JPH01298009A - Production of metal multiple chalcogenides - Google Patents

Abstract

PURPOSE:To easily form a thin film on a large-area substrate of an intricate shape by pyrolyzing a composition consisting of a specified compd. and an org. solvent in an inert gas atmosphere. CONSTITUTION:Plural compds. having different chalcogen elements and selected from metal N,N-dialkylchalcogenocarbamates [e.g., Cu(X2CNEt2)2] shown by formula I [M is metallic element, R is a 1-10C org. group, X is S, Se, Te, (n) is 1-5C, x is 1, 2] and metal alkoxychalcogenocarbonates [e.g., Cd(XOCOPr)2] shown by formula II and an org. solvent such as pentane are mixed to obtain a mixed composition. The composition is sprayed by spray pyrolysis, etc., in a heated inert gas atmosphere, and pyrolyzed to produce the fine spherical powder of the single metal multiple chalcogenides or multiple metals multiple chalcogenides having 0.3-0.4mu diameter.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention produces gold, The present invention relates to a method for producing 17j1'eM chalcogenides.

Metal chalcogenides are used as pigments that take advantage of their colors, as well as solar cells that take advantage of their semiconductor and conductor properties.
El that utilizes light receiving elements, video recording devices, and phosphor characteristics
It is widely used in devices, etc.

By combining chalcogen elements and metals, it is possible to adjust the color and control the band gap as a semiconductor, making it possible to handle even more advanced applications. For example, Cd
In the 5-CdSe system, the color tone of the film can be adjusted from yellow to red by changing the composition ratio of S and Se.

[Prior art and its problems]

Conventionally, methods for synthesizing metal chalcogenides include: ■) Hydrogen sulfide H2S, hydrogen selenide H2Se, hydrogen telluride I
Method of reacting t2Te with metals, metal salts, organometallic compounds, etc., 2) Sodium sulfide Na2S, sodium selenide Na25e, sodium telluride Na2T in aqueous solution
Method of synthesis by reaction of a compound such as e with a metal salt, 3
) A method based on a direct reaction between simple sulfur and a metal is known. However, these methods cannot necessarily be said to be suitable production methods for obtaining thin film-like metal chalcogenides, whose applications have recently expanded. For example, ZnS, Z
n5e, ZnTe, CdS, CdSe, CdTe,
The production of thin films of metallic lucogenes such as CuInSe2 and CuInTe3 has become an important technology. The thin film production method includes a method in which a fine powder of Metallic Lucogenia 1 is made into a paste with an organic binder, printed on a substrate, and then fired;
There are physical methods for thinning metal chalcogenide by vacuum evaporation, sputtering, etc., but all of these methods require considerable effort and effort in the thinning treatment after producing metal chalcogenide. Furthermore, since the film is formed by sintering the powder, the uniformity of the film depends on the particle size and particle size distribution of the metal chalcogenide. Furthermore, several hundred to several liters, O″OOA
Since it is difficult to obtain metal chalcogenide powder with a good OOA level, it is difficult to form a thin film on the order of microns or less. In addition, CVD methods, which make thin films by reacting H2S, H2Se, H2Te, and organometallic compound gases on the surface of a substrate, require complicated equipment, making it difficult to reduce production costs by 1 or more, and making it difficult to create films with large areas, making production difficult. inferior to sex. Furthermore, the shape of the substrate on which the coating is formed is also limited.

[Knowledge related to problem solving]

The present inventors have conducted research on a method for producing metal chalcogenide, which is easy to form into a thin film and can be made into a uniform thin film even when applied as a paste and sintered. It has been found that a metal composite chalcogenide can be easily produced by thermally decomposing a composition in which a plurality of metal chalcogenides having different Te) are dissolved in an appropriate solvent in an inert atmosphere. Furthermore, it is possible to obtain a highly uniform metal composite chalcogenide coating by applying the above composition to a substrate by dipping, spin coating, spraying, etc., followed by drying and baking in an inert atmosphere. By decomposing the material by spray pyrolysis method, the particle size is 0.2 to 0.
．． It has been found that it is also possible to obtain a fine powder of about 8μ. Furthermore, we found that it is possible to produce composite chalcogenides made of composite metals by combining different metals.

[Structure of the invention]

According to the present invention, metal N, N-dialkyl chalcogenocarbonates, and CM (XxO2-xCNR,),] metal alkoxychalcogenocarbonates CM (XxO,,COR)
n) (M=metal element, R=charcoal ~10(7) organic u
; X=S, Se, Te; n=1-5; x=1
, 2). Provided is a method for producing a single metal complex chalcogenide or a multimetal complex chalcogenide by thermally decomposing a composition comprising a plurality of compounds containing different chalcogen elements and an organic solvent in an inert atmosphere.

In the present invention, Structural formula (In the formula, M is a metal element, and R is an organic group having 1 to 0 carbon atoms.

