JP4526861B2 - Zinc based complex oxide - Google Patents
Zinc based complex oxide Download PDFInfo
- Publication number
- JP4526861B2 JP4526861B2 JP2004128038A JP2004128038A JP4526861B2 JP 4526861 B2 JP4526861 B2 JP 4526861B2 JP 2004128038 A JP2004128038 A JP 2004128038A JP 2004128038 A JP2004128038 A JP 2004128038A JP 4526861 B2 JP4526861 B2 JP 4526861B2
- Authority
- JP
- Japan
- Prior art keywords
- hours
- zinc
- oxide
- purity
- mobility
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011701 zinc Substances 0.000 title claims description 109
- 229910052725 zinc Inorganic materials 0.000 title claims description 78
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 77
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 43
- 239000002131 composite material Substances 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 19
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 16
- 150000002602 lanthanoids Chemical class 0.000 claims description 16
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 229910052706 scandium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 61
- 239000000203 mixture Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002202 Polyethylene glycol Substances 0.000 description 30
- 229920001223 polyethylene glycol Polymers 0.000 description 30
- 238000009694 cold isostatic pressing Methods 0.000 description 29
- 239000011812 mixed powder Substances 0.000 description 29
- 239000004570 mortar (masonry) Substances 0.000 description 29
- 238000000465 moulding Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000002156 mixing Methods 0.000 description 23
- 238000013329 compounding Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000011135 tin Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000002772 conduction electron Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 2
- 229940075624 ytterbium oxide Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Silicon Compounds (AREA)
Description
本発明は、亜鉛系複合酸化物に関する。 The present invention relates to a zinc-based composite oxide.
酸化亜鉛（ＺｎＯ）は、古くからセンサー、透明導電体、表面弾性波素子として利用されている材料であり、近年においても、原料が豊富で安価なこと等から用途開発が盛んに行われている。最近では、透明電界トランジスターや希薄磁性半導体及び熱電変換材料としての研究開発も盛んである。 Zinc oxide (ZnO) is a material that has been used as a sensor, a transparent conductor, and a surface acoustic wave device for a long time. In recent years, its application has been actively developed because it is abundant and inexpensive. . Recently, research and development as a transparent field transistor, a diluted magnetic semiconductor, and a thermoelectric conversion material are also active.
酸化亜鉛をこれらの分野に応用する場合、電子の移動度を上げることは性能向上のために必須のことである。例えば、トランジスターにおいては、そのスイッチング周波数を高めるために高移動度とする必要がある。
また、酸化亜鉛に透明導電性を付与するためには、少ない伝導電子数とすることで透明性を上げ、また、移動度を増加させることで導電性を確保することが望ましい。
さらに、熱電変換材料においては、熱電変換性能を向上させるために熱起電力と電気伝導度の両方を上げることが望ましいが、酸化亜鉛のような縮退型半導体では、一般に電気伝導度を上げるために伝導電子の数を増やすと、熱起電力が低下してしまう。従って、熱起電力を下げないで電気伝導度を向上させるには、移動度を増加させる必要がある。
When applying zinc oxide to these fields, increasing the mobility of electrons is essential for improving the performance. For example, a transistor needs to have high mobility in order to increase its switching frequency.
In addition, in order to impart transparent conductivity to zinc oxide, it is desirable to increase transparency by setting the number of conduction electrons to be small and to ensure conductivity by increasing mobility.
Furthermore, in thermoelectric conversion materials, it is desirable to increase both thermoelectromotive force and electrical conductivity in order to improve thermoelectric conversion performance, but degenerate semiconductors such as zinc oxide generally increase electrical conductivity. Increasing the number of conduction electrons decreases the thermoelectromotive force. Therefore, to improve the electrical conductivity without lowering the thermoelectromotive force, it is necessary to increase the mobility.
導電性酸化亜鉛の製造方法としては、例えば、特許文献１−６に開示されている様に、酸化亜鉛粉末に、活性化剤としてアルミニウム、ガリウム、インジウム等の金属の酸化物を添加混合し、還元性雰囲気下で６００〜１，２００℃の温度において加熱焼成する方法が知られている。
しかし、これらの方法は、いずれも伝導電子を増加させて導電性を向上させる方法であり、移動度を向上させる方法としては役立たない。
一方、酸化亜鉛の移動度を向上させるには、結晶の欠陥を少なくするため、多結晶体を単結晶化させることが通常行われるが、酸化亜鉛を単結晶化するには、多くのエネルギーと時間が必要となる。
However, any of these methods is a method for improving conductivity by increasing conduction electrons and is not useful as a method for improving mobility.
On the other hand, in order to improve the mobility of zinc oxide, a polycrystal is usually made into a single crystal in order to reduce crystal defects. However, in order to make a single crystal of zinc oxide, much energy and Time is needed.
本発明は、上記事情に鑑みなされたものであり、多結晶体であっても移動度が大きな亜鉛系複合酸化物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a zinc-based composite oxide having a high mobility even if it is a polycrystalline body.
上記目的を達成するため、本発明者等は鋭意検討を重ねた結果、亜鉛と、特定の金属元素を、特定のモル比で含む亜鉛系複合酸化物の移動度が大きくなることを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors have conducted extensive studies and found that the mobility of zinc-based composite oxide containing zinc and a specific metal element in a specific molar ratio is increased. Completed the invention.
本発明によれば、以下の亜鉛系複合酸化物等が提供される。
１．亜鉛、及び
ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素、
の複合酸化物からなり、亜鉛と第一の金属元素のモル比が１：０．０００１〜０．５である亜鉛系複合酸化物。
２．亜鉛、
ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素、及び
Ｍｇ、Ｓｉ、Ｃａ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｒｈから選ばれる少なくとも一種の第二の金属元素、
の複合酸化物からなり、亜鉛、第一の金属元素及び第二の金属元素のモル比が１：０．０００１〜０．５：０．０００１〜０．３である亜鉛系複合酸化物。
３．移動度が４０ｃｍ２／Ｖｓ以上である１又は２に記載の亜鉛系複合酸化物。
４．前記第一の金属元素がランタノイドである１〜３のいずれかに記載の亜鉛系複合酸化物。
５．前記ランタノイドが、Ｃｅ、Ｎｄ、Ｅｕ、Ｇａ、Ｈｏ、Ｅｒ、Ｙｂである１〜４のいずれかに記載の亜鉛系複合酸化物。
６．酸化亜鉛に、ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素を含む材料を、亜鉛と第一の金属元素のモル比が１：０．０００１〜０．５となるように、添加する酸化亜鉛の移動度向上方法。
７．酸化亜鉛に、ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素を含む材料、及びＭｇ、Ｓｉ、Ｃａ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｒｈから選ばれる少なくとも一種の第二の金属元素を含む材料を、亜鉛、第一の金属元素及び第二の金属元素のモル比が１：０．０００１〜０．５：０．０００１〜０．３となるように、添加する酸化亜鉛の移動度向上方法。
８．１〜５のいずれかに記載の亜鉛系複合酸化物からなる熱電変換材料。
According to the present invention, the following zinc-based composite oxide and the like are provided.
