Sn-Zn-O-BASED OXIDE SINTERED BODY AND METHOD FOR PRODUCING THE SAME
20210206697 ยท 2021-07-08
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Inventors
Cpc classification
C04B2235/3286
CHEMISTRY; METALLURGY
C04B2235/604
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C04B35/49
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C04B2235/3256
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C04B2235/3284
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C04B2235/3293
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C04B2235/3251
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C04B2235/3258
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C04B2235/5436
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C04B2235/80
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C04B2235/3298
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C04B2235/6585
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C04B2235/3418
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C04B2235/3287
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C04B2235/3232
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C04B2235/3217
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C04B2235/3229
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C04B35/62655
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C04B2235/5445
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C04B35/453
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International classification
C04B35/49
CHEMISTRY; METALLURGY
C04B35/626
CHEMISTRY; METALLURGY
Abstract
[Object] An object is to provide a SnZnO-based oxide sintered body which has a mechanical strength, a high density, and a low resistance characteristic and which is applied as a sputtering target, and a method for producing the same.
[Solving Means] In this oxide sintered body, Sn is contained with an atomic ratio of Sn/(Sn+Zn) being 0.1 or more and 0.9 or less, and a first additional element M is contained with an atomic ratio of M/(Sn+Zn+M+X) being 0.0001 or more and 0.04 or less relative to a total amount of all the metal elements, and a second additional element X is contained with an atomic ratio of X/(Sn+Zn+M+X) being 0.0001 or more and 0.1 or less relative to the total amount of all the metal elements, where the first additional element M is at least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga, and the second additional element X is at least one selected from Nb, Ta, W, and Mo, and a relative density of the sintered body is 90% or more and a specific electrical resistance of the sintered body is 1 .Math.cm or less.
Claims
1: A SnZnO-based oxide sintered body comprising Zn and Sn as main components, wherein Sn is contained with an atomic ratio of Sn/(Sn+Zn) being 0.1 or more and 0.33 or less, a first additional element M is contained with an atomic ratio of M/(Sn+Zn+M+X) being 0.0001 or more and 0.04 or less relative to a total amount of all the metal elements, and a second additional element X is contained with an atomic ratio of X/(Sn+Zn+M+X) being 0.0001 or more and 0.1 or less relative to the total amount of all the metal elements, where the first additional element M is at least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga, and the second additional element X is at least one selected from Nb, Ta, W, and Mo, a relative density of the sintered body is 90% or more and a specific electrical resistance of the sintered body is 1 .Math.cm or less, and an X-ray diffraction peak position of the (101) plane of a ZnO phase is 36.25 degrees to 36.31 degrees, and an X-ray diffraction peak position of the (311) plane of a Zn.sub.2SnO.sub.4 phase is 34.32 degrees to 34.42 degrees, as measured by X-ray diffraction using the CuK radiation.
2. (canceled)
3: A SnZnO-based oxide sintered body comprising Zn and Sn as main components, wherein Sn is contained with an atomic ratio of Sn/(Sn+Zn) being more than 0.33 and 0.9 or less, a first additional element M is contained with an atomic ratio of M/(Sn+Zn+M+X) being 0.0001 or more and 0.04 or less relative to a total amount of all the metal elements, and a second additional element X is contained with an atomic ratio of X/(Sn+Zn+M+X) being 0.0001 or more and 0.1 or less relative to the total amount of all the metal elements, where the first additional element M is at least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga, and the second additional element X is at least one selected from Nb, Ta, W, and Mo, a relative density of the sintered body is 90% or more and a specific electrical resistance of the sintered body is 1 .Math.cm or less, and an X-ray diffraction peak position of the (311) plane of a Zn.sub.2SnO.sub.4 phase is 34.32 degrees to 34.42 degrees, and an X-ray diffraction peak position of the (101) plane of a SnO.sub.2 phase is 33.86 degrees to 33.91 degrees, as measured by X-ray diffraction using the CuK radiation.
4: A method for producing a SnZnO-based oxide sintered body according to claim 1, wherein the method comprises: a granulated powder production step of producing a granulated powder by drying a slurry obtained by mixing a ZnO powder, a SnO.sub.2 powder, an oxide powder containing at least one first additional element M selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga, and an oxide powder containing at least one second additional element X selected from Nb, Ta, W, and Mo, with pure water, an organic binder, and a dispersing agent, followed by granulation; a compact production step of obtaining a compact by pressing the granulated powder; and a sintered body production step of obtaining a sintered body by sintering the compact inside a sintering furnace in an atmosphere with an oxygen concentration of 70% by volume or more under conditions of 1200 C. or more and 1450 C. or less and 10 hours or more and 30 hours or less.
5: A method for producing a SnZnO-based oxide sintered body according to claim 3, wherein the method comprises: a granulated powder production step of producing a granulated powder by drying a slurry obtained by mixing a ZnO powder, a SnO.sub.2 powder, an oxide powder containing at least one first additional element M selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga, and an oxide powder containing at least one second additional element X selected from Nb, Ta, W, and Mo, with pure water, an organic binder, and a dispersing agent, followed by granulation; a compact production step of obtaining a compact by pressing the granulated powder; and a sintered body production step of obtaining a sintered body by sintering the compact inside a sintering furnace in an atmosphere with an oxygen concentration of 70% by volume or more under conditions of 1200 C. or more and 1450 C. or less and 10 hours or more and 30 hours or less.
Description
MODES FOR PRACTICING THE INVENTION
[0036] Hereinafter, embodiments of the present invention will be described in detail.
[0037] It is possible to produce a SnZnO-based oxide sintered body according to the present invention having a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less by: first preparing a raw material powder which contains Sn with an atomic ratio of Sn/(Sn+Zn) being 0.1 or more and 0.9 or less, which contains at least one first additional element M selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga with an atomic ratio of M/(Sn+Zn+M+X) being 0.0001 or more and 0.04 or less relative to the total amount of all metal elements, and which contains at least one second additional element X selected from Nb, Ta, W, and Mo with an atomic ratio of X/(Sn+Zn+M+X) being 0.0001 or more and 0.1 or less relative to the total amount of all metal elements; producing a compact by pressing a granulated powder obtained by granulating the raw material powder; and sintering the compact inside the sintering furnace in an atmosphere with an oxygen concentration of 70% by volume or more under the conditions of 1200 C. or more and 1450 C. or less and 10 hours or more and 30 hours or less.
