JPH0244259B2 - - Google Patents
Info
- Publication number
- JPH0244259B2 JPH0244259B2 JP4115287A JP4115287A JPH0244259B2 JP H0244259 B2 JPH0244259 B2 JP H0244259B2 JP 4115287 A JP4115287 A JP 4115287A JP 4115287 A JP4115287 A JP 4115287A JP H0244259 B2 JPH0244259 B2 JP H0244259B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oxide
- heated
- metallic
- ingazn
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 5
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Description
産業上の利用分野
本発明は光機能材料、半導体材料および触媒材
料として有用な新規化合物であるInGaZn4O7で示
される六方晶系の層状構造を有する化合物および
その製造法に関する。
従来技術
従来、(Yb3+Fe3+O3)oFe2+O(nは整数を表わ
す)で示される六方晶系の層状構造を有する化合
物は本出願人によつて合成され知られている。
YbFe2O4、Yb2Fe3O7、Yb3Fe4O10及び
Yb4Fe5O13の六方晶系としての格子定数、YbO1.5
層、FeO1.5層、Fe2O2.5層の単位格子内における
層数を示すと表−1の通りである。
これらの化合物は酸化鉄1モルに対して、
YbFeO3がnモルの割合で化合していると考えら
れる層状構造を持つ化合物である。
INDUSTRIAL APPLICATION FIELD The present invention relates to a compound having a hexagonal layered structure represented by InGaZn 4 O 7 , which is a new compound useful as an optical functional material, a semiconductor material, and a catalyst material, and a method for producing the same. Prior Art Conventionally, a compound having a hexagonal layered structure represented by (Yb 3+ Fe 3+ O 3 ) o Fe 2+ O (n represents an integer) was synthesized by the applicant and was known. There is. YbFe 2 O 4 , Yb 2 Fe 3 O 7 , Yb 3 Fe 4 O 10 and
Lattice constant of Yb 4 Fe 5 O 13 as hexagonal system, YbO 1.5
Table 1 shows the number of layers in the unit cell, FeO 1.5 layer, and Fe 2 O 2.5 layer. These compounds are per mole of iron oxide,
It is a compound with a layered structure that is thought to be composed of n moles of YbFeO 3 .
【表】
発明の目的
本発明は(YbFeO3)oFeOの化学式において、
n=1/4に相当し、Yb3+の代わりにIn3+を、Fe3+
の代わりにGa3+を、Fe2+の代わりにZn2+を置き
かえて得られた新規化合物を提供するにある。
発明の構成
本発明のInGaZn4O7で示される化合物は、イオ
ン結晶モデルでは、In3+(Ga3+、Zn2+)
Zn3 2+O7 2-として記載され、その構造はInO1.5層、
(Ga3+、Zn2+)O2.5層およびZnO層の積層によつ
て形成されており、著しい構造異方性を持つこと
がその特徴の一つである。Zn2+イオンの1/4は
Ga3+と共に(Ga3+、Zn2+)O2.5層を作り、残り
の3/4はZnO層を作つている。六方晶系としての
格子定数は次の通りである。
a=3.284±0.001(Å)
c=32.89±0.01(Å)
この化合物の面指数(hkl)、面間隔(d(Å))
(dpは実測値、dcは計算値を示す)およびX線に
対する相対反射強度(I%)を示すと、表−2の
通りである。
この化合物は光機能材料、半導体材料、触媒材
料等に有用なものである。[Table] Purpose of the invention The present invention is based on the chemical formula of (YbFeO 3 ) o FeO,
Corresponds to n = 1/4, In 3+ instead of Yb 3+ , Fe 3+
The present invention provides a novel compound obtained by replacing Ga 3+ with Zn 2+ and Fe 2+ with Zn 2+ . Structure of the Invention In the ionic crystal model, the compound represented by InGaZn 4 O 7 of the present invention is In 3+ (Ga 3+ , Zn 2+ )
Described as Zn 3 2+ O 7 2- , its structure is InO 1.5 layers,
It is formed by laminating a (Ga 3+ , Zn 2+ )O 2.5 layer and a ZnO layer, and one of its characteristics is that it has significant structural anisotropy. 1/4 of Zn 2+ ions are
Together with Ga 3+ , (Ga 3+ , Zn 2+ ) forms an O 2.5 layer, and the remaining 3/4 forms a ZnO layer. The lattice constants as a hexagonal crystal system are as follows. a = 3.284 ± 0.001 (Å) c = 32.89 ± 0.01 (Å) Planar index (hkl), interplanar spacing (d (Å)) of this compound
(d p is an actual measured value, d c is a calculated value) and the relative reflection intensity (I%) for X-rays is shown in Table 2. This compound is useful for optical functional materials, semiconductor materials, catalyst materials, etc.
