of intentionally adding a reduction treatment step is lost, and conversely the productivity is lowered.
- the reduction temperature exceeds 1300 ° C., zinc oxide is volatilized on the surface of the sintered tablet, and the surface becomes a fragile layer having a high resistance, which greatly impairs productivity. From this viewpoint, it is preferable that the reduction temperature is in the range of 900 ° C. to 1100 ° C.
- the reduction pressure is higher than 1 ⁇ 10 ⁇ 3 Pa, the reduction does not proceed to the inside of the sintered body tablet, and the conductivity of the sintered body tablet becomes insufficient.
- the reduction pressure is preferably set to 1 ⁇ 10 ⁇ 4 Pa or more in consideration of efficiency such as vacuum processing time and cost.
- the time for the reduction treatment is arbitrary depending on the treatment conditions, and it is sufficient to set a time during which the reduction to the inside of the sintered tablet can be sufficiently performed and the volatilization of zinc can be suppressed. Considering the efficiency of reduction treatment and production cost, it is usually 1 minute to 1 hour, preferably 1 minute to 10 minutes.
- this reduction process is particularly applied to the production of a sintered tablet made of only zinc oxide having a high resistance. Further, it may be applied to the manufacture of a relatively low resistance zinc oxide sintered body tablet containing a dopant to further reduce the resistance.
- Example 1 First, a predetermined amount of zinc oxide powder having an average particle diameter of 1 ⁇ m or less was prepared as a raw material powder.
- the granulated powder was fired at 1000 ° C. for 20 hours in an atmospheric pressure sintering furnace, and pulverized after firing to obtain a calcined powder having a particle size of 300 ⁇ m or less.
- the mixed powder of calcined powder and uncalcined powder was obtained by mixing this calcined powder and the raw powder of uncalcined prepared first.
- the mixed powder was again formulated with pure water, polyvinyl alcohol as an organic binder, and polycarboxylic acid ammonium salt as a dispersant so that the powder concentration would be 70% by mass, and a slurry was prepared in a mixing tank. Then, using the same spray dryer, the slurry is sprayed and dried at an outlet temperature of the apparatus chamber of 90 ° C. and an exhaust air volume of 15 m 3 / min. A sintered body material powder made of a certain granulated powder was obtained. Among the secondary particles constituting the sintered body material powder, the number ratio of donut-shaped secondary particles was 60%.
- the sintered body material powder is uniaxially pressed at a pressure of 90 MPa (0.92 tonf / cm 2 ) in a mold of a molding press machine (manufactured by Sansho Industry Co., Ltd., a wave molding press machine).
- a molding press machine manufactured by Sansho Industry Co., Ltd., a wave molding press machine.
- the obtained 200 compacts were sintered in an atmospheric pressure atmosphere in an electric furnace, respectively, to obtain a normal pressure sintered compact tablet composed of 200 zinc oxides.
- the sintering temperature at this time was 1000 ° C., and the sintering time was 20 hours.
- the obtained 200 atmospheric pressure sintered tablets were each placed in a graphite container, and 1000 ° C. (maximum) at a heating rate of 5 ° C./min in a vacuum of 1 ⁇ 10 ⁇ 3 Pa.
- 200 zinc oxide sintered tablets were manufactured by performing a reduction treatment that was maintained at this temperature for 3 minutes.
- resistivity The surface resistivity of 50 samples was measured using a four-point probe resistivity meter Loresta EP (manufactured by Mitsubishi Chemical Analytech Co., Ltd., model MCP-T360). The average value of the resistivity was 8. It was 5 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Example 1, and Table 2 shows the results of the inspection and test (evaluation).
- Example 2 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was produced with the chamber outlet temperature set at 80 ° C. and the exhaust air flow rate at 15 m 3 / min. Body material powder was obtained. Among the secondary particles constituting the sintered body material powder, the number ratio of donut-shaped secondary particles was 72%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered body tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 60% and the average value of specific resistance was 5.7 ⁇ ⁇ cm.
- the degree of orientation of the obtained zinc oxide sintered body tablet calculated as in Example 1 was 0.578.
- Table 1 shows the manufacturing conditions of Example 2, and Table 2 shows the results of the inspection and test (evaluation).
- Example 3 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was produced by setting the chamber outlet temperature to 90 ° C. and the exhaust air amount to 5 m 3 / min. Body material powder was obtained. Of the secondary particles constituting the sintered body material powder, the number ratio of doughnut-shaped secondary particles was 68%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered body tablet was inspected in the same manner as in Example 1.