[0038] In the following, a method for producing a SnZn-0-based oxide sintered body according to the present invention will be described.
[Additional Elements]
[0039] The first additional element M and the second additional element X are required under the condition that Sn is contained with an atomic ratio of Sn/(Sn+Zn) being 0.1 or more and 0.9 or less because, if only the first additional element M is contained, the density improves but a low resistance characteristic cannot be obtained. On the other hand, if only the second additional element X is contained, a low resistance is achieved but a high density cannot be obtained.
[0040] Thus, by adding the first additional element M and the second additional element X, it is possible to obtain a high density and low resistance SnZnO-based oxide sintered body.
(First Additional Element M)
[0041] In the densification of an oxide sintered body, it is possible to obtain an effect of achieving a high density by adding at least one first additional element M selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga. The first additional element M described above is considered to contribute to densification by promoting grain boundary diffusion and helping neck growth among particles to strengthen the interparticle bonding. Here, the first additional element is represented by M, and the first additional element M has an atomic ratio of M/(Sn+Zn+M+X) being 0.0001 or more and 0.04 or less relative to the total amount of all metal elements because if the above atomic ratio of M/(Sn+Zn+M+X) is less than 0.0001, an effect of achieving a high density is not exhibited (see Comparative Example 9). On the other hand, if the above atomic ratio of M/(Sn+Zn+M+X) exceeds 0.04, the electrical conductivity of the oxide sintered body does not increase even when a second additional element X to be described later is added (see Comparative Example 10). Moreover, it is impossible to obtain a desired film characteristic in the film formation due to the generation of another compound such as a compound of SiO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, ZnAl.sub.2O.sub.4, ZnSiO.sub.4, Zn.sub.2Ge.sub.3O.sub.2, ZnTa.sub.2O.sub.6, or Ti.sub.0.5Sn.sub.0.5O.sub.2.
[0042] As described above, if only the first additional element M is added, the density of the oxide sintered body improves but the electrical conductivity is not improved.
(Second Additional Element)
[0043] Regarding the SnZnO-based oxide sintered body added with the above first additional element M under the condition that Sn is contained with an atomic ratio of Sn/(Sn+Zn) being 0.1 or more and 0.9 or less, the density improves as described above but there remains a problem of electrical conductivity.
[0044] In light of the above, at least one second additional element X selected from Nb, Ta, W, and Mo is added. By adding the second additional element X, the electrical conductivity is improved while maintaining the high density of the oxide sintered body. Note that the second additional element X is an element having a valence of 5 or more such as Nb, Ta, W, and Mo.
[0045] The amount added is required such that the second additional element X has an atomic ratio of X/(Sn+Zn+M+X) being 0.0001 or more and 0.1 or less relative to the total amount of all metal elements. If the above atomic ratio of X/(Sn+Zn+M+X) is less than 0.0001, the electrical conductivity does not increase (see Comparative Example 7). On the other hand, if the above atomic ratio of X/(Sn+Zn+M+X) exceeds 0.1, the electrical conductivity is deteriorated due to the generation of another compound phase such as a compound phase of Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, WO.sub.3, MoO.sub.3, ZnTa.sub.2O.sub.6, ZnWO.sub.4, and ZnMoO.sub.4 (see Comparative Example 8).
(X-Ray Diffraction Peak)
[0046] In the SnZnO-based oxide sintered body according to the present invention, the main components are a ZnO phase of a wurtzite-type crystal structure and a Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure as described above if the atomic ratio of Sn/(Sn+Zn) is 0.1 to 0.33, and the main components are a Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and a SnO.sub.2 phase of a rutile-type crystal structure if the atomic ratio of Sn/(Sn+Zn) is more than 0.33 and 0.9 or less. In addition, an appropriate amount of first additional element M and second additional element X is substituted for Zn in the ZnO phase, Zn or Sn in the Zn.sub.2SnO.sub.4 phase, and Sn in the SnO.sub.2 phase, followed by solid dissolution. For this reason, no additional compound phase is formed except for the ZnO phase of a wurtzite-type crystal structure, the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure, and the SnO.sub.2 phase of a rutile-type crystal structure.
[0047] It is possible to acquire knowledge on the crystal structure by carrying out X-ray diffraction analysis on powder obtained by grinding a portion of the above oxide sintered body and then analyzing the obtained diffraction peak. For example, in X-ray diffraction analysis using CuK radiation, the standard diffraction peak position of the wurtzite-type ZnO (101) plane is 36.253 degrees according to ICDD reference code 00-036-1451. The standard diffraction peak position of the Zn SnO.sub.4 (311) plane of a spinel type crystal structure is 34.291 degrees according to ICDD reference code 00-041-1470, and the standard diffraction peak position of the rutile-type SnO.sub.2 (101) plane is 33.893 degrees according to ICDD reference code 00-041-1445.
[0048] Note that the position of diffraction peak is affected by e.g. the type, amount of the additional element, sintering temperature, atmosphere, and retention time and varies because of, for example, expansion, contraction, or distortion of the crystal structure attributed to the substitution position of the additional element in the crystal, oxygen deficiency, internal stress, and the like.
[0049] Moreover, in the SnZnO-based oxide sintered body according to the present invention, the diffraction peak position of the ZnO (101) plane by X-ray diffraction analysis using CuK radiation is preferably 36.25 degrees to 36.31 degrees including the standard diffraction peak position of 36.253 degrees. In addition, the above diffraction peak position of the Zn SnO.sub.4 (311) plane is preferably 34.32 degrees to 34.42 degrees being angles higher than the standard diffraction peak position of 34.291 degrees, and the diffraction peak position of the SnO.sub.2 (101) plane is preferably 33.86 degrees to 33.91 degrees including the standard diffraction peak position of 33.893 degrees. Out of these ranges, expansion, contraction, or distortion of the ZnO, Zn SnO.sub.4, and SnO.sub.2 crystal proceeds to a large extent, which may cause cracks in the oxide sintered body, a decrease in sintering density, and a decrease in electrical conductivity.
[0050] As described above, by adding an appropriate amount of first additional element M and second additional element X, it is possible to obtain a SnZnO-based oxide sintered body which is high in density and excellent in electrical conductivity.