1. Zinc, and at least one first metal element selected from lanthanoid, Sn, and Sc,
A zinc-based composite oxide having a molar ratio of zinc to the first metal element of 1: 0.0001 to 0.5.
2. zinc,
At least one first metal element selected from lanthanoid, Sn, Sc, and at least one second metal element selected from Mg, Si, Ca, Mn, Fe, Co, Ni, Mo, Rh,
A zinc-based composite oxide having a molar ratio of zinc, the first metal element, and the second metal element of 1: 0.0001 to 0.5: 0.0001 to 0.3.
3. 3. The zinc-based composite oxide according to 1 or 2, having a mobility of 40 cm 2 / Vs or higher.
4). The zinc-based composite oxide according to any one of 1 to 3, wherein the first metal element is a lanthanoid.
5). The zinc-based composite oxide according to any one of 1 to 4, wherein the lanthanoid is Ce, Nd, Eu, Ga, Ho, Er, or Yb.
6). A material containing at least one first metal element selected from lanthanoid, Sn, and Sc in zinc oxide, so that the molar ratio of zinc to the first metal element is 1: 0.0001 to 0.5. A method for improving the mobility of zinc oxide to be added.
7). A material containing at least one first metal element selected from lanthanoid, Sn, and Sc in zinc oxide, and at least one second selected from Mg, Si, Ca, Mn, Fe, Co, Ni, Mo, and Rh Oxidation to be added so that the molar ratio of zinc, the first metal element and the second metal element is 1: 0.0001 to 0.5: 0.0001 to 0.3 A method for improving the mobility of zinc.
A thermoelectric conversion material comprising the zinc-based composite oxide according to any one of 8.1 to 5.
本発明によれば、多結晶体であっても移動度が大きな亜鉛系複合酸化物が提供できる。 According to the present invention, a zinc-based composite oxide having a high mobility can be provided even if it is a polycrystal.
本発明の亜鉛系複合酸化物は、亜鉛、及びランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素、の複合酸化物である。亜鉛と第一の金属元素のモル比は、１：０．０００１〜０．５、好ましくは１：０．００１〜０．２である。第一の金属元素のモル比がこの範囲より少ないと効果が少なく、この範囲より多いと第一の金属元素の酸化物が散乱原因となり、移動度が逆に低下してしまう。 The zinc-based composite oxide of the present invention is a composite oxide of zinc and at least one first metal element selected from lanthanoids, Sn, and Sc. The molar ratio of zinc to the first metal element is 1: 0.0001 to 0.5, preferably 1: 0.001 to 0.2. If the molar ratio of the first metal element is less than this range, the effect is small, and if it is more than this range, the oxide of the first metal element causes scattering, and the mobility is reduced.
また、本発明の亜鉛系複合酸化物は、亜鉛、ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素、及びＭｇ、Ｓｉ、Ｃａ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｒｈから選ばれる少なくとも一種の第二の金属元素、の複合酸化物である。亜鉛、第一の金属元素及び第二の金属元素のモル比は、１：０．０００１〜０．５：０．０００１〜０．３、好ましくは１：０．００１〜０．２：０．００１〜０．２である。第一及び第二の金属元素のモル比がこの範囲より少ないと効果が少なく、この範囲より多いと第一及び第二の金属元素の酸化物が散乱原因となり、移動度が逆に低下してしまう。 The zinc-based composite oxide of the present invention is composed of at least one first metal element selected from zinc, lanthanoid, Sn, and Sc, and Mg, Si, Ca, Mn, Fe, Co, Ni, Mo, and Rh. It is a composite oxide of at least one second metal element selected. The molar ratio of zinc, the first metal element and the second metal element is 1: 0.0001 to 0.5: 0.0001 to 0.3, preferably 1: 0.001 to 0.2: 0. 001 to 0.2. If the molar ratio of the first and second metal elements is less than this range, the effect is small, and if it exceeds this range, the oxides of the first and second metal elements cause scattering and the mobility decreases conversely. End up.
第一の金属元素のうち、好ましくはランタノイドであり、中でもＣｅ、Ｎｄ、Ｅｕ、Ｇａ、Ｈｏ、Ｅｒ、Ｙｂがより好ましい。 Of the first metal elements, lanthanoids are preferable, and Ce, Nd, Eu, Ga, Ho, Er, and Yb are more preferable.
本発明の亜鉛系複合酸化物は、移動度が、好ましくは４０ｃｍ２／Ｖｓ以上、より好ましくは５０ｃｍ２／Ｖｓ以上である。
尚、本発明において、「移動度」とは電子移動度を意味する。
The mobility of the zinc-based composite oxide of the present invention is preferably 40 cm 2 / Vs or more, more preferably 50 cm 2 / Vs or more.
In the present invention, “mobility” means electron mobility.
本発明の亜鉛系複合酸化物は、亜鉛源に、第一の金属元素を含む材料、又は第一の金属元素を含む材料及び第二の金属元素を含む材料を、上記のモル比となるように添加して、均一に混合し、焼成することにより製造できる。このとき、亜鉛源、第一及び第二の金属元素を含む材料は、粉末等として混合することが好ましい。
第一及び第二の金属元素を含む材料を上記のモル比で添加することにより、酸化亜鉛の移動度を向上させることができる。
In the zinc-based composite oxide of the present invention, the material containing the first metal element or the material containing the first metal element and the material containing the second metal element in the zinc source have the above molar ratio. It can be manufactured by adding to and mixing uniformly and firing. At this time, the zinc source and the material containing the first and second metal elements are preferably mixed as a powder or the like.
By adding the material containing the first and second metal elements in the above molar ratio, the mobility of zinc oxide can be improved.
本発明の亜鉛系複合酸化物の製造に際して用いられる原料としては、各成分元素、各成分元素の酸化物又はその焼成時に酸化物となる原料が使用できる。 本発明では、亜鉛源として、例えば、金属（Ｚｎ）、酸化物（ＺｎＯ）、水酸化物〔Ｚｎ（ＯＨ）２〕、硝酸塩〔Ｚｎ（ＮＯ３）２〕等が用いられる。 As a raw material used in the production of the zinc-based composite oxide of the present invention, each component element, an oxide of each component element, or a raw material that becomes an oxide at the time of firing can be used. In the present invention, for example, metal (Zn), oxide (ZnO), hydroxide [Zn (OH) 2 ], nitrate [Zn (NO 3 ) 2 ] and the like are used as the zinc source.