【表】【table】
【表】
この化合物は次の方法によつて製造し得られ
る。
金属インジウムあるいは酸化インジウムもしく
は加熱により酸化インジウムに分解される化合物
と、金属ガリウムあるいは酸化ガリウムもしくは
加熱により酸化ガリウムに分解される化合物と、
金属亜鉛あるいは酸化亜鉛もしくは加熱により酸
化亜鉛に分解される化合物とを、Sc、Gaおよび
Znの割合が原子比で1対1対4の割合で混合し、
該混合物を800℃以上の温度で、大気中、酸化性
雰囲気中あるいはInおよびGaが各々3価イオン
状態、Znが2価イオン状態より還元されない還
元雰囲気中で加熱することによつて製造し得られ
る。
本発明に用いる出発物質は市販のものをそのま
ま使用してもよいが、化学反応を速やかに進行さ
せるためには粒径が小さい方がよく、特に10μm
以下であることが好ましい。
また光機能材料、半導体材料として用いる場合
には不純物の混入をきらうので、純度の高いこと
が好ましい。出発物質が加熱により金属酸化物を
得る化合物としては、それぞれの金属の水酸化
物、炭酸塩、硝酸塩等が挙げられる。
原料はそのまま、あるいはアルコール類、アセ
トン等と共に充分に混合する。
原料の混合割合は、In、Ga、及びZnの割合が
原子比で1対1対4の割合であることが必要であ
る。これをはずすと目的とする化合物の単一相を
得ることができない。
この混合物を大気中、酸化性雰囲気中あるいは
InおよびGaが各々3価イオン状態、Znが2価イ
オン状態から還元されない還元雰囲気中で800℃
以上のもとで加熱する。加熱時間は数時間もしく
はそれ以上である。加熱の際の昇温速度には制約
はない。加熱終了後急冷するか、あるいは大気中
に急激に引き出せばよい。
得られたInGaZn4O7化合物の粉末は無色であ
り、粉末X線回折法によつて結晶構造を有するこ
とが分かつた。その結晶構造は層状構造であり、
InO1.5層、(Ga、Zn)O2.5層、およびZnO層の積
み重ねによつて形成されていることが分かつた。
実施例
純度99.99%以上の酸化インジウム(In2O3)粉
末、純度99.99%以上の酸化ガリウム(Ga2O3)
粉末、および試薬特級の酸化亜鉛(ZnO)粉末を
モル比で1対1対8の割合に秤量し、めのう乳鉢
内でエタノールを加えて、約30分間混合し、平均
粒径数μmの微粉末混合物を得た。該混合物を白
金管内に封入し、1450℃に設定された管状シリコ
ニツト炉内に入れ3日間加熱し、その後、試料を
炉外にとりだし室温まで急速に冷却した。得られ
た試料はInGaZn4O7単一相であり、粉末X線回折
法によつて面指数(hkl)、面間隔(dp)および相
対反射強度(I%)を測定した。その結果は表−
2の通りであつた。
六方晶系としての格子定数は
a=3.284±0.001(Å)
c=32.89±0.01(Å)
であつた。
上記の格子定数および表−2の面指数(hkl)
より算出した面間隔(dc(Å))は、実測の面間隔
(dp(Å))と極めてよく一致した。
発明の効果
本発明は光機能材料、半導体材料及び触媒とし
て有用な新規化合物を提供する。[Table] This compound can be produced by the following method. Metallic indium or indium oxide or a compound that is decomposed into indium oxide by heating; Metallic gallium or gallium oxide or a compound that is decomposed into gallium oxide by heating;
Metallic zinc or zinc oxide or a compound that is decomposed into zinc oxide by heating is
Mixing Zn at an atomic ratio of 1:1:4,
It can be produced by heating the mixture at a temperature of 800° C. or higher in the air, in an oxidizing atmosphere, or in a reducing atmosphere in which In and Ga are not reduced to a trivalent ion state, and Zn is not reduced to a divalent ion state. It will be done. Commercially available starting materials used in the present invention may be used as they are, but in order for the chemical reaction to proceed quickly, it is better to have a small particle size, especially 10 μm.
It is preferable that it is below. Furthermore, when used as an optical functional material or a semiconductor material, it is preferable to have high purity since contamination with impurities is avoided. Examples of compounds whose starting materials yield metal oxides by heating include hydroxides, carbonates, and nitrates of the respective metals. The raw materials are thoroughly mixed as they are or together with alcohols, acetone, etc. The mixing ratio of the raw materials needs to be such that the ratio of In, Ga, and Zn is 1:1:4 in atomic ratio. If this is removed, a single phase of the target compound cannot be obtained. This mixture is stored in the air, in an oxidizing atmosphere, or
At 800℃ in a reducing atmosphere where In and Ga are not reduced from the trivalent ion state and Zn from the divalent ion state.
Heat under the above conditions. Heating time is several hours or more. There are no restrictions on the rate of temperature increase during heating. After heating, it can be rapidly cooled, or it can be rapidly drawn out into the atmosphere. The obtained InGaZn 4 O 7 compound powder was colorless and was found to have a crystal structure by powder X-ray diffraction. Its crystal structure is layered,
It was found that it was formed by stacking 1.5 layers of InO, 2.5 layers of (Ga, Zn)O, and a layer of ZnO. Examples Indium oxide (In 2 O 3 ) powder with a purity of 99.99% or more, gallium oxide (Ga 2 O 3 ) with a purity of 99.99% or more
Powder and reagent grade zinc oxide (ZnO) powder were weighed at a molar ratio of 1:1:8, ethanol was added in an agate mortar, and the mixture was mixed for about 30 minutes to form a fine powder with an average particle size of several μm. A mixture was obtained. The mixture was sealed in a platinum tube, placed in a tubular siliconite furnace set at 1450°C, and heated for 3 days, and then the sample was taken out of the furnace and rapidly cooled to room temperature. The obtained sample had a single phase of InGaZn 4 O 7 , and the planar index (hkl), interplanar spacing (d p ), and relative reflection intensity (I%) were measured by powder X-ray diffraction. The results are shown in the table-
2 was true. The lattice constants as a hexagonal crystal system were a=3.284±0.001 (Å) and c=32.89±0.01 (Å). The above lattice constants and the surface index (hkl) in Table 2
The calculated interplanar spacing (d c (Å)) agreed extremely well with the actually measured interplanar spacing (d p (Å)). Effects of the Invention The present invention provides novel compounds useful as optical functional materials, semiconductor materials, and catalysts.
Claims (1)
有する化合物。 2 金属インジウムあるいは酸化インジウムもし
くは加熱により酸化インジウムに分解される化合
物と、金属ガリウムあるいは酸化ガリウムもしく
は加熱により酸化ガリウムに分解される化合物
と、金属亜鉛あるいは酸化亜鉛もしくは加熱によ
り酸化亜鉛に分解される化合物とを、In、Gaお
よびZnの割合が原子比で1対1対4の割合で混
合し、該混合物を800℃以上の温度で、大気中、
酸化性雰囲気中あるいはInおよびGaが各々3価
イオン状態、Znが2価イオン状態より還元され
ない還元雰囲気中で加熱することを特徴とする
InGaZn4O7で示される六方晶系の層状構造を有す
る化合物の製造法。[Claims] 1. A compound having a hexagonal layered structure represented by InGaZn 4 O 7 . 2 Metallic indium or indium oxide or a compound that decomposes into indium oxide when heated; Metallic gallium or gallium oxide or a compound that decomposes into gallium oxide when heated; Metallic zinc or zinc oxide or a compound that decomposes into zinc oxide when heated. and In, Ga, and Zn in an atomic ratio of 1:1:4, and the mixture was heated in the air at a temperature of 800°C or higher,
It is characterized by heating in an oxidizing atmosphere or in a reducing atmosphere in which In and Ga are not reduced to a trivalent ion state and Zn is not reduced to a divalent ion state.
A method for producing a compound having a hexagonal layered structure represented by InGaZn 4 O 7 .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4115287A JPS63210023A (en) | 1987-02-24 | 1987-02-24 | Compound having laminar structure of hexagonal crystal system expressed by ingazn4o7 and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4115287A JPS63210023A (en) | 1987-02-24 | 1987-02-24 | Compound having laminar structure of hexagonal crystal system expressed by ingazn4o7 and its production |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63210023A JPS63210023A (en) | 1988-08-31 |
JPH0244259B2 true JPH0244259B2 (en) | 1990-10-03 |
Family
ID=12600446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4115287A Granted JPS63210023A (en) | 1987-02-24 | 1987-02-24 | Compound having laminar structure of hexagonal crystal system expressed by ingazn4o7 and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63210023A (en) |
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