[Conditions for Sintering Compact]
(Atmosphere Inside Furnace)
[0051] It is preferable to sinter a compact inside the sintering furnace in an atmosphere with an oxygen concentration of 70% by volume or more. This is because an effect of promoting diffusion of ZnO, SnO.sub.2, and Zn.sub.2SnO.sub.4 compounds, improving a sintering property, and improving electrical conductivity is obtained. In a high-temperature range, an effect of suppressing vaporization of ZnO and Zn.sub.2SnO.sub.4 is also obtained.
[0052] On the other hand, if the oxygen concentration inside the sintering furnace is less than 70% by volume, the diffusion of ZnO, SnO.sub.2, and Zn.sub.2SnO.sub.4 compounds reduces. Furthermore, in a high-temperature range, vaporization of the Zn component is promoted and it is impossible to fabricate a dense sintered body (see Comparative Example 3).
(Sintering Temperature)
[0053] The sintering temperature is preferably 1200 C. or more and 1450 C. or less. If the sintering temperature is less than 1200 C. (see Comparative Example 4), the temperature is so low that grain boundary diffusion of sintering in the ZnO, SnO.sub.2, and Zn.sub.2SnO.sub.4 compounds does not proceed. On the other hand, if the temperature exceeds 1450 C. (see Comparative Example 5), grain boundary diffusion is promoted and sintering proceeds. However, even if sintering is performed in a furnace with an oxygen concentration or 70% by volume or more, it is impossible to suppress vaporization of the Zn component. As a result, there remain large pores inside the sintered body.
(Retention Time)
[0054] The retention time is preferably 10 hours or more and 30 hours or less. A retention time less than 10 hours results in insufficient sintering. As a result, the sintered body has a large distortion or warpage, and grain boundary diffusion does not proceed. Hence, sintering does not proceed. Consequently, it is impossible to fabricate a dense sintered body (see Comparative Example 6). On the other hand, if the retention time exceeds 30 hours, it is impossible to obtain a time effect in particular. This results in low work efficiency and high cost.
[0055] Since the SnZnO-based oxide sintered body containing Zn and Sn as main components obtained under the above conditions also has an improved electrical conductivity, film formation by DC sputtering is possible. In addition, the sintered body is applicable to a cylindrical target because no special production method is employed.
EXAMPLES
[0056] Hereinafter, a specific description is provided for the examples of the present invention by using comparative examples. It is a matter of course that the technical scope according to the present invention is not limited to the description of the examples below and that modifications can be made within a scope not departing from the present invention.
Example 1
[0057] A SnO.sub.2 powder having an average particle diameter of 10 m or less, a ZnO powder having an average particle diameter of 10 m or less, a Bi.sub.2O.sub.3 powder having an average particle diameter of 20 m or less as the first additional element M, and a Ta.sub.2O.sub.5 powder having an average particle diameter of 20 m or less as the second additional element X were prepared.
[0058] The SnO.sub.2 powder and the ZnO powder were formulated so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.5, and the Bi.sub.2O.sub.3 powder and the Ta.sub.2O.sub.5 powder were formulated so that the first additional element M would have an atomic ratio of Bi/(Sn+Zn+Bi+Ta) being 0.001 and that the second additional element X would have an atomic ratio of Ta/(Sn+Zn+Bi+Ta) being 0.001.
[0059] Then, the formulated raw material powder was mixed with pure water, an organic binder, and a dispersing agent in a mixing tank so that the concentration of the raw material powder would be 60% by mass.
[0060] Next, the mixture was ground in a wet manner by using a bead mill apparatus (manufactured by Ashizawa Finetech Ltd., Model: LMZ) into which hard ZrO.sub.2 balls were introduced, until the average particle diameter of the raw material powder became 1 m or less. Then, the mixture was stirred for mixing for 10 hours or more to obtain a slurry. Note that a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, SALD-2200) was used for measuring the average particle diameter of the raw material powder.
[0061] Next, the obtained slurry was spray dried by using a spray dryer apparatus (manufactured by OHKAWARA KAKOHKI CO., LTD., Model: ODL-20) to obtain a granulated powder.
[0062] Next, the obtained granulated powder was filled in a rubber mold and pressed by applying a pressure of 294 MPa (3 ton/cm) thereto with a cold isostatic press to obtain a compact having a diameter of approximately 250 mm. Then, the compact was introduced into an atmospheric-pressure sintering furnace, and air (oxygen concentration of 21% by volume) was introduced into the sintering furnace until the temperature reached 700 C. After it was confirmed that the temperature inside the sintering furnace reached 700 C., oxygen was introduced thereinto so that oxygen concentration would be 80% by volume. Thereafter, the temperature was raised to 1400 C. followed by retention at 1400 C. for 15 hours.
[0063] After the retention time was finished, introduction of oxygen was stopped for cooling. Thus, a SnZnO-based oxide sintered body according to Example 1 was obtained.
[0064] Next, a plane grinding machine and a grinding center were used to process the SnZnO-based oxide sintered body according to Example 1 to have a diameter of 200 mm and a thickness of 5 mm.
[0065] When the density of this processed body was measured by the Archimedes method, the relative density was 99.7%. In addition, when the specific electrical resistance was measured by the four-point probe method, the value was 0.003 .Math.cm.
[0066] Next, a portion of this processed body was cut and formed into a powder by mortar grinding. Analysis was carried out on this powder by an X-ray diffraction apparatus [XPert-PRO (manufactured by PANalytical)] using CuK radiation. As a result, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.39 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.89 degrees, which were normal diffraction peak positions.
[0067] Table 1-1, Table 1-2, and Table 1-3 show these results.
Example 2
[0068] A SnZnO-based oxide sintered body according to Example 2 was obtained in the same way as Example 1 except that the formulation was carried out so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.1. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the wurtzite-type ZnO phase and the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the ZnO (101) plane was 36.28 degrees and the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.34 degrees, which were normal diffraction peak positions. In addition, the relative density was 93.0% and the specific electrical resistance value was 0.57 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show these results.
Example 3
[0069] A SnZnO-based oxide sintered body according to Example 3 was obtained in the same way as Example 1 except that the formulation was carried out so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.3. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the wurtzite-type ZnO phase and the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the ZnO (101) plane was 36.26 degrees and the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.41 degrees, which were normal diffraction peak positions. In addition, the relative density was 94.2% and the specific electrical resistance value was 0.042 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show these results.
Example 4
[0070] A SnZnO-based oxide sintered body according to Example 4 was obtained in the same way as Example 1 except that the formulation was carried out so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.7. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.36 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.87 degrees, which were normal diffraction peak positions. In addition, the relative density was 99.7% and the specific electrical resistance value was 0.006 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show these results.
