JPS60191006A - Production of chalcogenide powder - Google Patents

Abstract

PURPOSE:To obtain submicroscopic chalcogenide powder of high purity by reacting a metallic alkoxide with H2S, H2Se or H2Te. CONSTITUTION:A metallic alkoxide represented by a formula M(OR)n (where M is Ge, Si, Sn, Al, Ga, In, As, Sb, Mg, Ca, Sr, Ba, Y, Sc, La, Ti, Zr, V, Nb, Mo, Fe, Cd, Zn or Mn, and R is alkyl) is reacted with a compound represented by a formula H2X (where X is S, Se or Te) optionally in the presence of an inorg. or org. acid to obtain chalcogenide powder made of the sulfide, solenide or telluride of said metal.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for producing raw materials for sulfides, selenides, and tellurides used for phosphors, optical disks, and the like.

[Background of the invention]

Conventionally, metal sulfides are made of metal and H2 at 400-500°C.
Synthesis has been carried out by directly reacting S or by reacting metal chloride with H2S at room temperature. Among these sulfide synthesis methods, Zabumicron powder cannot be synthesized in the former method due to the high temperature. Furthermore, when the latter chloride is made into JJK size, it generally has a low vapor pressure, making it difficult to purify by distillation and making it difficult to synthesize high-purity powder. Furthermore, in the synthesis of selenide and telluride, synthesis is carried out by depositing selenium or tellurium on a target at the same time as other metals, but the products that can be synthesized using this method are limited to thin films. The manufacturing method of directly synthesizing compounds of selenium, tellurium, and metals in a crucible or the like has the disadvantage that the number of elements is limited to a small number and that compositionally homogeneous products cannot be obtained.

[Purpose of the invention]

An object of the present invention is to provide a manufacturing method for synthesizing highly pure submicron powders of sulfides, selenides, and tellurides.

[Summary of the invention]

The present invention originates from the inventor's detailed study of the reaction process of a metal alkoxide hydrolysis reaction. That is, metal alkoxide M(OR).

[M: metal, O: oxygen, R: alkyl group] and water 1120
When reacting, an oxide is generally synthesized according to the following formula.

M(OR),,+mH,O-+MOx+n ROH At this time, as a result of detailed investigation of the elementary process of one reaction, the reaction in the above equation separates H and O into OH- and H1 ions, and the generated Ol-
Toion is M(OR). It has become clear that the reaction proceeds by attacking M and H + ions attacking OR. As a result, the oxygen atoms of the generated oxide MO, H2
The inventors focused on this fact and discovered that H2S and H2Se have the same isosceles triangular molecular structure as H and O instead of H and O.

) (, Te, etc., these gases react directly with the metal in the metal alkoxide, forming sulfides, selenides,
I came up with the idea that telluride could be synthesized. The method of synthesizing sulfides, selenides, and tellurides by such reactions with metal alkoxides is a reaction that has not been previously known. The inventors were able to produce sulfides, selenides, and tellurides by flowing H, S, )'I, Se, or H, Te gas into the metal alkoxide itself or into a solution of the metal alkoxide dissolved in an appropriate solvent. They discovered that the powder obtained was extremely fine and highly pure, and that the wood method was extremely effective in producing high-purity fine powder.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in detail according to examples.

Example 1. Synthesis of Ge sulfide Ge(OCH,)4 29.6m124:C1-1,O
Pour the solution containing H2OmQ into a bubbler and add 9% N
, gas dilution H2SI was poured in at a ratio of 100 mQ/1 m1n. After a while of flowing gas, the liquid began to become cloudy, indicating that a reaction had occurred between G e (OCHs)- and lI,S.

2 mol of H, S for 41 mol of Ge(COHa)
After flowing H and S in such a ratio, the solution was allowed to stand for one day in a humidity-free room, and after removing the supernatant, it was dried in a vacuum dryer to produce a dry powder. The obtained white powder was amorphous according to
The powder was identified to be a52 and was an extremely fine powder with a BET specific surface area of 24.5n/'g and an average particle size of 800nm.