第一の金属元素のうち、ランタノイドを含む材料としては、Ｃｅ源として、例えば、金属（Ｃｅ）、酸化物（ＣｅＯ２）、炭酸化物〔Ｃｅ２（ＣＯ３）３・８Ｈ２Ｏ〕、硝酸塩〔Ｃｅ（ＮＯ３）３・６Ｈ２Ｏ〕〕、酢酸塩〔（ＣＨ３ＣＯＯ）３Ｃｅ・Ｈ２Ｏ〕等が用いられる。Ｎｄ源としては、例えば、酸化物（Ｎｄ２Ｏ３）、炭酸化物〔Ｎｄ２（ＣＯ３）３〕、硝酸塩〔Ｎｄ（ＮＯ３）３〕等が用いられる。Ｙｂ源としては、例えば、酸化物（Ｙｂ２Ｏ３）、炭酸化物〔Ｙｂ２（ＣＯ３）３〕、硝酸塩〔Ｙｂ（ＮＯ３）３〕等が用いられる。Ｅｕ源としては、例えば、酸化物（Ｅｕ２Ｏ３）等が用いられる。Ｇａ源としては、例えば、酸化物（Ｇａ２Ｏ３）等が用いられる。Ｈｏ源としては、例えば、酸化物（Ｈｏ２Ｏ３）等が用いられる。Ｅｒ源としては、例えば、酸化物（Ｅｒ２Ｏ３）等が用いられる。
また、Ｓｎを含む材料としては、例えば、酸化物（ＳｎＯ）等が用いられる。Ｓｃを含む材料としては、例えば、酸化物（Ｓｃ２Ｏ３）等が用いられる。
Among the first metal elements, the lanthanoid-containing material includes, for example, a metal (Ce), oxide (CeO 2 ), carbonate [Ce 2 (CO 3 ) 3 · 8H 2 O], and nitrate as a Ce source. [Ce (NO 3 ) 3 · 6H 2 O]], acetate [(CH 3 COO) 3 Ce · H 2 O] and the like are used. As the Nd source, for example, oxide (Nd 2 O 3 ), carbonate [Nd 2 (CO 3 ) 3 ], nitrate [Nd (NO 3 ) 3 ] and the like are used. As the Yb source, for example, oxide (Yb 2 O 3 ), carbonate [Yb 2 (CO 3 ) 3 ], nitrate [Yb (NO 3 ) 3 ] and the like are used. For example, an oxide (Eu 2 O 3 ) or the like is used as the Eu source. As the Ga source, for example, an oxide (Ga 2 O 3 ) or the like is used. As the Ho source, for example, an oxide (Ho 2 O 3 ) or the like is used. As the Er source, for example, an oxide (Er 2 O 3 ) or the like is used.
As the material containing Sn, for example, oxide (SnO) or the like is used. As the material containing Sc, for example, an oxide (Sc 2 O 3 ) or the like is used.
第二の金属元素を含む材料としては、Ｍｇ源として、例えば、酸化物（ＭｇＯ）等が、Ｓｉ源として、例えば、酸化物（ＳｉＯ２）等が、Ｃａ源として、例えば、酸化物（ＣａＯ）、水酸化物〔Ｃａ（ＯＨ）２〕等が、Ｍｎ源として、例えば、酸化物（Ｍｎ２Ｏ３）等が、Ｆｅ源として、例えば、酸化物（Ｆｅ２Ｏ３、Ｆｅ３Ｏ４）等が、Ｃｏ源として、例えば、酸化物（Ｃｏ２Ｏ３、Ｃｏ３Ｏ４）等が、Ｎｉ源として、例えば、酸化物（ＮｉＯ）等が、Ｍｏ源として、例えば、酸化物（ＭｏＯ３）等が、Ｒｈ源として、例えば、酸化物（Ｒｈ２Ｏ３）等が、それぞれ用いられる。 Examples of the material containing the second metal element include an Mg source such as an oxide (MgO), an Si source such as an oxide (SiO 2 ), and a Ca source such as an oxide (CaO). ), Hydroxide [Ca (OH) 2 ] and the like as the Mn source, for example, oxide (Mn 2 O 3 ) and the like as the Fe source, for example, oxides (Fe 2 O 3 and Fe 3 O 4). ) Or the like as a Co source, for example, an oxide (Co 2 O 3 , Co 3 O 4 ) or the like, and as a Ni source, for example, an oxide (NiO) or the like as a Mo source, for example, an oxide (MoO) 3 ) and the like are used as the Rh source, for example, an oxide (Rh 2 O 3 ) or the like.
本発明の亜鉛系複合酸化物は、亜鉛及び第一の金属元素、又は亜鉛、第一の金属元素及び第二の金属元素、の複合酸化物であるが、本発明の効果を損なわない範囲で、微量の不純物等を含むことができる。 The zinc-based composite oxide of the present invention is a composite oxide of zinc and the first metal element, or zinc, the first metal element and the second metal element, but within a range not impairing the effects of the present invention. , Trace amounts of impurities and the like.
また、本発明では、亜鉛系複合酸化物の製造に際し、各種添加剤、例えば、ポリエチレングリコール、ポリビニルアルコール、ステアリン酸等を必要に応じて添加することができる。 In the present invention, various additives such as polyethylene glycol, polyvinyl alcohol, stearic acid, and the like can be added as necessary when producing the zinc-based composite oxide.
以下、実施例に基づき本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されない。
実施例１
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１１．７５２ｇ、酸化セリウム（純度９９．９％、平均粒径約０．４μｍ）０．２４８ｇ、及びポリエチレングリコール０．２４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけて冷間等方圧加圧法（ＣＩＰ）成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＣｅのモル比は、Ｚｎ１モルに対してＣｅが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．５４ｇ／ｃｍ３であった。
EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to these Examples.
Example 1
Weigh out 11.752 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.248 g of cerium oxide (purity 99.9%, average particle size of about 0.4 μm), and 0.24 g of polyethylene glycol. After mixing with a mortar, the mixture was pulverized with a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The compact was further subjected to cold isostatic pressing (CIP) molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Ce was 0.01 mol with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.54 g / cm 3 .
得られた焼結体の表面を約１ｍｍ研磨し、３ｍｍ角の角柱とした後、厚さ０．６ｍｍの薄片を切り出してホール係数測定用の試料とした。ホール係数測定のための電極は、薄片の四隅に金スパッタした後、銀ペーストでリード線を接着し形成した。ホール係数測定装置（東洋テクニカ株式会社製ＲｅｓｉＴｅｓｔ８３００）を用い、室温で、キャリア数、移動度、比抵抗（電気伝導度の逆数）を測定した。尚、電気伝導度（σ）、キャリア数（ｎ）、移動度（μ）は、σ＝ｎμｅの関係にあり、ｅは電荷を表す。
結果を表１に示したが、移動度は、焼結体としては非常に高い値が得られ、比較例１のＺｎＯ焼結体に比べ、移動度の大幅な向上が見られた。
The surface of the obtained sintered body was polished by about 1 mm to form a 3 mm square prism, and then a 0.6 mm thick slice was cut out to obtain a sample for Hall coefficient measurement. Electrodes for measuring the Hall coefficient were formed by sputtering gold at the four corners of a thin piece and then bonding the lead wire with silver paste. The number of carriers, mobility, and specific resistance (reciprocal of electrical conductivity) were measured at room temperature using a Hall coefficient measuring device (ResiTest 8300 manufactured by Toyo Technica Co., Ltd.). The electrical conductivity (σ), the number of carriers (n), and the mobility (μ) are in a relationship of σ = nμe, and e represents electric charge.