Example 5
[0071] A SnZnO-based oxide sintered body according to Example 5 was obtained in the same way as Example 1 except that the formulation was carried out so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.9. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.40 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.90 degrees, which were normal diffraction peak positions. In addition, the relative density was 92.7% and the specific electrical resistance value was 0.89 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show these results.
Example 6
[0072] A SnZnO-based oxide sintered body according to Example 6 was obtained in the same way as Example 1 except that the formulation was carried out so that the second additional element X would have an atomic ratio of Ta/(Sn+Zn+Bi+Ta) being 0.0001. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.33 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.87 degrees, which were normal diffraction peak positions. In addition, the relative density was 98.5% and the specific electrical resistance value was 0.085 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show the results.
Example 7
[0073] A SnZnO-based oxide sintered body according to Example 7 was obtained in the same way as Example 1 except that the oxygen concentration was 100% by volume. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.42 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.90 degrees, which were normal diffraction peak positions. In addition, the relative density was 99.6% and the specific electrical resistance value was 0.013 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show the results.
Example 8
[0074] A SnZnO-based oxide sintered body according to Example 8 was obtained in the same way as Example 1 except that the formulation was carried out so that the second additional element X would have an atomic ratio of Ta/(Sn+Zn+Bi+Ta) being 0.1, the retention time was 10 hours, and the oxygen concentration was 70% by volume. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.37 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.87 degrees, which were normal diffraction peak positions. In addition, the relative density was 94.6% and the specific electrical resistance value was 0.023 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show the results.
Example 9
[0075] A SnZnO-based oxide sintered body according to Example 9 was obtained in the same way as Example 1 except that the formulation was carried out so that the first additional element M would have an atomic ratio of Bi/(Sn+Zn+Bi+Ta) being 0.0001 and the sintering temperature was 1450 C. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.35 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.91 degrees, which were normal diffraction peak positions. In addition, the relative density was 97.3% and the specific electrical resistance value was 0.08 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show the results.
Example 10
[0076] A SnZnO-based oxide sintered body according to Example 10 was obtained in the same way as Example 1 except that the formulation was carried out so that the first additional element M would have an atomic ratio of Bi/(Sn+Zn+Bi+Ta) being 0.04 and the sintering temperature was 1200 C. When X-ray diffraction analysis was carried out on the powder in the same way as Example 1, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. The diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.36 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.88 degrees, which were normal diffraction peak positions. In addition, the relative density was 96.4% and the specific electrical resistance value was 0.11 .Math.cm. Table 1-1, Table 1-2, and Table 1-3 show the results.
TABLE-US-00001 TABLE 1-1 First Second Additional Additional Atomic Ratio Element M Element X Sn/(Sn + Zn) M/(Sn + Zn + M + X) X/(Sn + Zn + M + X) Example 1 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.001 Example 2 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.1 0.001 0.001 Example 3 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.3 0.001 0.001 Example 4 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.7 0.001 0.001 Example 5 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.9 0.001 0.001 Example 6 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.0001 Example 7 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.001 Example 8 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.1 Example 9 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.001 Example 10 Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.001
TABLE-US-00002 TABLE 1-2 Specific Sintering Reten- Oxygen Electrical Temper- tion Concen- Relative Resistance ature Time tration Density Value ( C.) (Hours) (% by Volume) (%) ( .Math. cm) Example 1 1400 15 80 99.7 0.003 Example 2 1400 15 80 93.0 0.57 Example 3 1400 15 80 94.2 0.042 Example 4 1400 15 80 99.7 0.006 Example 5 1400 15 80 92.7 0.89 Example 6 1400 15 80 98.5 0.085 Example 7 1400 15 100 99.6 0.013 Example 8 1400 10 70 94.6 0.023 Example 9 1450 15 80 97.3 0.08 Example 10 1200 15 80 96.4 0.11
TABLE-US-00003 TABLE 1-3 X-Ray Diffraction Peak Position (Degrees) ZnO (101) Zn2SnO4 (311) SnO2 (101) Example 1 34.39 33.89 Example 2 36.28 34.34 Example 3 36.26 34.41 Example 4 34.36 33.87 Example 5 34.40 33.90 Example 6 34.33 33.87 Example 7 34.42 33.90 Example 8 34.37 33.87 Example 9 34.35 33.91 Example 10 34.36 33.88
Examples 11 to 17
[0077] SnZnO-based oxide sintered bodies according to Examples 11 to 17 were obtained in the same way as Example 1 except that the formulation was carried out such that a SiO.sub.2 powder (Example 11), a TiO.sub.2 powder (Example 12), a GeO.sub.2 powder (Example 13), a In.sub.2O.sub.3 powder (Example 14), a CeO.sub.2 powder (Example 15), an Al.sub.2O.sub.3 powder (Example 16), and a Ga.sub.2O.sub.3 powder (Example 17) were used as the first additional element M, the first additional element M had an atomic ratio of M/(Sn+Zn+M+Ta) being 0.04, the same Ta.sub.2O.sub.5 powder as Example 1 was used as the second additional element X, and the second additional element X had an atomic ratio of Ta/(Sn+Zn+M+Ta) being 0.1.
[0078] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.32 degrees and 33.87 degrees (Example 11), 34.36 degrees and 33.90 degrees (Example 12), 34.40 degrees and 33.86 degrees (Example 13), 34.32 degrees and 33.88 degrees (Example 14), 34.34 degrees and 33.91 degrees (Example 15), 34.35 degrees and 33.86 degrees (Example 16), and 34.38 degrees and 33.91 degrees (Example 17), which were normal diffraction peak positions. Table 2-1, Table 2-2, and Table 2-3 show the results.
[0079] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 94.5% and 0.08 .Math.cm (Example 11), 95.1% and 0.21 .Math.cm (Example 12), 97.0% and 0.011 .Math.cm (Example 13), 96.1% and 0.048 .Math.cm (Example 14), 94.8% and 0.013 .Math.cm (Example 15), 94.6% and 0.18 .Math.cm (Example 16), and 95.3% and 0.48 .Math.cm (Example 17). Table 2-1, Table 2-2, and Table 2-3 show the results.