Metal impurity analysis by emission spectroscopy showed that all of the impurities except Go were less than 1 yen), and the obtained powder had extremely high purity.

Example 2. Synthesis of Ta sulfide Ta(QC,H,)! , 4.6 g and CI,O
Pour a mixture of 16g of H into a bubbler and add 9% H,5
(N2 dilution) was bubbled at a flow rate of R100 mm/w+in. It was noted that when H and S were poured, a black precipitate began to form. The precipitate was dried using a vacuum drying method, and the composition was analyzed and the result was Tag.

The BET specific surface area was 15 cJ/g, and the amount of impurities of metal elements other than Ta and S was 5 PPII or less.

Example 3.60 selenide ae (oc, H,,) 42.5 g and C, H, OH 78 m
Put the mixed solution of Q into the bubbler J], 2% H2S
e (Ar diluted) at a flow rate of 500 m12/win. The obtained precipitate was amorphous according to X-rays, but the Raman spectrum revealed that it was a G e S e 2 compound.6 The specific surface area of the obtained precipitate was:
12 rtr/g, and all metal element impurities other than Ge and Se were 5 ppm or less.

Example 4. 42.6 g of Sb telluride S b (QC,HG) (,:, H
1% H, T p,
(Ar dilution) Gas was bubbled at a flow rate of 500 mQ/win. As a result of drying the obtained off-white powder and chemically analyzing it, it was determined that the produced powder was Sb, Te, etc. The obtained powder was an amorphous substance according to X-ray examination. The metal impurity concentration of the powder is l for each element.
It is less than 10PP and fii! It was a highly pure powder.

Example 5. In Catalyst Example 1, 0.1 mQ of acetic acid (100%) was added to the mixture of Ge alkoxide and alcohol. H
When 2S was added, white powder Ge52 was formed extremely quickly compared to Example 1, and it became clear that acetic acid had a catalytic effect in the reaction described in -1-.6 In the above examples, Ge, Examples of synthesis of Ta, Sb sulfide, selenide, and telluride have been given, but in addition, Si, AM
, Ga, In, Aq, Mg, Cm.

Sr, Ba, Y, Sc, La, Ti, Zr, V.

By reacting metal alkoxides such as Nb, MO, FO, Cd, Zn, and Mn with H, S, H2S5, or H, Te, it is possible to synthesize high-purity fine powders of sulfides, selenides, and tellurides. In addition, it is extremely important to add acid in each reaction to promote the reaction.
In addition to il acid, helical acid, hydrogen chloride, sulfuric acid, nitric acid, etc. are effective as these acids.6 As described above, according to the present invention, high purity can be obtained by an unprecedented synthetic reaction. can produce sulfide, selenide, and telluride powder.

〔Effect of the invention〕

The present invention is a novel method for synthesizing sulfides, selenides, and tellurides of various metals, and has a groundbreaking effect in that highly pure and ultrafine powder-like compound -E can be easily obtained. be.

Agent: Patent Attorney Takahashi “Beast” ゝ()′

Claims (1)

[Claims] 1. Metal alkoxide M (OR). (M is Qe. S I HS rl gΔQ, Ga, In, As, Sb
. M g g Ca + S r p B a, HY
HS c HI, a. Ti, Zr, V, Nb, Mo, Fe, Cd. at least one element of metal selected from the group of Zn and Mn;
0 is oxygen, R is an alkyl group) and H2X (X is S, Se,
1. A method for producing chalcogenide powder, which comprises reacting at least - elements selected from Te to synthesize sulfides, selenides, and tellurides of the above metals. 2. The method for producing chalcogenide powder according to item 1 of the patent application, characterized in that an inorganic acid or an organic acid is added to a metal alkoxide and reacted.