The results are shown in Table 1. As for the mobility, a very high value was obtained for the sintered body, and the mobility was significantly improved as compared with the ZnO sintered body of Comparative Example 1.
実施例２
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．５９４ｇ、酸化セリウム（純度９９．９％、平均粒径約０．４μｍ）０．４０６ｇ、及びポリエチレングリコール０．２ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＣｅのモル比は、Ｚｎ１モルに対してＣｅが０．０１９モルであり、配合比とほぼ等しかった。また、密度は５．６５ｇ／ｃｍ３であった。ホール係数測定装置による移動度、キャリア数及び電気伝導度の測定は、実施例１と同様に行った。以下の実施例及び比較例についても同様である。
結果を表１に示したが、移動度は、焼結体としては非常に高い値が得られ、比較例１のＺｎＯ焼結体に比べ、移動度の大幅な向上が見られた。
Example 2
Weigh 9.594 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.406 g of cerium oxide (purity 99.9%, average particle size of about 0.4 μm), and 0.2 g of polyethylene glycol. After mixing with a mortar, the mixture was pulverized with a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of compositional analysis of the obtained sintered body, the molar ratio of Zn and Ce was 0.019 mol of Ce with respect to 1 mol of Zn, which was almost equal to the blending ratio. The density was 5.65 g / cm 3 . The measurement of the mobility, the number of carriers, and the electrical conductivity using the Hall coefficient measuring device was performed in the same manner as in Example 1. The same applies to the following examples and comparative examples.
The results are shown in Table 1. As for the mobility, a very high value was obtained for the sintered body, and the mobility was significantly improved as compared with the ZnO sintered body of Comparative Example 1.
実施例３
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．０４４ｇ、酸化セリウム（純度９９．９％、平均粒径約０．４μｍ）０．９５６ｇ、及びポリエチレングリコール０．２ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＣｅのモル比は、Ｚｎ１モルに対してＣｅが０．０４９モルであり、配合比とほぼ等しかった。また、密度は５．７０ｇ／ｃｍ３であった。
結果を表１に示したが、移動度は、焼結体としては非常に高い値が得られ、比較例１のＺｎＯ焼結体に比べ、移動度の大幅な向上が見られた。
Example 3
Weighed 9.044 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.956 g of cerium oxide (purity 99.9%, average particle size of about 0.4 μm), and 0.2 g of polyethylene glycol. After mixing with a mortar, the mixture was pulverized with a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Ce was 0.049 mol of Ce with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.70 g / cm 3 .
The results are shown in Table 1. As for the mobility, a very high value was obtained for the sintered body, and the mobility was significantly improved as compared with the ZnO sintered body of Comparative Example 1.
実施例４
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．８８６ｇ、酸化ネオジウム（純度９９．９％）０．１１４ｇ、及びポリエチレングリコール０．２ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＮｄのモル比は、Ｚｎ１モルに対してＮｄが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．５６ｇ／ｃｍ３であった。
結果を表１に示したが、移動度は、焼結体としては非常に高い値が得られ、比較例１のＺｎＯ焼結体に比べ、移動度の大幅な向上が見られた。
Example 4
9.886 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.114 g of neodymium oxide (purity 99.9%), and 0.2 g of polyethylene glycol were weighed and mixed in a mortar, then the planet The mixture was pulverized for 2 hours with a ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Nd was 0.009 mol of Nd with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.56 g / cm 3 .
The results are shown in Table 1. As for the mobility, a very high value was obtained for the sintered body, and the mobility was significantly improved as compared with the ZnO sintered body of Comparative Example 1.
実施例５
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．７６３ｇ、酸化イッテルビウム（純度９９．９％）０．２３７ｇ、及びポリエチレングリコール０．２ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＹｂのモル比は、Ｚｎ１モルに対してＹｂが０．０１モルであり、配合比と等しかった。また、密度は５．６７ｇ／ｃｍ３であった。
結果を表１に示したが、移動度は焼結体としては非常に高い値が得られ、比較例１のＺｎＯ焼結体に比べ、移動度の大幅な向上が見られた。
Example 5
Zinc oxide powder (purity 99.9%, average particle size of about 2 μm) 9.763 g, ytterbium oxide (purity 99.9%) 0.237 g, and polyethylene glycol 0.2 g were weighed and mixed in a mortar, and then planets The mixture was pulverized for 2 hours with a ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Yb was 0.01 mol with respect to 1 mol of Zn, which was equal to the compounding ratio. The density was 5.67 g / cm 3 .
The results are shown in Table 1. As for the mobility, a very high value was obtained for the sintered body, and the mobility was significantly improved as compared with the ZnO sintered body of Comparative Example 1.
比較例１
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１０ｇ、ポリエチレングリコール０．２ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。得られた焼結体の密度は５．５４ｇ／ｃｍ３であった。結果を表１に示す。
Comparative Example 1
10 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and 0.2 g of polyethylene glycol were weighed and mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours. The density of the obtained sintered body was 5.54 g / cm 3 . The results are shown in Table 1.
比較例２
酸化亜鉛粉（純度９９．９％，平均粒径約２μｍ）１９．９０１ｇ、酸化マグネシウム（純度９９．９％）０．０９９ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＭｇのモル比は、Ｚｎ１モルに対してＭｇが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．５３ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は比較的小さく、比較例１のＺｎＯ焼結体とほぼ同等であり、キャリヤー数も少ないため、電気伝導性は向上しなかった。
Comparative Example 2
Zinc oxide powder (purity 99.9%, average particle size about 2 μm) 19.901 g, magnesium oxide (purity 99.9%) 0.099 g, and polyethylene glycol 0.4 g were weighed and mixed in a mortar, and then planets The mixture was pulverized for 2 hours with a ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn and Mg was 0.009 mol of Mg with respect to 1 mol of Zn, which was almost equal to the blending ratio. The density was 5.53 g / cm 3 .
The results are shown in Table 2. The mobility was relatively small, almost the same as that of the ZnO sintered body of Comparative Example 1, and the number of carriers was small, so the electrical conductivity was not improved.
実施例６
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．１８ｇ及び酸化マグネシウム（純度９９．９％）０．０９５ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７８７ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｍｇ、Ｃｅのモル比は、Ｚｎ１モルに対してＭｇが０．００９モル、Ｃｅが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．４５ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例２のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 6
0.787 g of cerium acetate monohydrate was added as a Ce source to 19.18 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and magnesium oxide (purity 99.9%) 0.095 g, To this, 0.4 g of polyethylene glycol was weighed and added, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn, Mg, and Ce was 0.009 mol of Mg and 0.01 mol of Ce with respect to 1 mol of Zn, which was almost equal to the blending ratio. The density was 5.45 g / cm 3 .