X is a chalcogen element, n is an integer of 1 to 5) metal N, N-dialkyl dihydrucogeno Rubamate, structural formula (wherein M is a metal element, R is an organic group having 1 to 10 carbon atoms,
is a chalcogen element; is an integer of 1 to 5), N-dialkylmonochalcogenocarbamate, Mizozo formula (where M is a metal element, R is an organic group having 1 to 10 carbon atoms,
An organometallic compound selected from the group consisting of a metal alkoxymonochalcogenocarbonate represented by a chalcogen element and n an integer of 1 to 5 is used.

Examples of metal elements include zinc Zn, copper Cu, and thallium TQ.
, nickel Ni, palladium Pd, praseodymium Pr,
Cadmium CD, Indium In, Antimony SB, Niobium Rei, Tantalum Ta, Molybdenum MO, Tungsten W, Chromium Cr, Rhodium Rh, Cobalt CO1 Iron F
e, etc.

There are no particular restrictions on the substituent R, but for the purpose of preparing a highly concentrated solution, a substituent with a large number of carbon atoms is more advantageous; however, if the number of carbon atoms is too large, carbon tends to remain when thermally decomposed. It is desirable that the number of carbon atoms does not exceed 10.

Specific examples of the organometallic compounds used in the present invention are shown below. Note that the above-mentioned organometallic compounds are not limited to these.

Sokyo Fallen Copper (II) N,N-diethyl dirucogenolbamate Cu (X2CNEt2).

Copper (I[)N,N-dibutyldichalcogenolbamate Cu (X2 CxBuz)zzinc (n)N,N-
Dibutyl dichalcogenolbamate Zn (X2Cλ
BI42).

Zinc (1'l)N,N-dipropyl lucogenorubamate Zn (X2Cλ'Pr,).

Iron(n)N,N-dibutyldichalcogenolbamate
Fe(X2CNBu,)28! (II)-dibutyl dichalcogenolbame h Sn (X, 0NBu, )
.

Nickel N, N-diethyl dilucogenolbamate
N1(X2C\F!j2)j to nickel, N-dipropyl dihydrocogenolubamate Nj (X2CNPr2
).

Indium N,N-diethyldihydrucogenolbamate In (X2CNEt).

Indium NlN-dibutyldichalcogenocarbamate In(X2Cλ"I3u□)3Indium N,N-diethylmochalcogenocarbamate In(X2CNPe
nt, )3 Cadmium N, N-dipropyl dichalcogenocarbamate Cd (X2CNPr2)z Cobalt N
, N-dibropyrudichalcogenocarbame-1-co(X
2C-containing Prz) r antimony N, N-dibutyl dichalcogenol rubamate Sb (Xz CNBuz) 3 germanium N, N-dipropyl dichalcogen rubamate □□□ (X2CNPr2).

Titanium N,N-diethyldilucogenolubamate Ti(X2CNEt,)4! Gourd copper(n)-pentyl dichalcogenocarbonate Cu(
X2COPent)2Iron(U)-pentyldichalcogenocarbonate Fe(X2COPent)2button-ethyldichalcogenocarbonate Pb (X2COEt)3
Catomium move butyl dilucogenolubonate ω(X
2cOB,) 2-1-mium-propyl di-lucogenocarboner+” cd(X2COPr)2-antimony-
Probil dichalcogenocarbonate 5b (X, C0P
r).

Town hakama■.

Zinc (U) N, N-dibutyl monochalcogenocarbamate M4 (II) x, x-diethyl monochalcogenocarbamate Cu (X2CNEt2)2 Indium N-dibutyl monochalcogenocarbamate 1.

As the cadmium-propyl monochalcogenocarbonate solvent, the following can be used.

aliphatic hydrocarbons such as pentane, n-hexane, and cyclohexane; hard oils such as Solvent Nabtha; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; tetrahydrofuran; Cyclic ethers such as dioxane, ether solvents such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, methylcellulosolve,
Cellulosolves such as ethylcellulosolve, formamides such as dimethylformamide and diethylformamide,
These include amines such as diethylamine, ethylenediamine, and 1-liethanolamine, ketones such as acetone and methyl ethyl ketone, and carbon disulfide. The solvents may be used alone or in combination. In addition, celluloses such as methyl cellulose and ethyl cellulose, and other polymeric substances such as polyethylene oxide and polyvinyl butyral may be added to improve coating performance and apply to screen printing.

In order to obtain a composite chalcogenide of a single metal, it is sufficient to thermally decompose a composition in which a plurality of compounds with different chalcogen elements of the target metal and a solvent are selected from among the above compounds, and the mixture is thermally decomposed to form a thin film. It is coated on top using a conventional coating method such as spin cord, dipping, spraying, or brush coating, and after drying at room temperature or by heating, it is coated under an inert gas atmosphere for 2
What is necessary is just to bake at 50-600 degreeC. In order to increase the viscosity for screen printing, it is sufficient to add a polymeric substance such as the one mentioned above, and it is best to choose one that decomposes sufficiently below the film firing temperature. The fine powder can be produced by spraying the above composition in a heated inert atmosphere using a conventional spray pyrolysis method and thermally decomposing it, which usually produces a spherical fine powder of metal composite chalcogenide with a size of about 0.3 to 0.8μ. is obtained. Furthermore, in order to compound the total bending composition, a composition obtained by selecting and mixing different compounds and solvents of a plurality of metals with the desired composition from among the above compounds is used, and a thin film is formed by coating, drying, and baking.
A spherical fine powder can be obtained by spray pyrolysis.

A composite metal composite chalcogenide can be obtained by the method of the present invention using a composition in which compounds of a plurality of different metals and different chalcogen elements are uniformly mixed in a solution. It has become possible to adjust the shape and control the bandgap width as a semiconductor. Furthermore, by controlling the atmosphere during firing to be oxidizing, it is also possible to generate metal chalcogenates and metal oxides. Further, it is also possible to reduce the metal to a metal by raising the temperature to a higher temperature in a reducing atmosphere during the same firing.

In this way, by skillfully controlling the firing conditions, it is possible to finely control the color tone, semiconductor characteristics, etc.

The film thickness varies from a minimum of 1 OA to a maximum of 1 OA, depending on the coating conditions when thinning the film and overcoating by repeating coating and baking.
It is adjustable from about 0 to 20μ.

〔Effect of the invention〕

If the metal chalcogenide manufacturing method of the present invention is used, Zn(S-5e ), Cd (S-5e), CuIn(S
It becomes possible to form thin films of diluted metal sulfides (e-Te), and it becomes possible to mass-produce high-performance solar cells at low cost by taking advantage of their semiconductor properties.

(Example) Next, examples of the present invention will be shown.

Example 1 Zinc (II) N,N-dibutyldithiocarbamate: (
211 (N2 (, NBu2)2) 4-5 g, zinc (
■) N,N-dibutydiselenolbamate: (Zn(
Se2CNBu2)2) 5.0g of dibutylamine2
After dissolving the solution in 00 g and refluxing for 30 minutes, the solution was spin-coded onto a Pyrex substrate at a rotation speed of 300 rpm, and the solution was refluxed for 30 minutes at room temperature.
After drying for 30 minutes and baking at 500°C for 30 minutes under an Ar flow, a uniform Zn (S-5e) film with a thickness of 280 OA and pale yellow color was obtained.
Got a coating.

Example 2 Cadmium 0-isopropyldithiocarbonate: (C
d(SzCOPr')2)5g, cadmium O-isoprobyl diselenocarbonate: [Cd(S
e2COPr”)2) 5g of ethyl cellulosolve 50
A solution dissolved in 0 g was brushed onto the tile surface, dried at room temperature for 30 minutes, and baked at 600° C. for 125 minutes under a N2 stream to obtain a light-colored Cd(S'Se) thin film with a film thickness of 5000 A.

Example 3 Cadmium 0-isopropylthiocarbonate: (Cd
(SOCOPrl)z )5g, cadmium loisopropyl selenocarbonate: (Cd(Se2CO
Pr'')2) 5g of ethyl cellulosolve dissolved in 500g of ethyl cellulosolve was applied to the surface of the tile with a brush, dried at room temperature for 30 minutes, and baked at 600℃ for 525 minutes under a N2 stream to form a film with a thickness of 3000A and a light-colored Cd ( S-5e) A thin film was obtained.

Example 4 Copper(II) N,N-dibutyl ditellururbamate:
(Cu(Te2CNBu2)2) 5.0g, indium(III)N,N-diethyldithiocarbamate: 335.9g of (In(Se2CNBu2) was dissolved in 500g of diethylamine and refluxed for 30 minutes. The solution was placed on a Pyrex substrate at a rotation speed of 300 rpm. A uniform black CuIn film with a thickness of 3800A was obtained by spin-coding, drying at room temperature for 10 minutes, and baking at 550℃ for 45 minutes under an Ar flow.
Three samples of Se-Te) were obtained.

Example 5 fi(II)N,N-diethyldithiocarbamate; (Cu(S2CNEt2)2)3.9H, indium(III)N,N-diethyldithelenocarbamate:
(In (Se2CNEtz):+)9.1g to T
After dissolving in 500 g of HF, the solution was refluxed for 30 minutes and placed in an annular furnace heated to SOO℃ with a carrier gas flow rate of 500 m1/m.
A spherical fine powder of CuIn (S-3e) having a particle size of 0.6 to 0.8 μm was obtained by spraying with Ar from a spray nozzle.

Claims (1)

[Scope of Claims] Metal N,N-dialkyl chalcogenocarbamates and [M(X_xO_2_-_xCNR_2)_n] metal alkoxychalcogenocarbonates [M(X_xO_2_-_xCOR)_n] (M=metal element, R = organic group having 1 to 10 carbon atoms; X=S
, Se, Te; n = 1 to 5; A method for producing a composite chalcogenide or a composite metal composite chalcogenide.