Examples 18 to 24
[0080] SnZnO-based oxide sintered bodies according to Examples 18 to 24 were obtained in the same way as Example 1 except that the formulation was carried out such that a SiO.sub.2 powder (Example 18), a TiO.sub.2 powder (Example 19), a GeO.sub.2 powder (Example 20), a In.sub.2O.sub.3 powder (Example 21), a CeO.sub.2 powder (Example 22), an Al.sub.2O.sub.3 powder (Example 23), and a Ga.sub.2O.sub.3 powder (Example 24) were used as the first additional element M, the first additional element M had an atomic ratio of M/(Sn+Zn+M+Ta) being 0.0001, the same Ta.sub.2O.sub.5 powder as Example 1 was used as the second additional element X, and the second additional element X had an atomic ratio of Ta/(Sn+Zn+M+Ta) being 0.1.
[0081] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.33 degrees and 33.89 degrees (Example 18), 34.32 degrees and 33.90 degrees (Example 19), 34.41 degrees and 33.88 degrees (Example 20), 34.39 degrees and 33.87 degrees (Example 21), 34.42 degrees and 33.89 degrees (Example 22), 34.37 degrees and 33.89 degrees (Example 23), and 34.38 degrees and 33.88 degrees (Example 24), which were normal diffraction peak positions. Table 2-1, Table 2-2, and Table 2-3 show the results.
[0082] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 93.3% and 0.011 .Math.cm (Example 18), 96.1% and 0.07 .Math.cm (Example 19), 95.0% and 0.021 .Math.cm (Example 20), 94.6% and 0.053 .Math.cm (Example 21), 96.1% and 0.08 .Math.cm (Example 22), 95.2% and 0.14 .Math.cm (Example 23), and 96.0% and 0.066 .Math.cm (Example 24). Table 2-1, Table 2-2, and Table 2-3 show the results.
Examples 25 to 31
[0083] SnZnO-based oxide sintered bodies according to Examples 25 to 31 were obtained in the same way as Example 1 except that the formulation was carried out such that a SiO.sub.2 powder (Example 25), a TiO.sub.2 powder (Example 26), a GeO.sub.2 powder (Example 27), a In.sub.2O.sub.3 powder (Example 28), a CeO.sub.2 powder (Example 29), an Al.sub.2O.sub.3 powder (Example 30), and a Ga.sub.2O.sub.3 powder (Example 31) were used as the first additional element M, the first additional element M had an atomic ratio of M/(Sn+Zn+M+Ta) being 0.04, the same Ta.sub.2O.sub.5 powder as Example 1 was used as the second additional element X, and the second additional element X had an atomic ratio of Ta/(Sn+Zn+M+Ta) being 0.0001.
[0084] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.32 degrees and 33.91 degrees (Example 25), 34.37 degrees and 33.86 degrees (Example 26), 34.42 degrees and 33.91 degrees (Example 27), 34.34 degrees and 33.88 degrees (Example 28), 34.40 degrees and 33.91 degrees (Example 29), 34.34 degrees and 33.86 degrees (Example 30), and 34.38 degrees and 33.90 degrees (Example 31), which were normal diffraction peak positions. Table 2-1, Table 2-2, and Table 2-3 show the results.
[0085] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 97.6% and 0.092 .Math.cm (Example 25), 97.9% and 0.0082 .Math.cm (Example 26), 97.9% and 0.0033 .Math.cm (Example 27), 97.5% and 0.0032 .Math.cm (Example 28), 98.7% and 0.009 .Math.cm (Example 29), 97.0% and 0.0054 .Math.cm (Example 30), and 99.1% and 0.009 .Math.cm (Example 31). Table 2-1, Table 2-2, and Table 2-3 show the results.
Examples 32 to 38
[0086] SnZnO-based oxide sintered bodies according to Examples 32 to 38 were obtained in the same way as Example 1 except that the formulation was carried out such that a SiO.sub.2 powder (Example 32), a TiO.sub.2 powder (Example 33), a GeO.sub.2 powder (Example 34), a In.sub.2O.sub.3 powder (Example 35), a CeO.sub.2 powder (Example 36), an Al.sub.2O.sub.3 powder (Example 37), and a Ga.sub.2O.sub.3 powder (Example 38) were used as the first additional element M, the first additional element M had an atomic ratio of M/(Sn+Zn+M+Ta) being 0.0001, the same Ta.sub.2O.sub.5 powder as Example 1 was used as the second additional element X, and the second additional element X had an atomic ratio of Ta/(Sn+Zn+M+Ta) being 0.0001.
[0087] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.36 degrees and 33.91 degrees (Example 32), 34.35 degrees and 33.87 degrees (Example 33), 34.42 degrees and 33.87 degrees (Example 34), 34.42 degrees and 33.86 degrees (Example 35), 34.41 degrees and 33.90 degrees (Example 36), 34.32 degrees and 33.87 degrees (Example 37), and 34.40 degrees and 33.88 degrees (Example 38), which were normal diffraction peak positions. Table 2-1, Table 2-2, and Table 2-3 show the results.
[0088] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 98.0% and 0.013 .Math.cm (Example 32), 97.5% and 0.0021 .Math.cm (Example 33), 97.8% and 0.012 .Math.cm (Example 34), 97.9% and 0.027 .Math.cm (Example 35), 98.0% and 0.0053 .Math.cm (Example 36), 98.5% and 0.0066 .Math.cm (Example 37), and 98.8% and 0.0084 .Math.cm (Example 38). Table 2-1, Table 2-2, and Table 2-3 show the results.