The results are shown in Table 2. It was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 2.
比較例３
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．８５３ｇ、二酸化ケイ素（純度９９．９％）０．１４７ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＳｉのモル比は、Ｚｎ１モルに対してＳｉが０．０１モルであり、配合比と等しかった。また、密度は４．８９ｇ／ｃｍ３と非常に小さかった。
結果を表２に示したが、移動度は極めて小さく、キャリヤー数も少ないため、電気伝導性は向上しなかった。
Comparative Example 3
Zinc oxide powder (purity 99.9%, average particle size about 2 μm) 19.853 g, silicon dioxide (purity 99.9%) 0.147 g and polyethylene glycol 0.4 g were weighed and mixed in a mortar, then The mixture was pulverized for 2 hours with a ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Si was 0.01 mole of Si with respect to 1 mole of Zn, which was equal to the blending ratio. Further, the density was very small as 4.89 g / cm 3 .
The results are shown in Table 2. As the mobility was extremely small and the number of carriers was small, the electrical conductivity was not improved.
実施例７
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．０７４ｇ及び酸化ケイ素（純度９９．９％）０．１４１ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７８６ｇ加え、これにポリエチレングリコール０．４ｇを秤量し加えて乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｓｉ、Ｃｅのモル比は、Ｚｎ１モルに対してＳｉが０．０１モル、Ｃｅが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．２９ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例３のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 7
Add 0.786 g of cerium acetate monohydrate as Ce source to 19.074 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and 0.141 g of silicon oxide (purity 99.9%), 0.4 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of compositional analysis of the obtained sintered body, the molar ratio of Zn, Si, and Ce was 0.01 mol of Si and 0.01 mol of Ce with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.29 g / cm 3 .
The results are shown in Table 2, and it was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 3.
比較例４
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．８３９ｇ、水酸化カルシウム（純度９９．９％）０．１６１ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＣａのモル比は、Ｚｎ１モルに対してＣａが０．０１モルであり、配合比と等しかった。また、密度は５．５３ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は極めて小さい値であった。
Comparative Example 4
After weighing 19.839 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.161 g of calcium hydroxide (purity 99.9%) and 0.4 g of polyethylene glycol, they were mixed in a mortar, The mixture was pulverized for 2 hours using a planetary ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn and Ca was 0.01 mol of Ca with respect to 1 mol of Zn, which was equal to the blending ratio. The density was 5.53 g / cm 3 .
The results are shown in Table 2, and the mobility was extremely small.
実施例８
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．０６０ｇ及び水酸化カルシウム（純度９９．９％）０．１５５ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７８５ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｃａ、Ｃｅのモル比は、Ｚｎ１モルに対してＣａが０．０１モル、Ｃｅが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．４４ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例４のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 8
Add 0.785 g of cerium acetate monohydrate as Ce source to 19.060 g of zinc oxide powder (purity 99.9%, average particle size about 2 μm) and calcium hydroxide (purity 99.9%) 0.155 g Then, 0.4 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn, Ca, and Ce was 0.01 mol of Ca and 0.01 mol of Ce with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.44 g / cm 3 .
The results are shown in Table 2, and it was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 4.
比較例５
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．９０４ｇ、酸化マンガン（Ｍｎ２Ｏ３、純度９９．９％）０．０９６ｇ、及びポリエチレングリコール０．２ｇを秤量し、乳鉢で混合した後、遊星ボールミルで３時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＭｎのモル比は、Ｚｎ１モルに対してＭｎが０．０１モルであり、配合比と等しかった。また、密度は５．２８ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は極めて小さい値であった。
Comparative Example 5
Weigh 9.904 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.096 g of manganese oxide (Mn 2 O 3 , purity 99.9%), and 0.2 g of polyethylene glycol in a mortar. After mixing, the mixture was pulverized by a planetary ball mill for 3 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the compositional analysis of the obtained sintered body, the molar ratio of Zn and Mn was 0.01 mol with respect to 1 mol of Zn, which was equal to the compounding ratio. The density was 5.28 g / cm 3 .
The results are shown in Table 2, and the mobility was extremely small.
実施例９
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．５１６ｇ及び酸化マンガン（Ｍｎ２Ｏ３、純度９９．９％）０．０９２ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．３９２ｇ加え、これにポリエチレングリコール０．２ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｍｎ、Ｃｅのモル比は、Ｚｎ１モルに対してＭｎが０．０１モル、Ｃｅが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．３８ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例５のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 9
To 9.516 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and 0.092 g of manganese oxide (Mn 2 O 3 , purity 99.9%), cerium acetate monohydrate was added as a Ce source. 0.392 g was added, 0.2 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn, Mn, and Ce was 0.01 mole of Mn and 0.009 mole of Ce with respect to 1 mole of Zn, which was almost equal to the blending ratio. The density was 5.38 g / cm 3 .
The results are shown in Table 2. It was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 5.
比較例６
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．８０６ｇ、酸化鉄（Ｆｅ２Ｏ３、純度９９．９％）０．１９４ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＦｅのモル比は、Ｚｎ１モルに対してＦｅが０．０１モルであり、配合比と等しかった。また、密度は５．６３ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は極めて小さい値であった。
Comparative Example 6
Weigh 19.806 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.194 g of iron oxide (Fe 2 O 3 , purity 99.9%), and 0.4 g of polyethylene glycol in a mortar. After mixing, the mixture was pulverized by a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the compositional analysis of the obtained sintered body, the molar ratio of Zn and Fe was 0.01 mole of Fe with respect to 1 mole of Zn, which was equal to the blending ratio. The density was 5.63 g / cm 3 .
The results are shown in Table 2, and the mobility was extremely small.
実施例１０
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．０２９ｇ及び酸化鉄（Ｆｅ２Ｏ３、純度９９．９％）０．１８７ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７２４ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｆｅ、Ｃｅのモル比は、Ｚｎ１モルに対してＦｅが０．０１モル、Ｃｅが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．５０ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例６のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 10
To 19.029 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and 0.187 g of iron oxide (Fe 2 O 3 , purity 99.9%), further cerium acetate monohydrate as a Ce source. 0.724 g was added, 0.4 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the compositional analysis of the obtained sintered body, the molar ratio of Zn, Fe, and Ce was 0.01 mole Fe and 0.009 mole Ce with respect to 1 mole Zn, which was almost equal to the blending ratio. The density was 5.50 g / cm 3 .
The results are shown in Table 2, and it was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 6.
比較例７
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．７９８ｇ、酸化コバルト（Ｃｏ２Ｏ３、純度９９．９％）０．２０２ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＣｏのモル比は、Ｚｎ１モルに対してＣｏが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．５４ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は小さい値であった。
Comparative Example 7
Weigh 19.798 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.202 g of cobalt oxide (Co 2 O 3 , purity 99.9%), and 0.4 g of polyethylene glycol in a mortar. After mixing, the mixture was pulverized for 2 hours using a planetary ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn and Co was 0.009 mol of Co with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.54 g / cm 3 .