- the average value of the relative density was 61%, and the average value of the specific resistance was 6.2 ⁇ ⁇ cm.
- the degree of orientation of the obtained zinc oxide sintered body tablet calculated as in Example 1 was 0.551.
- Table 1 shows the manufacturing conditions of Example 3, and Table 2 shows the results of the inspection and test (evaluation).
- Example 4 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was produced with the chamber outlet temperature set at 80 ° C. and the exhaust air flow rate at 5 m 3 / min. Body material powder was obtained. Among the secondary particles constituting the sintered body material powder, the number ratio of donut-shaped secondary particles was 79%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered body tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 61%, and the average value of specific resistance was 5.5 ⁇ ⁇ cm.
- the degree of orientation of the obtained zinc oxide sintered body tablet calculated as in Example 1 was 0.605.
- Table 1 shows the manufacturing conditions of Example 4, and Table 2 shows the results of the inspection and test (evaluation).
- Example 5 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was produced by setting the outlet temperature of the chamber to 100 ° C. and the exhaust air amount to 15 m 3 / min. Body material powder was obtained. Of the secondary particles constituting the sintered body material powder, the number ratio of doughnut-shaped secondary particles was 54%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 60% and the average value of specific resistance was 6.1 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Example 5, and Table 2 shows the results of the inspection and test (evaluation).
- Example 6 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was prepared with the chamber outlet temperature set at 90 ° C. and the exhaust air flow rate set at 25 m 3 / min. Body material powder was obtained. Of the secondary particles constituting the sintered body material powder, the number ratio of doughnut-shaped secondary particles was 55%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered body tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 60%, and the average value of specific resistance was 6.5 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Example 6, and Table 2 shows the results (evaluations) of the inspection and test.
- Example 7 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was produced by setting the outlet temperature of the chamber to 100 ° C. and the exhaust air amount to 25 m 3 / min. Body material powder was obtained. Among the secondary particles constituting the sintered body material powder, the number ratio of donut-shaped secondary particles was 51%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 60% and the average value of specific resistance was 6.2 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Example 7, and Table 2 shows the results of the inspection and test (evaluation).
- Example 8 A zinc oxide sintered tablet was produced under the same conditions as in Example 1 except that the sintering temperature was changed to 800 ° C.
- the obtained zinc oxide sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 59%, and the average value of specific resistance was 1.2 ⁇ 10 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Example 8, and Table 2 shows the results of the inspection and test (evaluation).
- Example 9 A zinc oxide sintered tablet was produced under the same conditions as in Example 1 except that the sintering temperature was changed to 1300 ° C.
- the obtained zinc oxide sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 62% and the average value of specific resistance was 6.3 ⁇ ⁇ cm.
- the degree of orientation of the obtained zinc oxide sintered body tablet calculated as in Example 1 was 0.516.
- Table 1 shows the production conditions of Example 9, and Table 2 shows the results of the inspection and test (evaluation).
- Example 10 A zinc oxide sintered tablet was produced under the same conditions as in Example 1 except that the reduction treatment temperature (maximum temperature reached) was changed to 800 ° C.
- the obtained zinc oxide sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 59% and the average value of specific resistance was. It was 2.5 ⁇ 10 ⁇ ⁇ cm.
- the degree of orientation of the obtained zinc oxide sintered body tablet calculated as in Example 1 was 0.505.
- Table 1 shows the manufacturing conditions of Example 10, and Table 2 shows the results (evaluations) of the inspections and tests.
- Example 11 A zinc oxide sintered tablet was produced under the same conditions as in Example 1 except that the reduction treatment temperature (maximum temperature reached) was changed to 1300 ° C.
- the obtained sintered tablet was examined in the same manner as in Example 1. As a result, the average value of the relative density was 61% and the average value of the specific resistance was 6.0 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Example 11, and Table 2 shows the results of the inspection and test (evaluation).
- Example 12 A zinc oxide sintered body tablet was produced under the same conditions as in Example 1 except that the reduction treatment was not performed.
- the obtained sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 60%, and the average value of specific resistance was 3.2 ⁇ 10 5 ⁇ ⁇ cm.
- Table 1 shows the production conditions of Example 12, and Table 2 shows the results (evaluations) of the inspection and test.