TABLE-US-00004 TABLE 2-1 First Second Additional Additional Atomic Ratio Element M Element X Sn/(Sn + Zn) M/(Sn + Zn + M + X) X/(Sn + Zn + M + X) Example 11 SiO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 12 TiO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 13 GeO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 14 In.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 15 CeO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 16 Al.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 17 Ga.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.1 Example 18 SiO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 19 TiO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 20 GeO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 21 In.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 22 CeO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 23 Al.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 24 Ga.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.1 Example 25 SiO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 26 TiO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 27 GeO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 28 In.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 29 CeO.sub.2 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 30 Al.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 31 Ga.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.04 0.0001 Example 32 SiO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.0001 Example 33 TiO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.0001 Example 34 GeO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.0001 Example 35 In.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.0001 Example 36 CeO.sub.2 Ta.sub.2O.sub.5 0.5 0.0001 0.0001 Example 37 Al.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.0001 Example 38 Ga.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.0001 0.0001
TABLE-US-00005 TABLE 2-2 Specific Sintering Reten- Oxygen Electrical Temper- tion Concen- Relative Resistance ature Time tration Density Value ( C.) (Hours) (% by Volume) (%) ( .Math. cm) Example 11 1400 15 80 94.5 0.08 Example 12 1400 15 80 95.1 0.21 Example 13 1400 15 80 97.0 0.011 Example 14 1400 15 80 96.1 0.048 Example 15 1400 15 80 94.8 0.013 Example 16 1400 15 80 94.6 0.18 Example 17 1400 15 80 95.3 0.48 Example 18 1400 15 80 93.3 0.011 Example 19 1400 15 80 96.1 0.07 Example 20 1400 15 80 95.0 0.021 Example 21 1400 15 80 94.6 0.053 Example 22 1400 15 80 96.1 0.08 Example 23 1400 15 80 95.2 0.14 Example 24 1400 15 80 96.0 0.066 Example 25 1400 15 80 97.6 0.092 Example 26 1400 15 80 97.9 0.0082 Example 27 1400 15 80 97.9 0.0033 Example 28 1400 15 80 97.5 0.0032 Example 29 1400 15 80 98.7 0.009 Example 30 1400 15 80 97.0 0.0054 Example 31 1400 15 80 99.1 0.009 Example 32 1400 15 80 98.0 0.013 Example 33 1400 15 80 97.5 0.0021 Example 34 1400 15 80 97.8 0.012 Example 35 1400 15 80 97.9 0.027 Example 36 1400 15 80 98.0 0.0053 Example 37 1400 15 80 98.5 0.0066 Example 38 1400 15 80 98.8 0.0084
TABLE-US-00006 TABLE 2-3 X-Ray Diffraction Peak Position (Degrees) ZnO (101) Zn2SnO4 (311) SnO2 (101) Example 11 34.32 33.87 Example 12 34.36 33.90 Example 13 34.40 33.86 Example 14 34.32 33.88 Example 15 34.34 33.91 Example 16 34.35 33.86 Example 17 34.38 33.91 Example 18 34.33 33.89 Example 19 34.32 33.90 Example 20 34.41 33.88 Example 21 34.39 33.87 Example 22 34.42 33.89 Example 23 34.37 33.89 Example 24 34.38 33.88 Example 25 34.32 33.91 Example 26 34.37 33.86 Example 27 34.42 33.91 Example 28 34.34 33.88 Example 29 34.40 33.91 Example 30 34.34 33.86 Example 31 34.38 33.90 Example 32 34.36 33.91 Example 33 34.35 33.87 Example 34 34.42 33.87 Example 35 34.42 33.86 Example 36 34.41 33.90 Example 37 34.32 33.87 Example 38 34.40 33.88
Examples 39 to 41
[0089] SnZnO-based oxide sintered bodies according to Examples 39 to 41 were obtained in the same way as Example 1 except that the formulation was carried out such that the same Bi.sub.2O.sub.3 powder as Example 1 was used as the first additional element M, the first additional element M had an atomic ratio of Bi/(Sn+Zn+Bi+X) being 0.04, a Nb.sub.2O.sub.5 powder (Example 39), a WO.sub.3 powder (Example 40), and a MoO.sub.3 powder (Example 41) were used as the second additional element X, and the second additional element X had an atomic ratio of X/(Sn+Zn+Bi+X) being 0.1.
[0090] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.40 degrees and 33.89 degrees (Example 39), 34.35 degrees and 33.90 degrees (Example 40), and 34.39 degrees and 33.86 degrees (Example 41), which were normal diffraction peak positions. Table 3-1, Table 3-2, and Table 3-3 show the results.
[0091] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 97.7% and 0.029 .Math.cm (Example 39), 95.9% and 0.069 .Math.cm (Example 40), and 96.9% and 0.19 .Math.cm (Example 41). Table 3-1, Table 3-2, and Table 3-3 show the results.
Examples 42 to 44
[0092] SnZnO-based oxide sintered bodies according to Examples 42 to 44 were obtained in the same way as Example 1 except that the formulation was carried out such that the same Bi.sub.2O.sub.3 powder as Example 1 was used as the first additional element M, the first additional element M had an atomic ratio of Bi/(Sn+Zn+Bi+X) being 0.0001, a Nb.sub.2O.sub.5 powder (Example 42), a WO.sub.3 powder (Example 43), and a MoO.sub.3 powder (Example 44) were used as the second additional element X, and the second additional element X had an atomic ratio of X/(Sn+Zn+Bi+X) being 0.1.
[0093] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.32 degrees and 33.89 degrees (Example 42), 34.34 degrees and 33.87 degrees (Example 43), and 34.39 degrees and 33.90 degrees (Example 44), which were normal diffraction peak positions. Table 3-1, Table 3-2, and Table 3-3 show the results.
[0094] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 94.8% and 0.021 .Math.cm (Example 42), 96.6% and 0.0096 .Math.cm (Example 43), and 95.6% and 0.0092 .Math.cm (Example 44). Table 3-1, Table 3-2, and Table 3-3 show the results.
Examples 45 to 47
[0095] SnZnO-based oxide sintered bodies according to Examples 45 to 47 were obtained in the same way as Example 1 except that the formulation was carried out such that the same Bi.sub.2O.sub.3 powder as Example 1 was used as the first additional element M, the first additional element M had an atomic ratio of Bi/(Sn+Zn+Bi+X) being 0.04, a Nb.sub.2O.sub.5 powder (Example 45), a WO.sub.3 powder (Example 46), and a MoO.sub.3 powder (Example 47) were used as the second additional element X, and the second additional element X had an atomic ratio of X/(Sn+Zn+Bi+X) being 0.0001.
[0096] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.36 degrees and 33.86 degrees (Example 45), 34.42 degrees and 33.88 degrees (Example 46), and 34.34 degrees and 33.90 degrees (Example 47), which were normal diffraction peak positions. Table 3-1, Table 3-2, and Table 3-3 show the results.
[0097] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 98.1% and 0.022 .Math.cm (Example 45), 97.6% and 0.0066 .Math.cm (Example 46), and 97.7% and 0.0077 .Math.cm (Example 47). Table 3-1, Table 3-2, and Table 3-3 show the results.