The results are shown in Table 2, and the mobility was a small value.
実施例１１
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．０２９ｇ及び酸化コバルト（Ｃｏ２Ｏ３、純度９９．９％）０．１９４ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７８４ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｃｏ、Ｃｅのモル比は、Ｚｎ１モルに対してＣｏが０．０１モル、Ｃｅが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．４４ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例７のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 11
To 19.029 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and 0.194 g of cobalt oxide (Co 2 O 3 , purity 99.9%), further cerium acetate monohydrate as a Ce source. 0.784 g was added, 0.4 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of compositional analysis of the obtained sintered body, the molar ratio of Zn, Co, and Ce was 0.01 mol of Co and 0.009 mol of Ce with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.44 g / cm 3 .
The results are shown in Table 2. It was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 7.
比較例８
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．８１８ｇ、酸化ニッケル（ＮｉＯ、純度９９．９％）０．１８２ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＮｉのモル比は、Ｚｎ１モルに対してＮｉが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．５９ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は小さい値であった。
Comparative Example 8
After weighing 19.818 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), 0.182 g of nickel oxide (NiO, purity 99.9%), and 0.4 g of polyethylene glycol, and mixing them in a mortar The mixture was pulverized with a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Ni was 0.01 mol with respect to 1 mol of Zn, and was almost equal to the blending ratio. The density was 5.59 g / cm 3 .
The results are shown in Table 2, and the mobility was a small value.
実施例１２
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．０４１ｇ及び酸化ニッケル（ＮｉＯ、純度９９．９％）０．１７５ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７８４ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｎｉ、Ｃｅのモル比は、Ｚｎ１モルに対してＮｉが０．０１モル、Ｃｅが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．４６ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例８のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 12
Zinc oxide powder (purity 99.9%, average particle size about 2 μm) 19.041 g and nickel oxide (NiO, purity 99.9%) 0.175 g, and further 0.784 g of cerium acetate monohydrate as Ce source In addition, 0.4 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the compositional analysis of the obtained sintered body, the molar ratio of Zn, Ni, and Ce was 0.01 mol of Ni and 0.009 mol of Ce with respect to 1 mol of Zn. The density was 5.46 g / cm 3 .
The results are shown in Table 2. It was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 8.
比較例９
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．６５２ｇ、酸化モリブデン（純度９９．９％）０．３４８ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＭｏのモル比は、Ｚｎ１モルに対してＭｏが０．００８モルであり、配合比とほぼ等しかった。また、密度は５．１８ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は小さい値であった。
Comparative Example 9
Zinc oxide powder (purity 99.9%, average particle size about 2 μm) 19.652 g, molybdenum oxide (purity 99.9%) 0.348 g, and polyethylene glycol 0.4 g were weighed and mixed in a mortar, and then planets The mixture was pulverized for 2 hours with a ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn and Mo was 0.008 mol of Mo with respect to 1 mol of Zn, which was almost equal to the blending ratio. The density was 5.18 g / cm 3 .
The results are shown in Table 2, and the mobility was a small value.
実施例１３
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１８．８８８ｇ及び酸化モリブデン（純度９９．９％）０．３３４ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７７８ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｍｏ、Ｃｅのモル比は、Ｚｎ１モルに対してＭｏが０．００９モル、Ｃｅが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．０８ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例９のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 13
0.778 g of cerium acetate monohydrate was added as a Ce source to 18.888 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and molybdenum oxide (purity 99.9%) 0.334 g, To this, 0.4 g of polyethylene glycol was weighed and added, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn, Mo, and Ce was 0.009 mol of Mo and 0.01 mol of Ce with respect to 1 mol of Zn, which was almost equal to the blending ratio. The density was 5.08 g / cm 3 .
The results are shown in Table 2. It was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 9.
比較例１０
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．６９３ｇ、酸化ロジウム（Ｒｈ２Ｏ３、純度９９．９％）０．３０７ｇ、及びポリエチレングリコール０．４ｇを秤量し、乳鉢で混合した後、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、ＺｎとＲｈのモル比は、Ｚｎ１モルに対してＲｈが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．５５ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は小さい値であった。
Comparative Example 10
Weigh 19.693 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm), rhodium oxide (Rh 2 O 3 , purity 99.9%) 0.307 g, and 0.4 g of polyethylene glycol in a mortar. After mixing, the mixture was pulverized for 2 hours using a planetary ball mill. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of compositional analysis of the obtained sintered body, the molar ratio of Zn and Rh was 0.009 mol of Rh with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.55 g / cm 3 .
The results are shown in Table 2, and the mobility was a small value.
実施例１４
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１８．９２５ｇ及び酸化ロジウム（Ｒｈ２Ｏ３、純度９９．９％）０．２９５ｇに、さらにＣｅ源として酢酸セリウム１水和物を０．７８０ｇ加え、これにポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｒｈ、Ｃｅのモル比は、Ｚｎ１モルに対してＲｈが０．０１モル、Ｃｅが０．００９モルであり、配合比とほぼ等しかった。また、密度は５．４２ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例１０のＣｅ無添加試料に較べて大きく増大していることが明らかになった。
Example 14
To 18.925 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and rhodium oxide (Rh 2 O 3 , purity 99.9%) 0.295 g, further cerium acetate monohydrate as a Ce source. 0.780 g was added, 0.4 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn, Rh, and Ce was 0.01 mol and 0.19 mol of Ce with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.42 g / cm 3 .
The results are shown in Table 2, and it was revealed that the mobility was greatly increased as compared with the Ce-free sample of Comparative Example 10.
実施例１５
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．６７２ｇ及び酸化マンガン（Ｍｎ２Ｏ３、純度９９．９％）０．０９４ｇに、さらに酸化イッテルビウム（Ｙｂ２Ｏ３、純度９９．９％）０．２３４ｇを加え、これにポリエチレングリコール０．２ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで３時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｍｎ、Ｙｂのモル比は、Ｚｎ１モルに対してＭｎが０．０１モル、Ｙｂが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．４２ｇ／ｃｍ３であった。
結果を表２に示したが、移動度は、比較例５のＹｂ無添加試料に較べて大きく増大していることが明らかになった。
Example 15
Zinc oxide powder (purity 99.9%, average particle size about 2 μm) 9.672 g and manganese oxide (Mn 2 O 3 , purity 99.9%) 0.094 g, and further ytterbium oxide (Yb 2 O 3 , purity 99 .9%) 0.234 g was added, 0.2 g of polyethylene glycol was weighed and added thereto, mixed in a mortar, and then mixed and ground in a planetary ball mill for 3 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the compositional analysis of the obtained sintered body, the molar ratio of Zn, Mn, and Yb was 0.01 mole of Mn and 0.01 mole of Yb with respect to 1 mole of Zn, which was almost equal to the blending ratio. The density was 5.42 g / cm 3 .
