JPS606894B2 - Compound having hexagonal layered structure represented by TmGaZnO↓4 and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound TmGaZn04 having a hexagonal layered structure and a method for producing the same.

Conventionally, a compound having a hexagonal layered structure represented by YFe204 was synthesized by the present applicant, and its existence is already known.

In this compound, as shown in Y30Fe2Fe30042-, divalent and trivalent iron ions are surrounded by five-coordinated oxygen ions, and yttrium (Y) has six-coordinated oxygen ions. It is a compound that surrounds it and has magnetism. The present invention provides that, instead of Y30 in the Y30Fe20FeX30042-compound, Tm3
10. To provide a novel compound in which Zn20 is substituted for Fe20 and Ga30 is substituted for Fe30, and a method for producing the same.

In the compound represented by TmGaZn04 of the present invention, thulium has a Tm30 ion, and gallium has a Ga3
Juzinc exists as Z 〆, and can be represented as TM2 10 GA3 Ten Z Sques 042-. This crystal has a hexagonal layered structure as shown in FIG. The largest circle indicates oxygen, the middle circle indicates thulium, and the smallest black circle indicates gallium and zinc. Gallium and zinc are randomly distributed. The divalent ions of zinc and the trivalent ions of gallium are surrounded by five-coordinated oxygen ions. Crystallographically, they occupy the same position. Thulium also has six-coordinated oxygen molecules around it. Oxygen, an anion, has a delicate structure. s, t and u indicate positions within the unit cell. This crystal's plane index (hkl), plane spacing (d(A)), [d.

is an actual measurement, and dc is a calculated value. ], the relative reflection intensity for the x-ray, 1 (%), is as shown in Table 1. The space group in Table 1 is Rhym, its crystal habit is plate-like, and its lattice constant is as follows.

a.

=3.4300 ±0.0004 (A)
c. =25.066 ±0.006 (
A) This compound is useful as a semiconductor material and a catalyst. This compound can be produced by the following method.

Thulium metal (Tm) or thulium oxide (Tm20
3) Alternatively, thulium oxide (
A compound that decomposes to Tm203) and metal gallium, or gallium oxide (Ga203), or a compound that decomposes to gallium oxide (Ga203) when heated and zinc or zinc oxide (Zn○), or a compound that decomposes when heated A compound that produces zinc oxide (Zn○) is mixed with thulium, gallium, and zinc in an atomic ratio of 1:1:1, and the mixture is oxidized in the air at a temperature of 1,300 or higher. It can be produced by heating in an atmosphere or in a reducing atmosphere to the extent that gallium and zinc are not reduced from the trivalent ion state or the divalent ion state, respectively.

Commercially available starting materials used in the present invention may be used as they are, but in order for the chemical reaction between the starting materials to proceed quickly, the particle size should be as small as possible, especially 10 mm or less. is preferred.

Further, when used as a semiconductor material, since contamination with impurities is to be avoided, it is preferable that the starting material has a higher purity.

This raw material is thoroughly mixed as is or with alcohol or acetone. The mixing ratio of these is such that the atomic ratio of thulium, gallium, and zinc is 1:1:1.

If this ratio is exceeded, the target compound cannot be obtained. This mixture is exposed to air or an oxidizing atmosphere, or when gallium and zinc are in the trivalent ion state and in the divalent ion state.
Heating is carried out at a temperature of 130,000 or higher in a reducing atmosphere to such an extent that the valence ion state cannot be reduced. The heating time is one day or more. There are no restrictions on the rate of temperature increase during heating. After the reaction is completed, it may be rapidly cooled to 0°C or rapidly drawn out into the atmosphere. The obtained TmGaZ
The n04 compound was colorless and was found to have a crystalline structure by powder X-ray diffraction. It was found that its crystal structure was the same as that of YFe204 already obtained by the applicant. The weights of the starting mixed sample and the reaction product were precisely weighed, and the stoichiometry of the resulting sample was determined. Examples Thulium oxide (Tm203) powder with a purity of 99.9% or more, gallium oxide (Ga203) with a purity of 99.9% or more
Powder and reagent-grade zinc oxide (Zn○) powder were weighed at a molar ratio of 1:1:2, and ethyl alcohol was added in a mortar and mixed thoroughly to form a fine powder with an average particle size of a few degrees. I got it.

The mixture was filled in a platinum Lurubo and placed in a box-shaped siliconite furnace set at 1550 oo and heated for 2 days, after which the sample was taken out of the furnace and rapidly cooled to room temperature. The obtained sample was TmGaZn04, and it was confirmed by powder X-ray diffraction that it was crystallographically the same as YFe204, which has already been reported. The weight of the sample was precisely weighed before and after heating, and the stoichiometry of the resulting sample was determined. Table 1 shows the crystallographic properties of the samples obtained.

[Brief explanation of drawings]

The drawing is a diagram of a TmGaZn04 crystal of the present invention. The largest circle indicates oxygen, the middle circle indicates thulium, and the smallest black circle indicates zinc and potassium. grandchild habe

Claims (1)

[Claims] 1. A compound having a hexagonal layered structure represented by TmGaZnO_4. 2 Thulium metal (Tm) or thulium oxide (Tm
_2O_3) or a compound that decomposes into thulium oxide (Tm_2O_3) when heated, and metallic gallium (Ga) or gallium oxide (Ga_2O_
3) Alternatively, gallium oxide (G
a_2O_3) and zinc (Zn) or zinc oxide (ZnO) or a compound that is decomposed to produce zinc oxide (ZnO) when heated, when the ratio of thulium, gallium, and zinc is 1 in atomic ratio. Mix at a ratio of 1:1 and in the atmosphere at a temperature of 1300℃ or higher.
TmGaZn characterized by heating in an oxidizing atmosphere or a reducing atmosphere to the extent that gallium and zinc are not reduced from their trivalent ion state and divalent ion state, respectively.
A method for producing a compound having a hexagonal layered structure represented by O_4.