Examples 48 to 50
[0098] SnZnO-based oxide sintered bodies according to Examples 48 to 50 were obtained in the same way as Example 1 except that the formulation was carried out such that the same Bi.sub.2O.sub.3 powder as Example 1 was used as the first additional element M, the first additional element M had an atomic ratio of Bi/(Sn+Zn+Bi+X) being 0.0001, a Nb.sub.2O.sub.5 powder (Example 48), a WO.sub.3 powder (Example 49), and a MoO.sub.3 powder (Example 50) were used as the second additional element X, and the second additional element X had an atomic ratio of X/(Sn+Zn+Bi+X) being 0.0001.
[0099] Additionally, when X-ray diffraction analysis was carried out on each of the SnZnO-based oxide sintered bodies according to the examples, only the diffraction peaks of the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of other different compound phases were not measured. In addition, the combinations of diffraction peak positions of the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane for the SnZnO-based oxide sintered bodies according to the examples were 34.35 degrees and 33.88 degrees (Example 48), 34.41 degrees and 33.87 degrees (Example 49), and 34.33 degrees and 33.88 degrees (Example 50), which were normal diffraction peak positions. Table 3-1, Table 3-2, and Table 3-3 show the results.
[0100] In addition, the combinations of relative density and specific electrical resistance value for the SnZnO-based oxide sintered bodies according to the examples were 95.5% and 0.0099 .Math.cm (Example 48), 97.3% and 0.0074 .Math.cm (Example 49), and 97.4% and 0.009 .Math.cm (Example 50). Table 3-1, Table 3-2, and Table 3-3 show the results.
TABLE-US-00007 TABLE 3-1 First Second Additional Additional Atomic Ratio Element M Element X Sn/(Sn + Zn) M/(Sn + Zn + M + X) X/Sn + Zn + M + X) Example 39 Bi.sub.2O.sub.3 Nb.sub.2O.sub.5 0.5 0.04 0.1 Example 40 Bi.sub.2O.sub.3 WO.sub.3 0.5 0.04 0.1 Example 41 Bi.sub.2O.sub.3 MoO.sub.3 0.5 0.04 0.1 Example 42 Bi.sub.2O.sub.3 Nb.sub.2O.sub.5 0.5 0.0001 0.1 Example 43 Bi.sub.2O.sub.3 WO.sub.3 0.5 0.0001 0.1 Example 44 Bi.sub.2O.sub.3 MoO.sub.3 0.5 0.0001 0.1 Example 45 Bi.sub.2O.sub.3 Nb.sub.2O.sub.5 0.5 0.04 0.0001 Example 46 Bi.sub.2O.sub.3 WO.sub.3 0.5 0.04 0.0001 Example 47 Bi.sub.2O.sub.3 MoO.sub.3 0.5 0.04 0.0001 Example 48 Bi.sub.2O.sub.3 Nb.sub.2O.sub.5 0.5 0.0001 0.0001 Example 49 Bi.sub.2O.sub.3 WO.sub.3 0.5 0.0001 0.0001 Example 50 Bi.sub.2O.sub.3 MoO.sub.3 0.5 0.0001 0.0001
TABLE-US-00008 TABLE 3-2 Specific Sintering Reten- Oxygen Electrical Temper- tion Concen- Relative Resistance ature Time tration Density Value ( C.) (Hours) (% by Volume) (%) ( .Math. cm) Example 39 1400 15 80 97.7 0.029 Example 40 1400 15 80 95.9 0.069 Example 41 1400 15 80 96.9 0.19 Example 42 1400 15 80 94.8 0.021 Example 43 1400 15 80 96.6 0.0096 Example 44 1400 15 80 95.6 0.0092 Example 45 1400 15 80 98.1 0.022 Example 46 1400 15 80 97.6 0.0066 Example 47 1400 15 80 97.7 0.0077 Example 48 1400 15 80 95.5 0.0099 Example 49 1400 15 80 97.3 0.0074 Example 50 1400 15 80 97.4 0.009
TABLE-US-00009 TABLE 3-3 X-Ray Diffraction Peak Position (Degrees) ZnO (101) Zn2SnO4 (311) SnO2 (101) Example 39 34.40 33.89 Example 40 34.35 33.90 Example 41 34.39 33.86 Example 42 34.32 33.89 Example 43 34.34 33.87 Example 44 34.39 33.90 Example 45 34.36 33.86 Example 46 34.42 33.88 Example 47 34.34 33.90 Example 48 34.35 33.88 Example 49 34.41 33.87 Example 50 34.33 33.88
Comparative Example 1
[0101] A SnZnO-based oxide sintered body according to Comparative Example 1 was obtained in the same way as Example 1 except that the formulation was carried out so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.05.
[0102] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 1 in the same way as Example 1, the diffraction peaks of only the wurtzite-type ZnO phase and the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the ZnO (101) plane was 36.24 degrees and the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.33 degrees, meaning that the diffraction peak position of the ZnO (101) plane deviated from the normal position. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 88.0% and the specific electrical resistance value was 500 .Math.cm, meaning that the characteristics did not satisfy the conditions of a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 2
[0103] A SnZnO-based oxide sintered body according to Comparative Example 2 was obtained in the same way as Example 1 except that the formulation was carried out so that Sn and Zn would have an atomic ratio of Sn/(Sn+Zn) being 0.95.
[0104] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 2 in the same way as Example 1, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.33 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.92 degrees, meaning that the diffraction peak position of the SnO.sub.2 (101) plane deviated from the normal position. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 86.0% and the specific electrical resistance value was 700 .Math.cm, meaning that the characteristics did not satisfy the conditions of a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 3
[0105] A SnZnO-based oxide sintered body according to Comparative Example 3 was obtained in the same way as Example 1 except that the oxygen concentration inside the furnace was 68% by volume during the sintering at 1400 C.
[0106] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 3, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.39 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.93 degrees, meaning that the diffraction peak position of the SnO.sub.2 (101) plane deviated from the normal position. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 87.3% and the specific electrical resistance value was 53000 .Math.cm, meaning that the characteristics did not satisfy the conditions of a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 4
[0107] A SnZnO-based oxide sintered body according to Comparative Example 4 was obtained in the same way as Example 1 except that the sintering temperature was 1170 C.
[0108] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 4, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.29 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.88 degrees, meaning that the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane deviated from the normal position. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 82.2% and the specific electrical resistance value was 61000 .Math.cm, meaning that the characteristics did not satisfy the conditions of a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 5
[0109] A SnZnO-based oxide sintered body according to Comparative Example 5 was obtained in the same way as Example 1 except that the sintering temperature was 1500 C.
[0110] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 5, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.34 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.95 degrees, meaning that the diffraction peak position of the SnO.sub.2 (101) plane deviated from the normal position. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 88.6% and the specific electrical resistance value was 6 .Math.cm, meaning that the characteristics did not satisfy the conditions of a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 6
[0111] A SnZnO-based oxide sintered body according to Comparative Example 6 was obtained in the same way as Example 1 except that the retention time for sintering at 1400 C. was 8 hours.
[0112] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 6, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.33 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.83 degrees, meaning that the diffraction peak position of the SnO.sub.2 (101) plane deviated from the normal position. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 80.6% and the specific electrical resistance value was 800000 .Math.cm, meaning that the characteristics did not satisfy the conditions of a relative density of 90% or more and a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 7
[0113] A SnZnO-based oxide sintered body according to Comparative Example 7 was obtained in the same way as Example 1 except that the formulation was carried out so that the second additional element X would have an atomic ratio of Ta/(Sn+Zn+Bi+Ta) being 0.00009.
[0114] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 7, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.30 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.84 degrees, meaning that both the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane deviated from the normal diffraction peak positions. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 98.3% and the specific electrical resistance value was 120 .Math.cm, meaning that the characteristics satisfied the condition of a relative density of 90% or more but the characteristics did not satisfy the condition of a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 8
[0115] A SnZnO-based oxide sintered body according to Comparative Example 8 was obtained in the same way as Example 1 except that the formulation was carried out so that the second additional element X would have an atomic ratio of Ta/(Sn+Zn+Bi+Ta) being 0.15.
[0116] Then, when X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 8, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.37 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.88 degrees, both of which were the normal diffraction peak positions. However, a diffraction peak of the Ta.sub.2O.sub.5 phase was measured in addition to the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 94.4% and the specific electrical resistance value was 86 .Math.cm, meaning that the characteristics satisfied the condition of a relative density of 90% or more but the characteristics did not satisfy the condition of a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 9
[0117] A SnZnO-based oxide sintered body according to Comparative Example 9 was obtained in the same way as Example 1 except that the formulation was carried out so that the first additional element M would have an atomic ratio of Bi/(Sn+Zn+Bi+Ta) being 0.00009.
[0118] When X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 9, the diffraction peaks of only the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure were measured, and the diffraction peaks of different compound phases were not measured. However, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.26 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.85 degrees, meaning that both the Zn.sub.2SnO.sub.4 (311) plane and the SnO.sub.2 (101) plane deviated from the normal diffraction peak positions. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 86.7% and the specific electrical resistance value was 0.13 .Math.cm, meaning that the characteristics satisfied the condition of a specific electrical resistance of 1 .Math.cm or less but the characteristics did not satisfy the condition of a relative density of 90% or more. Table 4-1, Table 4-2, and Table 4-3 show the results.
Comparative Example 10
[0119] A SnZnO-based oxide sintered body according to Comparative Example 10 was obtained in the same way as Example 1 except that the formulation was carried out so that the first additional element M would have an atomic ratio of Bi/(Sn+Zn+Bi+Ta) being 0.05.
[0120] Then, when X-ray diffraction analysis was carried out on the SnZnO-based oxide sintered body according to Comparative Example 10, the diffraction peak position of the Zn.sub.2SnO.sub.4 (311) plane was 34.36 degrees and the diffraction peak position of the SnO.sub.2 (101) plane was 33.89 degrees, both of which were the normal diffraction peak positions. However, a diffraction peak of other unidentifiable compound phase was measured in addition to the Zn.sub.2SnO.sub.4 phase of a spinel type crystal structure and the SnO.sub.2 phase of a rutile-type crystal structure. In addition, in the measurement of the relative density and the specific electrical resistance value, the relative density was 97.2% and the specific electrical resistance value was 4700 .Math.cm, meaning that the characteristics satisfied the condition of a relative density of 90% or more but the characteristics did not satisfy the condition of a specific electrical resistance of 1 .Math.cm or less. Table 4-1, Table 4-2, and Table 4-3 show the results.
TABLE-US-00010 TABLE 4-1 First Second Additional Additional Atomic Ratio Element M Element X Sn/(Sn + Zn) M/(Sn + Zn + M + X) X/Sn + Zn + M + X) Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.05 0.001 0.001 Example 1 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.95 0.001 0.001 Example 2 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.001 Example 3 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.001 Example 4 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.001 Example 5 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.001 Example 6 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.00009 Example 7 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.001 0.15 Example 8 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.00009 0.001 Example 9 Comparative Bi.sub.2O.sub.3 Ta.sub.2O.sub.5 0.5 0.05 0.001 Example 10
TABLE-US-00011 TABLE 4-2 Specific Sintering Reten- Oxygen Electrical Temper- tion Concen- Relative Resistance ature Time tration Density Value ( C.) (Hours) (% by Volume) (%) ( .Math. cm) Comparative 1400 15 80 88.0 500 Example 1 Comparative 1400 15 80 86.0 700 Example 2 Comparative 1400 15 68 87.3 53000 Example 3 Comparative 1170 15 80 82.2 61000 Example 4 Comparative 1500 15 80 88.6 6 Example 5 Comparative 1400 8 80 80.6 800000 Example 6 Comparative 1400 15 80 98.3 120 Example 7 Comparative 1400 15 80 94.4 86 Example 8 Comparative 1400 15 80 86.7 0.13 Example 9 Comparative 1400 15 80 97.2 4700 Example 10
TABLE-US-00012 TABLE 4-3 X-Ray Diffraction Peak Position (Degrees) ZnO (101) Zn2SnO4 (311) SnO2 (101) Comparative 36.24 34.33 Example 1 Comparative 34.33 33.92 Example 2 Comparative 34.39 33.93 Example 3 Comparative 34.29 33.88 Example 4 Comparative 34.34 33.95 Example 5 Comparative 34.33 33.83 Example 6 Comparative 34.30 33.84 Example 7 Comparative 34.37 33.88 Example 8 Comparative 34.26 33.85 Example 9 Comparative 34.36 33.89 Example 10
POSSIBILITY OF INDUSTRIAL APPLICATION
[0121] The SnZnO-based oxide sintered body according to the present invention has characteristics such as a high density and a low resistance in addition to a mechanical strength, and thus has industrial applicability where it is applied to a sputtering target for forming a transparent electrode such as a solar cell and a touch panel.