The results are shown in Table 2, and it was revealed that the mobility was greatly increased as compared with the Yb-free sample of Comparative Example 5.
実施例１６
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．６７４ｇ及び酸化錫（ＳｎＯ、純度９９．９％）０．３２６ｇに、ポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｓｎのモル比は、Ｚｎ１モルに対してＳｎが０．０１モルであり、配合比とほぼ等しかった。また、密度は５．６７ｇ／ｃｍ３であった。
結果を表３に示したが、移動度は、比較例１のＺｎＯ焼結体に較べて大きく増大していることが明らかになった。
Example 16
To 19.674 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and tin oxide (SnO, purity 99.9%) 0.326 g, weigh 0.4 g of polyethylene glycol and add in a mortar. Then, the mixture was pulverized by a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Sn was 0.01 mol with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.67 g / cm 3 .
The results are shown in Table 3, and it was revealed that the mobility was greatly increased as compared with the ZnO sintered body of Comparative Example 1.
実施例１７
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１８．７５８ｇ及び酸化錫（ＳｎＯ、純度９９．９％）１．２４２ｇに、ポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｓｎのモル比は、Ｚｎ１モルに対してＳｎが０．０３８モルであり、配合比とほぼ等しかった。また、密度は５．７３ｇ／ｃｍ３であった。
結果を表３に示したが、移動度は、比較例１のＺｎＯ焼結体に較べて大きく増大していることが明らかになった。
Example 17
Weighing and adding 0.4 g of polyethylene glycol to 18.758 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and 1.242 g of tin oxide (SnO, purity 99.9%), and mixing in a mortar Then, the mixture was pulverized by a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Sn was 0.038 mol of Sn with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.73 g / cm 3 .
The results are shown in Table 3, and it was revealed that the mobility was greatly increased as compared with the ZnO sintered body of Comparative Example 1.
実施例１８
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）１９．８３２ｇ及び酸化スカンジウム（Ｓｃ２Ｏ３、純度９９．９％）０．１６８ｇに、ポリエチレングリコール０．４ｇを秤量して加え、乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｓｃのモル比は、Ｚｎ１モルに対してＳｃが０．００９モルであり、配合比とほぼ等しかった。また密度は５．６０ｇ／ｃｍ３であった。
結果を表３に示したが、移動度は、比較例１のＺｎＯ焼結体に較べて大きく増大していることが明らかになった。
Example 18
To 19.832 g of zinc oxide powder (purity 99.9%, average particle size of about 2 μm) and scandium oxide (Sc 2 O 3 , purity 99.9%) 0.168 g, weighed and added 0.4 g of polyethylene glycol, The mixture was mixed in a mortar and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of the composition analysis of the obtained sintered body, the molar ratio of Zn and Sc was 0.009 mol of Sc with respect to 1 mol of Zn, which was almost equal to the compounding ratio. The density was 5.60 g / cm 3 .
The results are shown in Table 3, and it was revealed that the mobility was greatly increased as compared with the ZnO sintered body of Comparative Example 1.
実施例１９
酸化亜鉛粉（純度９９．９％、平均粒径約２μｍ）９．７９ｇ及び酸化マグネシウム（純度９９．９％）０．０４８ｇに、さらに酸化錫（ＳｎＯ、純度９９．９％）０．１６２ｇを加え、これにポリエチレングリコール０．２ｇを加えて乳鉢で混合し、次いで、遊星ボールミルで２時間混合粉砕した。得られた混合粉を１００メッシュの篩にかけ、粒度を揃え、金型に入れて、約幅５ｍｍ厚さ５ｍｍ長さ２０ｍｍの棒状に加圧成形した。成形体をさらに１ｔ／ｃｍ２の水圧をかけてＣＩＰ成形した。こうして得られた成形体を、室温から４時間かけて１，４２５℃まで昇温し、７時間保持した後、２時間かけて冷却した。
得られた焼結体の組成分析の結果、Ｚｎ、Ｍｇ、Ｓｎのモル比は、Ｚｎ１モルに対してＭｇが０．００９モル、Ｓｎが０．００１モルであり、配合比とほぼ等しかった。また、密度は５．６３ｇ／ｃｍ３であった。
結果を表３に示したが、移動度は、比較例２の亜鉛−マグネシウム酸化物焼結体に較べて大きく増大していることが明らかになった。
Example 19
Zinc oxide powder (purity 99.9%, average particle size of about 2 μm) 9.79 g and magnesium oxide (purity 99.9%) 0.048 g, and further tin oxide (SnO, purity 99.9%) 0.162 g In addition, 0.2 g of polyethylene glycol was added thereto and mixed in a mortar, and then mixed and ground in a planetary ball mill for 2 hours. The obtained mixed powder was passed through a 100-mesh sieve, the particle sizes were made uniform, placed in a mold, and pressure-formed into a rod shape having a width of about 5 mm, a thickness of 5 mm, and a length of 20 mm. The molded body was further subjected to CIP molding by applying a water pressure of 1 t / cm 2 . The molded body thus obtained was heated from room temperature to 1,425 ° C. over 4 hours, held for 7 hours, and then cooled over 2 hours.
As a result of composition analysis of the obtained sintered body, the molar ratio of Zn, Mg, and Sn was 0.009 mol of Mg and 0.001 mol of Sn with respect to 1 mol of Zn, and was almost equal to the blending ratio. The density was 5.63 g / cm 3 .
The results are shown in Table 3, and it was revealed that the mobility was greatly increased as compared with the zinc-magnesium oxide sintered body of Comparative Example 2.
本発明の亜鉛系複合酸化物を用いることにより、性能の良い透明導電材料、透明導電膜、熱電変換材料、半導体素子（発光素子、トランジスタ）、導電性フィラー、透明トランジスター等が作製可能となる。 By using the zinc-based composite oxide of the present invention, it is possible to produce a transparent conductive material, a transparent conductive film, a thermoelectric conversion material, a semiconductor element (light emitting element, transistor), a conductive filler, a transparent transistor, and the like with good performance.
Claims (8)
ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素、
の複合酸化物からなり、亜鉛と第一の金属元素のモル比が１：０．００１〜０．２である亜鉛系複合酸化物。 Zinc, and at least one first metal element selected from lanthanoid, Sn, and Sc,
A zinc-based composite oxide having a molar ratio of zinc to the first metal element of 1: 0.001 to 0.2 .