- Example 1 Sintering made of granulated powder in the same manner as in Example 1 except that in the second stage granulation step, the granulated powder was produced with the chamber outlet temperature set at 110 ° C. and the exhaust air flow rate at 15 m 3 / min. Body material powder was obtained. Among the secondary particles constituting the sintered body material powder, the number ratio of donut-shaped secondary particles was 25%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 61% and the average value of specific resistance was 7.5 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Comparative Example 1
- Table 2 shows the results of the inspection and test (evaluation).
- Comparative Example 2 Sintering made of granulated powder in the same manner as in Example 1, except that in the second stage granulation step, the granulated powder was prepared with the chamber outlet temperature set at 70 ° C. and the exhaust air flow rate at 15 m 3 / min. Body material powder was obtained. Among the secondary particles constituting this sintered body material powder, the number ratio of doughnut-shaped secondary particles was 53%, but a sufficiently dry sintered body material powder could not be obtained, and its water content was Due to its high size, cracks occurred in 84 of 200 molded products obtained in the molding process. Therefore, it was judged that the productivity was greatly deteriorated under these conditions, and the production was stopped here.
- Table 1 shows the production conditions of Comparative Example 2
- Table 2 shows the results of the inspection and test (evaluation).
- Example 3 Sintering made of granulated powder in the same manner as in Example 1 except that the granulated powder was produced at the outlet temperature of the chamber at 90 ° C. and the exhaust air volume at 28 m 3 / min in the second stage granulation step. Body material powder was obtained. Among the secondary particles constituting the sintered body material powder, the number ratio of donut-shaped secondary particles was 42%. Using the obtained sintered body material, zinc oxide sintered body tablets were manufactured under the same conditions as in Example 1 after the molding.
- the obtained zinc oxide sintered body tablet was examined in the same manner as in Example 1. As a result, the average value of relative density was 60% and the average value of specific resistance was 7.4 ⁇ ⁇ cm.
- Table 1 shows the manufacturing conditions of Comparative Example 3
- Table 2 shows the results of the inspection and test (evaluation).
- Example 4 65% by mass of zinc oxide powder having a maximum particle size of 75 ⁇ m or less and an average particle size of 10 ⁇ m, calcined at about 1400 ° C. for 3 hours, uncalcined with a maximum particle size of 20 ⁇ m or less and an average particle size of about 1 ⁇ m
- the zinc oxide powders were weighed to 35% by mass, and these were dry-mixed by a ball mill.
- the number ratio of donut-shaped secondary particles was 0%.
- a zinc oxide sintered body tablet was manufactured under the same conditions as in Example 1 after the molding.
- Table 1 shows the production conditions of Comparative Example 4, and Table 2 shows the results of the inspection and test (evaluation).
- Example 5 A zinc oxide powder having a maximum particle size of 110 ⁇ m or less and an average particle size of 5 ⁇ m and calcined at about 900 ° C. for 3 hours was used as a sintered body material powder, and all the steps after molding were performed under the same conditions as in Example 1.
- a zinc oxide sintered body tablet was produced. Among the secondary particles constituting the sintered body material powder used at this time, the number ratio of the doughnut-shaped secondary particles was 0%. Moreover, when the obtained zinc oxide sintered compact tablet was test
- Table 1 shows the manufacturing conditions of Comparative Example 5, and Table 2 shows the results of the inspection and test (evaluation).
- Example 1 60% by mass was collected from each of the zinc oxide powder and the gallium oxide powder, and a granulated powder was obtained in the same manner as in the first-stage granulation step of Example 1.
- the granulated powder was fired at 1200 ° C. for 20 hours in an atmospheric pressure sintering furnace, and pulverized after firing to obtain a calcined powder having a particle size of 300 ⁇ m or less.
- Example 1 After obtaining the mixed powder of the calcined powder and the uncalcined powder by mixing the calcined powder and the initially prepared uncalcined raw material powder, the second stage of Example 1 is obtained.
- a sintered body material powder made of granulated powder having a particle size of 300 ⁇ m or less was obtained.
- the number ratio of the doughnut-shaped secondary particles is 60% (Example 13), 57% (Example 14), and 52% (Example 15), respectively. there were.
- the zinc oxide sintered body tablet was processed under the same conditions as in Example 1 except that the sintering temperature and the reduction treatment temperature were 1100 ° C. Manufactured.
- the amount of gallium oxide in the zinc oxide-based sintered tablet containing gallium oxide was 3.2% by mass (Example 13), 10.7% by mass (Example 14), and 51.9% by mass (implementation). are the example 15), the theoretical density of the sintered-body tablets having a density of zinc oxide and gallium oxide, respectively 5.78 g / cm 3, because it is 6.16 g / cm 3, respectively 5.79 g / cm 3 (Example 13) This is 5.82 g / cm 3 (Example 14) and 5.97 g / cm 3 (Example 15).
- the obtained sintered tablet was examined in the same manner as in Example 1.
- Example 13 the average relative density was 60% and the specific resistance was 6.6 ⁇ 10 ⁇ 4 ⁇ ⁇ cm (implemented).
- Example 13 8.9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm (Example 14), and 3.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm (Example 15).
- Example 13 when the orientation degree of a uniaxial pressurization surface was computed similarly to Example 1, 0.498 (Example 13), 0.495 (Example 14), 0.492 (Example 15).
- Table 3 shows the manufacturing conditions of Examples 13 to 15, and Table 4 shows the results (evaluations) of the inspections and tests.
- Example 16 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that boron oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of the doughnut-shaped secondary particles was 59%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 6.8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.508.
- Table 3 shows the production conditions of Example 16, and Table 4 shows the results of the inspection and test (evaluation).
- Example 17 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that aluminum oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 61%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 3.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.510.
- Table 3 shows the manufacturing conditions of Example 17, and Table 4 shows the results of the inspection and test (evaluation).
- Example 18 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that indium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 58%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 4.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.501.
- Table 3 shows the production conditions of Example 18, and Table 4 shows the results of the inspection and test (evaluation).
- Example 19 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that titanium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 58%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 1.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.508.
- Table 3 shows the production conditions of Example 19, and Table 4 shows the results of the inspection and test (evaluation).
- Example 20 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that zirconium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 57%, and the obtained sintered body was theoretically derived in the same manner as in Example 13. The average value of the relative density calculated from the inspection results was 59%, and the average value of the specific resistance was 4.5 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.492.
- Table 3 shows the manufacturing conditions of Example 20, and Table 4 shows the results (evaluations) of the inspection and test.
- Example 21 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that hafnium oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of the doughnut-shaped secondary particles was 59%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 59%, and the average value of the specific resistance was 7.2 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.500.
- Table 3 shows the production conditions of Example 21, and Table 4 shows the results of the inspection and test (evaluation).
- Example 22 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13, except that molybdenum oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 61%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 61%, and the average value of the specific resistance was 2.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.498.
- Table 3 shows the production conditions of Example 22, and Table 4 shows the results of the inspection and test (evaluation).
- Example 23 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that tungsten oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 60%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 9.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.510.
- Table 3 shows the manufacturing conditions of Example 23, and Table 4 shows the results of the inspection and test (evaluation).
- Example 24 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that vanadium oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of doughnut-shaped secondary particles was 56%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 8.6 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.505.
- Table 3 shows the manufacturing conditions of Example 24, and Table 4 shows the results of the inspection and test (evaluation).
- Example 25 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that niobium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 60%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 62%, and the average value of the specific resistance was 8.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.511.
- Table 3 shows the manufacturing conditions of Example 25, and Table 4 shows the results of the inspection and test (evaluation).
- Example 26 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that tantalum oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of the doughnut-shaped secondary particles was 59%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 3.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.504.
- Table 3 shows the production conditions of Example 26, and Table 4 shows the results of the inspection and test (evaluation).
- Example 27 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that cerium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 58%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 59%, and the average value of the specific resistance was 6.9 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.497.
- Table 3 shows the manufacturing conditions of Example 27, and Table 4 shows the results of the inspection and test (evaluation).
- Example 28 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that praseodymium oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of the doughnut-shaped secondary particles was 59%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 1.0 ⁇ 10 ⁇ 1 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.511.
- Table 3 shows the production conditions of Example 28, and Table 4 shows the results of the inspection and test (evaluation).
- Example 29 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that gadolinium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 62%, and the obtained sintered body was theoretically derived in the same manner as in Example 13. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 2.0 ⁇ 10 ⁇ 1 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.502.
- Table 3 shows the production conditions of Example 29, and Table 4 shows the results of the inspection and test (evaluation).
- Example 30 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that yttrium oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of the doughnut-shaped secondary particles was 59%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 58%, and the average value of the specific resistance was 9.2 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.502.
- Table 3 shows the production conditions of Example 30, and Table 4 shows the results of the inspection and test (evaluation).
- Example 31 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that tin oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 60%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 59%, and the average value of the specific resistance was 2.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.508.
- Table 3 shows the manufacturing conditions of Example 31, and Table 4 shows the results of the inspection and test (evaluation).
- Example 32 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that ruthenium oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of the doughnut-shaped secondary particles was 59%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 5.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.509.
- Table 3 shows the manufacturing conditions of Example 32, and Table 4 shows the results of the inspection and test (evaluation).
- Example 33 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that magnesium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 63%, and the obtained sintered body was theoretically derived in the same manner as in Example 13. The average value of the relative density calculated from the inspection results was 62%, and the average value of the specific resistance was 2.8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.501.
- Table 3 shows the production conditions of Example 33, and Table 4 shows the results of the inspection and test (evaluation).
- Example 34 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that iridium oxide powder was used instead of gallium oxide as the raw material powder. At this time, the number ratio of the doughnut-shaped secondary particles among the secondary particles constituting the sintered body material powder was 60%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 60%, and the average value of the specific resistance was 8.8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.510.
- Table 3 shows the production conditions of Example 34, and Table 4 shows the results of the inspection and test (evaluation).
- Example 35 A zinc oxide-based sintered tablet was produced under the same conditions as in Example 13 except that bismuth oxide powder was used instead of gallium oxide as the raw material powder. At this time, among the secondary particles constituting the sintered body material powder, the number ratio of doughnut-shaped secondary particles was 56%, and the theoretical density derived for the obtained sintered body in the same manner as in Example 13 was obtained. The average value of the relative density calculated from the inspection results was 58%, and the average value of the specific resistance was 2.2 ⁇ 10 ⁇ 1 ⁇ ⁇ cm. Further, the degree of orientation of the obtained sintered tablet was calculated in the same manner as in Example 1, and it was 0.503.
- Table 3 shows the production conditions of Example 35, and Table 4 shows the results of the inspection and test (evaluation).
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Abstract
Description
(配向度)
本発明の酸化亜鉛系焼結体タブレットは、昇華面となる1軸加圧面における結晶配向性に関して、(103)結晶配向性が大きいという特徴を有している。CuKα線を使用したX線回折による(103)面、(110)面のピーク積分強度をI(103)、I(110)としたとき、I(103)/(I(103)+I(110))で表される1軸加圧面の配向度が0.48以上であれば、成膜時におけるスプラッシュが抑制される。
本発明の酸化亜鉛焼結体タブレットでは、従来の真空蒸着用の酸化亜鉛焼結体タブレットと同様に、成膜時の割れやクラックの発生を防止する観点から、その相対密度(理論密度に対する嵩密度の割合)を50%~70%としている。ここで、相対密度を算出する際に用いられる酸化亜鉛の理論密度は、5.78g/cm3である。
本発明の酸化亜鉛焼結体タブレットは、上記したドーパントを含まない場合には、その比抵抗は密度にもよるが1.0×105Ω・cm~1.0×109Ω・cm程度となる。このような高抵抗の場合にも、本発明の酸化亜鉛焼結体タブレットは、昇華面における(103)結晶配向性が大きいことに起因して、昇華の均一性が向上し、スプラッシュ現象が発生しにくくなる。
[酸化亜鉛焼結体タブレットの製造方法]
(ドーナツ状の二次粒子の製造)
以上のような優れた特性を有する、酸化亜鉛焼結体タブレットは、本発明者が研究を重ねた結果、ドーナツ状の二次粒子の比率が50%以上である造粒粉末を焼結体材料として用いることにより得られるとの知見が得られたのである。なお、このドーナツ状の二次粒子の比率は、好ましくは60%以上、さらに好ましくは68%以上、最適には78%以上とする。
まず、酸化亜鉛粉末、またはドーパントとなる添加元素と酸化亜鉛との混合粉末からなる原料粉末を用意する。最初に用意される原料粉末については、焼結性の均一化の観点から、平均粒径が1μm以下のものを用いることが好ましい。また、粒度分布測定による累積重量が90%となるときの粒径(D90)が1.0μm以上2.0μm以下となる原料粉末を用いることにより、得られる焼結体の寸法や密度などがより安定し、歩留まりよく製造を行うことが可能となる。
本発明の酸化亜鉛焼結体タブレットの製造では、原料粉末を仮焼した仮焼粉末と、未仮焼の原料粉末とを混合したものを、焼結体材料とすることが好ましい。なお、混合方法は特に限定されることなく、公知の技術を利用することができる。
次に、上記の原料粉末を、純水と、ポリビニルアルコール、メチルセルロースなどの有機バインダ、ポリカルボン酸アンモニウム塩、アクリル酸系アミン塩などの分散剤とともに、原料粉末濃度が50質量%~80質量%、好ましくは65~75質量%、好適には70質量%程度となるように混合し、スラリーを作製する。なお、混合方法は特に限定されることなく、公知の技術を利用することができる。
次に、造粒粉末からなる焼結体材料粉末を、たとえば、金型中で加圧する機械プレス法などにより1軸加圧成形して、成形体を得る。該成形体を得る工程では、造粒粉末を49MPa(0.5tonf/cm2)以上147MPa(1.5tonf/cm2)以下の圧力で成形すると、所望の相対密度の焼結体タブレットが得られやすく望ましい。また、原料として使用している仮焼粉末の使用量と、該仮焼粉末の熱処理温度と、後工程での焼結温度を一定にすることで、焼結時の各タブレットの収縮率をほぼ同一にコントロールできる。
次に、上記成形体を常圧で焼結することにより、酸化亜鉛またはドーパントを含む酸化亜鉛からなる焼結体タブレットを得る。この際の焼結温度は、800℃~1300℃の範囲内とする。この範囲では、焼結温度の上昇に伴い、より高い相対密度、より低い比抵抗のものが得られる傾向となる。なお、焼結温度が800℃未満では、焼結が進行せず、機械的な強度の弱い常圧焼結体タブレットになる。また、焼結収縮が十分進んでいないために、焼結したタブレットの密度や寸法のばらつきが大きくなる。一方、焼結温度が1300℃を超えると、亜鉛が揮発し、所定の酸化亜鉛組成からずれてしまうことになる。この観点から、上記焼結温度を900℃~1100℃の範囲内とすることが好ましい。また、焼結を行う際の昇温速度に関しては、添加している有機分が蒸発する際の蒸気圧を考慮し、昇温中の割れを防ぐ目的で1.0℃/分とすることが好ましい。
本発明の製造工程においては、前記焼結により得られた常圧焼結体タブレットに対して、真空中にて還元処理をおこなってもよい。この場合は、還元圧力を1×10-3Pa以下とし、還元温度を800℃~1300℃の範囲内とする。焼結条件と同様に、この範囲では、還元温度の上昇に伴い、より高い相対密度およびより低い比抵抗を得られる傾向となる。
まず、原料粉末として、平均粒径が1μm以下の酸化亜鉛粉末を所定量秤量し、用意した。
[相対密度]
この酸化亜鉛焼結体タブレットの理論密度は、酸化亜鉛の密度である5.78g/cm3となる。一方、得られた200個の焼結体タブレットのすべてについて、直径、高さ、重量を測定して嵩密度を得て、前記理論密度に対する相対密度を算出した結果、その相対密度の平均値は60%であった。
50個の試料について、四探針法抵抗率計ロレスタEP(株式会社三菱化学アナリテック製、MCP-T360型)を用いて、表面の比抵抗を測定したところ、比抵抗の平均値は8.5Ω・cmであった。
試料のうちの2個を試験片とし、X線回折装置(スペクトリス株式会社製、X‘Pert-PRO/MPD)を用いてCuKα線を使用したX線解析(XRD)測定を実施した。その結果、得られた(103)面、(110)面のそれぞれ積分強度をI(103)、I(110)としたとき、I(103)/(I(103)+I(110))で表される1軸加圧面の配向度を算出したところ、0.513であった。
50個の試料について、真空蒸着装置に連続的に供給しつつ、それぞれの試料について電子ビームを照射して蒸着をおこなった。その結果、すべての焼結体タブレットについて、成膜時のスプラッシュ現象は発生せず、放電は安定していた。
第2段の造粒工程において、チャンバの出口温度を80℃、排風量を15m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は72%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を90℃、排風量を5m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は68%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を80℃、排風量を5m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は79%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を100℃、排風量を15m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は54%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を90℃、排風量を25m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は55%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を100℃、排風量を25m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は51%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
焼結温度を800℃に変えた点以外は、実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
焼結温度を1300℃に変えた点以外は、実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
還元処理温度(最高到達温度)を800℃に変えた点以外は、実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
還元処理温度(最高到達温度)を1300℃に変えた点以外は、実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
還元処理を実施しなかった点以外は、実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を110℃、排風量を15m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は25%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
第2段の造粒工程において、チャンバの出口温度を70℃、排風量を15m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は53%であったが、十分に乾燥した焼結体材料粉末が得られず、その水分量が高いために成形工程で得られた成形体200個のうち84個にクラックが発生した。したがって、この条件では生産性が大きく悪化すると判断し、ここで作製を中止した。
第2段の造粒工程において、チャンバの出口温度を90℃、排風量を28m3/分として造粒粉末を作製したこと以外は、実施例1と同様にして、造粒粉末からなる焼結体材料粉末を得た。この焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は42%であった。得られた焼結体材料を用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
最大粒子径が75μm以下で平均粒子径が10μmであり、約1400℃で3時間仮焼した酸化亜鉛粉末を65質量%と、最大粒子径が20μm以下で平均粒子径が約1μmの未仮焼の酸化亜鉛粉末を35質量%となるようそれぞれ秤量し、これらをボールミルによって乾式混合した。得られた混合粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は0%であった。この混合粉末からなる焼結体材料粉末を用いて、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。
最大粒子径が110μm以下で平均粒子径が5μmであり、約900℃で3時間仮焼した酸化亜鉛粉末を焼結体材料粉末として用い、成形以降の工程はすべて実施例1と同様の条件で、酸化亜鉛焼結体タブレットを製造した。このとき用いた焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は0%であった。また、得られた酸化亜鉛焼結体タブレットについて、実施例1と同様に検査をおこなったところ、相対密度の平均値は60%、比抵抗の平均値は8.8Ω・cmであった。
原料粉末として、平均粒径が1μm以下の酸化亜鉛粉末と、平均粒径が2μm以下の酸化ガリウム粉末とを、それぞれ「亜鉛:ガリウム=97原子%:3.0原子%」(実施例13)、「亜鉛:ガリウム=90原子%:10原子%」(実施例14)、「亜鉛:ガリウム=50原子%:50原子%」(実施例15)の割合となるように、所定量秤量し、用意した。
原料粉末として酸化ガリウムの代わりに酸化ホウ素粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は59%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は6.8×10-3Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.508であった。
原料粉末として酸化ガリウムの代わりに酸化アルミニウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は61%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は3.1×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.510であった。
原料粉末として酸化ガリウムの代わりに酸化インジウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は58%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は4.1×10-3Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.501であった。
原料粉末として酸化ガリウムの代わりに酸化チタン粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は58%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は1.2×10-3Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.508であった。
原料粉末として酸化ガリウムの代わりに酸化ジルコニウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は57%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は59%であり、比抵抗の平均値は4.5×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.492であった。
原料粉末として酸化ガリウムの代わりに酸化ハフニウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は59%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は59%であり、比抵抗の平均値は7.2×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.500であった。
原料粉末として酸化ガリウムの代わりに酸化モリブデン粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は61%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は61%であり、比抵抗の平均値は2.2×10-3Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.498であった。
原料粉末として酸化ガリウムの代わりに酸化タングステン粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は60%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は9.4×10-4Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.510であった。
原料粉末として酸化ガリウムの代わりに酸化バナジウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は56%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は8.6×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.505であった。
原料粉末として酸化ガリウムの代わりに酸化ニオブ粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は60%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は62%であり、比抵抗の平均値は8.1×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.511であった。
原料粉末として酸化ガリウムの代わりに酸化タンタル粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は59%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は3.5×10-3Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.504であった。
原料粉末として酸化ガリウムの代わりに酸化セリウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は58%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は59%であり、比抵抗の平均値は6.9×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.497であった。
原料粉末として酸化ガリウムの代わりに酸化プラセオジム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は59%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は1.0×10-1Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.511であった。
原料粉末として酸化ガリウムの代わりに酸化ガドリニウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は62%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は2.0×10-1Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.502であった。
原料粉末として酸化ガリウムの代わりに酸化イットリウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は59%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は58%であり、比抵抗の平均値は9.2×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.502であった。
原料粉末として酸化ガリウムの代わりに酸化スズ粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は60%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は59%であり、比抵抗の平均値は2.1×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.508であった。
原料粉末として酸化ガリウムの代わりに酸化ルテニウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は59%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は5.0×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.509であった。
原料粉末として酸化ガリウムの代わりに酸化マグネシウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は63%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は62%であり、比抵抗の平均値は2.8×10-3Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.501であった。
原料粉末として酸化ガリウムの代わりに酸化イリジウム粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は60%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は60%であり、比抵抗の平均値は8.8×10-2Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.510であった。
原料粉末として酸化ガリウムの代わりに酸化ビスマス粉末を使用したこと以外は、実施例13と同様の条件で、酸化亜鉛系焼結体タブレットを製造した。この際、焼結体材料粉末を構成する二次粒子のうち、ドーナツ状の二次粒子の個数比率は56%であり、得られた焼結体について、実施例13と同様に導出した理論密度と検査結果から算出した相対密度の平均値は58%であり、比抵抗の平均値は2.2×10-1Ω・cmであった。また、得られた焼結体タブレットについて、実施例1と同様に配向度を算出したところ、0.503であった。
Claims (11)
- 六方晶系の結晶構造を有する、酸化亜鉛またはドーパントを含む酸化亜鉛の焼結体からなり、CuKα線を使用したX線回折による(103)面、(110)面のそれぞれ積分強度をI(103)、I(110)としたとき、I(103)/(I(103)+I(110))で表される1軸加圧面の配向度が0.48以上である、酸化亜鉛焼結体タブレット。
- 前記配向度が0.5以上である、請求項1に記載の酸化亜鉛焼結体タブレット。
- 前記配向度が0.55以上である、請求項1に記載の酸化亜鉛焼結体タブレット。
- 前記配向度が0.6以上である、請求項1に記載の酸化亜鉛焼結体タブレット。
- 比抵抗が1×102Ω・cm以下である、請求項1~4のいずれかに記載の酸化亜鉛焼結体タブレット。
- 相対密度が50%以上70%以下である、請求項1~5のいずれかに記載の酸化亜鉛焼結体タブレット。
- ドーナツ状の二次粒子の比率が50%以上である、酸化亜鉛粉末またはドーパントとなる添加元素と酸化亜鉛との混合粉末からなる造粒粉末を加圧成形して得た成形体を、常圧にて、800℃~1300℃の温度で焼結させることを特徴とする、請求項1~6のいずれかに記載の酸化亜鉛焼結体タブレットの製造方法。
- 前記焼結により得られた常圧焼結体を、圧力が1×10-4Pa以上1×10-3Pa以下の真空中にて、800℃~1300℃の温度で、1分以上10分以下の時間保持し、還元処理することを特徴とする、請求項7に記載の酸化亜鉛焼結体タブレットの製造方法。
- 前記酸化亜鉛粉末または混合粉末の原料粉末をスラリーとし、該スラリーを、80℃~100℃の温度で、排風量を前記ドーナツ状の二次粒子の比率が50%以上となるように調整して、噴霧乾燥させることにより、前記造粒粉末を得る、請求項7または8に記載の酸化亜鉛焼結体タブレットの製造方法。
- 前記造粒粉末の一部を、800℃~1300℃の温度で1時間~30時間、仮焼する請求項9に記載の酸化亜鉛焼結体タブレットの製造方法。
- 前記仮焼後の造粒粉末と未仮焼の造粒粉末とを混合して使用する、請求項10に記載の酸化亜鉛焼結体タブレットの製造方法。
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JP5971201B2 (ja) * | 2013-06-17 | 2016-08-17 | 住友金属鉱山株式会社 | In−Ce−O系スパッタリングターゲットとその製造方法 |
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CN113666735B (zh) * | 2021-09-10 | 2022-07-05 | 山东大学 | 连续调控氧化锌陶瓷光吸收性质的方法、氧化锌陶瓷及制备方法 |
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- 2011-05-20 TW TW100117732A patent/TWI452027B/zh not_active IP Right Cessation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013057065A3 (de) * | 2011-10-18 | 2013-07-25 | Vaciontec GmbH | Keramisches erzeugnis zur verwendung als target |
JP2014231625A (ja) * | 2013-05-29 | 2014-12-11 | 住友金属鉱山株式会社 | 蒸着用タブレットとその製造方法 |
Also Published As
Publication number | Publication date |
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JPWO2011145665A1 (ja) | 2013-07-22 |
US9224513B2 (en) | 2015-12-29 |
JP5692224B2 (ja) | 2015-04-01 |
TWI452027B (zh) | 2014-09-11 |
KR101440712B1 (ko) | 2014-09-17 |
KR20130018321A (ko) | 2013-02-20 |
EP2573059A1 (en) | 2013-03-27 |
TW201202168A (en) | 2012-01-16 |
CN102906050A (zh) | 2013-01-30 |
EP2573059A4 (en) | 2014-01-29 |
US20130200314A1 (en) | 2013-08-08 |
CN102906050B (zh) | 2014-07-09 |
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