ランタノイド、Ｓｎ、Ｓｃから選ばれる少なくとも一種の第一の金属元素、及び
Ｍｇ、Ｓｉ、Ｃａ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｏ、Ｒｈから選ばれる少なくとも一種の第二の金属元素、
の複合酸化物からなり、亜鉛、第一の金属元素及び第二の金属元素のモル比が１：０．００１〜０．２：０．００１〜０．２である亜鉛系複合酸化物。 zinc,
At least one first metal element selected from lanthanoid, Sn, Sc, and at least one second metal element selected from Mg, Si, Ca, Mn, Fe, Co, Ni, Mo, Rh,
A zinc-based composite oxide having a molar ratio of zinc, the first metal element and the second metal element of 1: 0.001-0.2: 0.001-0.2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004128038A JP4526861B2 (en) | 2004-04-23 | 2004-04-23 | Zinc based complex oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004128038A JP4526861B2 (en) | 2004-04-23 | 2004-04-23 | Zinc based complex oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005306684A JP2005306684A (en) | 2005-11-04 |
| JP4526861B2 true JP4526861B2 (en) | 2010-08-18 |
Family
ID=35435860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004128038A Expired - Fee Related JP4526861B2 (en) | 2004-04-23 | 2004-04-23 | Zinc based complex oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4526861B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8389135B2 (en) * | 2006-06-08 | 2013-03-05 | Sumitomo Metal Mining Co., Ltd. | Oxide sintered body, target, transparent conductive film obtained by using the same, and transparent conductive substrate |
| JP2008192604A (en) * | 2007-01-12 | 2008-08-21 | Sumitomo Chemical Co Ltd | Transparent conductive film material |
| JP5125162B2 (en) * | 2007-03-16 | 2013-01-23 | 住友化学株式会社 | Transparent conductive material |
| KR101117797B1 (en) * | 2009-04-24 | 2012-03-09 | (주)석경에이티 | Preparation method of transparent conductive complex comprising Yb doped ZnO, transparent conductive composition, coating film and optical device comprising the same |
| KR20150084834A (en) * | 2012-11-19 | 2015-07-22 | 토소가부시키가이샤 | Oxide sinter, sputtering target using same, and oxide film |
| JP5613805B2 (en) * | 2013-09-02 | 2014-10-29 | 学校法人金沢工業大学 | Zinc oxide-based transparent conductive film, sintered compact target for magnetron sputtering, liquid crystal display and touch panel, and equipment comprising zinc oxide-based transparent conductive film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3538022A (en) * | 1967-07-28 | 1970-11-03 | St Joseph Lead Co | Electrically conductive zinc oxide |
| JP2000012915A (en) * | 1998-06-22 | 2000-01-14 | Daiken Kagaku Kogyo Kk | Thermoelectric conversion material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199862A (en) * | 1978-07-17 | 1980-04-29 | Westinghouse Electric Corp. | Method of constructing an electrical winding assembly |
| JPS55162477A (en) * | 1979-06-02 | 1980-12-17 | Honshu Chemical | Manufacture of electroconductive zinc oxide |
| JPS58145620A (en) * | 1982-02-24 | 1983-08-30 | Honjiyou Chem Kk | Preparation of electrically-conductive zinc oxide |
| JPS58161923A (en) * | 1982-03-17 | 1983-09-26 | Hakusui Kagaku Kogyo Kk | Manufacture of electrically conductive zinc oxide |
| JPS5997531A (en) * | 1982-11-22 | 1984-06-05 | Sumitomo Alum Smelt Co Ltd | Manufacture of electrically conductive white filler |
| JPH0843841A (en) * | 1994-07-27 | 1996-02-16 | Toppan Printing Co Ltd | Formation of transparent conductive film |
| JPH08277112A (en) * | 1995-04-06 | 1996-10-22 | Central Glass Co Ltd | Transparent conductive oxide material |
| JP3881407B2 (en) * | 1996-07-31 | 2007-02-14 | Ｈｏｙａ株式会社 | Conductive oxide thin film, article having this thin film, and method for producing the same |
-
2004
- 2004-04-23 JP JP2004128038A patent/JP4526861B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3538022A (en) * | 1967-07-28 | 1970-11-03 | St Joseph Lead Co | Electrically conductive zinc oxide |
| JP2000012915A (en) * | 1998-06-22 | 2000-01-14 | Daiken Kagaku Kogyo Kk | Thermoelectric conversion material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005306684A (en) | 2005-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4488184B2 (en) | Indium oxide-zinc oxide-magnesium oxide sputtering target and transparent conductive film | |
| US8569192B2 (en) | Sintered complex oxide, method for producing sintered complex oxide, sputtering target and method for producing thin film | |
| CN104671771A (en) | High voltage gradient zinc oxide based varistor material and preparation method thereof | |
| TW201116637A (en) | Oxide sintered body, method for producing same, and starting material powder for producing oxide sintered body | |
| JP4526861B2 (en) | Zinc based complex oxide | |
| CN109071359A (en) | Oxide sintered body, sputtering target, and oxide semiconductor film | |
| WO2016182011A1 (en) | Alumina sintered body and optical element base substrate | |
| JP5095517B2 (en) | Aluminum-containing zinc oxide n-type thermoelectric conversion material | |
| Park et al. | Influence of SnO2 addition on the thermoelectric properties of Zn1− xSnxO (0.01≤ x≤ 0.05) | |
| JP2006347861A (en) | Manufacturing method of zinc-based oxide and zinc-based oxide manufactured by the method | |
| JP5673794B2 (en) | Thermoelectric conversion material and thermoelectric conversion element | |
| JP5087605B2 (en) | Indium oxide-zinc oxide-magnesium oxide sputtering target and transparent conductive film | |
| JP6146773B2 (en) | Oxide sintered body and manufacturing method thereof | |
| JP2008115024A (en) | Conductive oxide powder and method of manufacturing conductive oxide powder | |
| JP5234861B2 (en) | Oxide sintered body sputtering target and method of manufacturing the same | |
| JP3379745B2 (en) | Transparent conductive oxide material | |
| KR102484797B1 (en) | p-type oxide material, method for fabricating the same, transparent electrode and electric device | |
| JP5562000B2 (en) | Oxide sintered body and manufacturing method thereof | |
| JP3379743B2 (en) | Transparent conductive oxide material | |
| JP2001284661A (en) | n-TYPE THERMOELECTRIC ELEMENT COMPOSITION FOR HIGH TEMPERATURE | |
| JP7493688B1 (en) | Sputtering target for forming oxide semiconductor thin film, method for manufacturing sputtering target for forming oxide semiconductor thin film, oxide semiconductor thin film, thin film semiconductor device and method for manufacturing same | |
| JP6356290B2 (en) | Oxide sintered body and manufacturing method thereof | |
| JP2010238894A (en) | SOLAR CELL WHOSE STRUCTURE LAYER IS (Zn, In, Al)O BASED TRANSPARENT ELECTRODE LAYER, AND ZnO-In2O3-Al BASED SPUTTERING TARGET USED FOR FORMING THE (Zn, In, Al)O BASED TRANSPARENT ELECTRODE LAYER | |
| JPH08277112A (en) | Transparent conductive oxide material | |
| JPH0971419A (en) | Electrically conductive transparent oxide material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061011 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090427 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090512 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090624 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100525 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100602 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130611 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |