JP2010132521A - Chalcogen compound powder - Google Patents

Chalcogen compound powder Download PDF

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JP2010132521A
JP2010132521A JP2009009241A JP2009009241A JP2010132521A JP 2010132521 A JP2010132521 A JP 2010132521A JP 2009009241 A JP2009009241 A JP 2009009241A JP 2009009241 A JP2009009241 A JP 2009009241A JP 2010132521 A JP2010132521 A JP 2010132521A
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se
chalcogen compound
metal
chalcogen
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Takeaki Fujino
Yuichi Ishikawa
Koji Tagami
幸治 田上
雄一 石川
剛聡 藤野
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Dowa Holdings Co Ltd
Dowaホールディングス株式会社
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Abstract

When a chalcogen compound is used as a film-like crystal, there is a method of forming a metal film made of Cu, In, and Ga, and then subjecting the metal film to Se treatment. However, there is a problem in film uniformity and productivity. is there. If there are CuIn x Ga 1-x Se nanoparticles, a highly uniform CuIn x Ga 1-x Se film can be obtained at a low cost by applying paste and the like containing the nanoparticles and baking them. However, such nanoparticles have not been obtained. Further, CuIn x Ga 1-x Se y S 2-y ( however, 0 ≦ x ≦ 1,0 ≦ y ≦ 2) nanoparticles have not been obtained.
A metal compound powder comprising one or more metal hydroxides or metal oxides and a reducing solvent are mixed, and one or more (single or compound) compounds selected from sulfur and selenium are added. A chalcogen compound powder having an average particle size (D TEM ) of 60 nm or less can be obtained by producing a mixed solvent and heating the mixed solvent at a temperature of 70 ° C. to 500 ° C.
[Selection] Figure 1

Description

The present invention relates to a chalcogen compound powder containing a chalcogen-based element used for forming a light absorption layer of a thin film solar cell, a phosphor, an electrode film for a Peltier device, and the like, and more particularly, a general formula CuIn x Ga 1-x Se y. The present invention relates to a chalcogen compound powder represented by S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2) and having an average particle diameter (D TEM ) of 1 nm to 60 nm.

Examples of nano-sized powders of metal compounds include semiconductor nanocrystals, particularly cadmium telluride (CdTe), cadmium selenide (CdSe), cadmium sulfide (CdS), copper indium gallium selenium (CuInGaSe), copper indium selenium (CuInSe). In addition to being able to control the light absorption spectrum and the light emission by the size effect of the diameter, the chalcogen compounds such as are capable of controlling the band gap of the compound by forming a solid solution. R & D is actively conducted. In particular, the material represented by CuIn x Ga 1-x Se y S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2) can easily control the band gap by changing the ratio of In to Ga. It is excellent in that it can be applied and is expected to be applied to solar cells and phosphors.

When using CuIn x Ga 1-x Se to the solar cell, used as a film-like crystals. At present, there is a method of forming a metal film made of Cu, In, and Ga and subjecting the metal film to Se treatment.

The synthesis of CdSe nanocrystals using dimethylcadmium (Cd (CH 3 ) 2 ) as a cadmium precursor as an example of a method for synthesizing CdSe nanocrystals that are nanoparticles of chalcogen compounds was first reported by Murray et al. Since 1), it has been developed. In the present application, the chalcogen compound refers to a compound having one or more metal elements and one or more elements selected from Se and S as constituent elements.

Barbera-Guillem et al. Discloses a continuous flow method for producing nanocrystals using the method of Murray et al. (See Patent Document 1).
In addition, a metal oxide or metal salt is used as a precursor as an inexpensive and non-ignitable material, and a metal oxide or metal salt is mixed with a ligand and a coordination solvent to form a soluble metal complex. A method of adding a chalcogen precursor (such as selenium (Se), tellurium (Te), or sulfur (S)) to form nanocrystals is also known (see Patent Document 2).

US Pat. No. 6,179,912 Japanese translation of PCT publication No. 2004-510678

Journal of the American Chemical Society (1993), 115, 8706-8715.

When a chalcogen compound is used as a film-like crystal, there is currently a method of forming a metal film made of Cu, In, and Ga and performing a Se treatment on the metal film. However, there is a problem in film uniformity and productivity. is there. CuIn x Ga 1-x Se nanoparticles (in this application, unless otherwise specified, nanoparticles have an average particle diameter (D TEM ) of 60 nm as measured by transmission electron microscope (hereinafter, TEM) observation) If the following powder is referred to as nano-particles), a highly uniform CuIn x Ga 1-x Se film can be obtained at low cost by applying a paste containing the powder into a film and baking it. However, such nanoparticles have not been obtained.

In addition, as an example of a method for synthesizing CdSe nanocrystals that are nanoparticles of chalcogen compounds, the method of Non-Patent Document 1 or Patent Document 1 is known, but CuIn x Ga 1-x Se y S 2-y is known. However, nanoparticles of 0 ≦ x ≦ 1, 0 ≦ y ≦ 2 are not obtained.

Furthermore, a method of producing nanocrystals using a metal oxide or a metal salt as a precursor as an inexpensive and non-ignitable material is also known (see Patent Document 2). However, CuIn x Ga 1-x is known. Se y S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2) is not obtained.

Thus, the conventional art, CuIn x Ga 1-x Se y S 2-y ( however, 0 ≦ x ≦ 1,0 ≦ y ≦ 2) can not be obtained nanoparticles. In particular, CuIn x Ga 1-x Se 2 (where 0.1 ≦ x ≦ 0.9) nanoparticles useful as a crystalline film material for solar cells could not be obtained.

The present invention has been made in view of such problems, and is represented by the general formula CuIn x Ga 1-x Se y S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2), and is transmitted. The problem is solved by obtaining a chalcogen compound powder having an average particle diameter (D TEM ) of 1 nm to 60 nm measured by observation with a scanning electron microscope.

The chalcogen compound powder is characterized by being represented by the general formula CuIn x Ga 1-x Se 2 (where 0.1 ≦ x ≦ 0.9).

The average particle diameter (D TEM ) is 20 nm or less.

  In addition, the chalcogen compound powder has an X-ray diffraction peak intensity ratio (a value obtained by dividing the highest peak height of the peak intensity of the desired chalcogen compound by the highest peak height of the peaks of other substances). It is characterized by being 8 or more.

  Furthermore, the chalcogen compound powder is characterized in that the peak intensity ratio of the X-ray diffraction is 15 or more.

According to the present embodiment, nanoparticles of CuIn x Ga 1-x Se y S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2) can be obtained using an inexpensive metal salt as a raw material. . In particular, CuIn x Ga 1-x Se 2 (where 0.1 ≦ x ≦ 0.9) nanoparticles that are useful as a crystalline film material for solar cells can be obtained. The chalcogen compound powder obtained in the present embodiment has an X-ray diffraction peak intensity ratio (the highest peak height among the peak intensities of the target chalcogen compound is the highest peak height among the peaks of other substances). (Divided value) is 8 or more, and particles composed of crystals having the target composition are included at a high concentration. By forming a film using this chalcogen compound powder, it is expected to improve the characteristics of CuIn x Ga 1-x Se y S 2-y formed using the powder as a raw material.

In addition, according to the present embodiment, a chalcogen compound in which the composition of the compound (x and y of CuIn x Ga 1-x Se y S 2- y) is appropriately adjusted according to the use of the crystal film material can be obtained. it can.

It is a flowchart explaining the manufacturing method for obtaining the chalcogen compound powder of embodiment of this invention. It is the result of having evaluated the particle size and state of the sample by Example 1 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 1 of this invention. It is the result of the analysis by the fluorescent X ray of the chalcogen compound by Example 1 of this invention. It is a graph which shows the X-ray-diffraction result of the chalcogen compound by Example 1 of this invention. It is the result of having evaluated the particle size and state of the sample by Example 2 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 2 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 2 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 3 of this invention. It is the result of the analysis by the fluorescent X ray of the chalcogen compound by Example 3 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 4 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 4 of this invention. It is the result of evaluating the production | generation state of the chalcogen compound by Example 5 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 5 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 6 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 6 of this invention. It is a graph which shows the X-ray-diffraction result of the chalcogen compound by Example 6 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 7 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 7 of this invention. It is a crystallite diameter of the chalcogen compound by Example 7 of this invention. It is the result of having evaluated the production | generation state of the chalcogen compound by Example 8 of this invention. It is a crystallite diameter of the chalcogen compound by Example 8 of this invention. It is a flowchart explaining the other manufacturing method of the chalcogen compound of embodiment of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by Example 9 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 9 of this invention. It is a graph which shows the X-ray-diffraction result of the chalcogen compound by Example 9 of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by Example 11 of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by Example 12 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 12 of this invention. It is a graph which shows the X-ray-diffraction result of the chalcogen compound by Example 12 of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by Example 13 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 13 of this invention. It is a graph which shows the X-ray-diffraction result of the chalcogen compound by Example 13 of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by Example 14 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 14 of this invention. It is a graph which shows the X-ray-diffraction result of the chalcogen compound by Example 14 of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by Example 15 of this invention. It is a result of the analysis by the fluorescent X ray of the chalcogen compound by Example 15 of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by the reference example of this invention. It is the result of the analysis by the fluorescent X ray of the chalcogen compound by the reference example of this invention. It is the result of having evaluated the production | generation state and reaction temperature of the chalcogen compound by the reference example of this invention. It is the result of the analysis by the fluorescent X ray of the chalcogen compound by the reference example of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 to 42.

The chalcogen compound powder of the present embodiment is represented by the general formula CuIn x Ga 1-x Se y S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2), and the average particle size (D TEM ) Is a compound of 1 nm to 60 nm.

  Further, the chalcogen compound of the present embodiment refers to a compound having one or more metal elements and one or more elements selected from Se and S as constituent elements.

  FIG. 1 is a flowchart for explaining an example of a production method for obtaining the chalcogen compound powder of the present embodiment.

  The manufacturing method of the chalcogen compound crystal powder of this embodiment mixes the metal compound powder which consists of 1 or more types of a metal hydroxide or a metal oxide, and a reducing solvent, and selects from sulfur (S) and selenium (Se). And a step of adding a compound (one or more) composed of one or more to produce a mixed solvent and a step of heating the mixed solvent at a temperature of 200 ° C to 500 ° C.

By this method, a chalcogen compound powder having an average particle size (D TEM ) of 60 nm or less can be obtained.

  The metal compound powder used as a raw material can be a metal hydroxide or a metal oxide powder. The metal hydroxide can be produced by dissolving a metal salt in a solvent and adding an alkali. The metal oxide powder can be obtained by oxidizing (dehydrating) a metal hydroxide.

  Hereinafter, the case where a metal salt or a metal oxide is produced as a starting material to produce a chalcogen compound will be described as an example. The metal hydroxide or metal compound powder of the metal oxide is used as a starting material. It can also be.

  That is, in this embodiment, after dissolving a metal salt in a solvent and adding an alkali to precipitate a metal hydroxide, decantation, centrifugal sedimentation, filtration, etc. are performed, washed with water as necessary, and dried. To obtain a metal hydroxide. Alternatively, a metal hydroxide metal compound powder obtained by oxidizing (dehydrating) a metal hydroxide, or a hydroxide or oxide metal compound powder as a starting material is mixed in a reducing solvent, and the reducing solvent is used. It heats in the state which added the chalcogen source, and produces | generates a predetermined | prescribed chalcogen compound. By selecting the type of metal compound and chalcogen source to be used, the composition of the obtained chalcogen compound powder can be adjusted.

  The metal salt of this embodiment is selected from any group of metal halides, metal carboxylates, metal carbonates, metal nitrates, and metal sulfates.

Specifically, as a metal salt used as a starting material, for example, a metal halide salt includes cupric chloride (CuCl 2 ), indium chloride (InCl 3 ), copper bromide (CuBr 2 ), copper iodide (CuI). 2 ) and the like are typically metal chlorides, metal bromides, metal iodides, metal fluorides, and as strong metal salts, copper sulfate (CuSO 4 ), cupric nitrate (Cu (NO 3 ) 2 ) And sulfates such as indium sulfate (In 2 (SO 4 ) 3 ) and nitrates. In addition, copper acetate (Cu (CH 3 COO) 2 ), cupric formate (Cu (HCOO) 2 ), copper oxalate (Cu (Cu (CH)) using carboxylic acids such as acetate, formate and oxalate There are metal salts such as COO) 2 ). These salts may contain water of crystallization. Types of metal elements contained in the metal salt include Cu, In, and Ga.

These metal salts are dissolved in a polar solvent such as water or alcohol. Then, it neutralizes by adding an alkali and produces | generates a metal hydroxide. Specifically, it is precipitated as a metal hydroxide by an aqueous ammonia solution, sodium hydroxide, potassium hydroxide, or an alkaline organic compound having an amino group. At this time, since the chalcogen compound to be obtained is a compound containing a plurality of metal elements, at least in order to obtain a precipitate of metal hydroxide having the same metal element ratio as the chalcogen compound as the metal salt composition, Metal hydroxide is generated using two or more metal salts. Specifically, for example, when manufacturing CuIn 0.7 Ga 0.3 Se 2 , the atomic ratio of copper (Cu), indium (In), and gallium (Ga) is 1: 0.7: 0.3. Thus, a metal hydroxide is produced using a copper salt, an indium salt, and a gallium salt as raw materials. For example, an aqueous solution of nitrate Cu (NO 3 ) 2 , indium trinitrate (In (NO 3 ) 3 ), and gallium nitrate (Ga (NO 3 ) 3 ) is converted into a hydroxide of Cu and In by an aqueous sodium hydroxide solution. Can be generated. It is also possible to separately produce copper hydroxide, indium hydroxide and gallium hydroxide and use them.

The slurry containing these metal hydroxides is removed once with a centrifugal dehydrator, a high-speed centrifugal settling tube, or a filter press, Nutsche, etc., and then redispersed in a polar solvent such as water or ethanol. Further, the operation of removing the solvent is repeated to perform washing. It is desirable to repeat the washing until the conductivity of the residual liquid (filtrate) becomes 10 −1 Sm −1 or less. In particular, if alkali metal remains, it does not volatilize and therefore remains as an impurity element, which may cause a problem.

  Reaction impurities can be removed by washing. The end point of the pH in the neutralization in this embodiment is preferably alkaline. The pH is not particularly limited, but may be 10 or more, for example. Moreover, the lower the conductivity of the filtrate by washing with water, the better. However, when the pH approaches neutral, the metal hydroxide itself elutes and the composition changes, so the pH of the filtrate is maintained at 7.5 or higher. It is desirable to do.

  Thereafter, the metal hydroxide is dried at, for example, 70 ° C. to 90 ° C. to obtain a metal hydroxide powder (metal compound powder). At this time, the drying temperature is not particularly limited, and the drying temperature can be lowered by vacuum drying. The drying temperature may be 200 ° C. or higher.

  Alternatively, the metal hydroxide may be heated and oxidized to produce a metal oxide powder (metal powder).

Specifically, the conductivity of the filtrate to 10 -1 Sm -1 or less by washing, the water content of the slurry containing the metal hydroxide is adjusted to below 50 percent, the slurry (or cake) again, Disperse in solvent.

  By introducing a gas such as air, nitrogen, or argon into a solvent containing a metal hydroxide to evaporate water (bubbling) to the outside, the solvent temperature is heated within a range of 70 ° C. to 300 ° C. The metal hydroxide inside becomes a metal oxide or a mixture of metal oxide and metal hydroxide, the aggregated metal hydroxide dissociates, and the size of primary particles in the solvent is 1 nm to 200 nm. It can be set as the state where powder exists in an unsintered state.

  At this time, the solvent molecules themselves may be dispersed in the solvent by wrapping the particles in the form of chemical bonds or physical adsorption. Alternatively, a surfactant may be added to the solvent to disperse the particles in the solvent. The particles dispersed in the solvent in this way are desirable because the particles can be prevented from agglomerating and sintering during surface treatment or other reaction treatment with the particles.

  Since the reaction during the oxidation releases water into the solvent, bubbling may be performed as described above, but the oxidation reaction may be promoted by raising the temperature in an autoclave.

  In this example, the metal oxide is produced after washing the metal hydroxide. However, after the metal hydroxide is produced and heated in the same solvent, the metal oxide is produced. A cleaning operation may be performed. Moreover, when performing a metal hydroxide production | generation and a chalcogenation reaction in the same solvent, you may perform washing | cleaning operation after a chalcogenation reaction. In any stage, the reaction impurities can be appropriately removed by washing.

  Next, a metal hydroxide or a metal oxide metal powder and a reducing solvent are mixed, and a simple substance selected from S and Se, or a compound containing one or more selected from the element group is added and mixed. A solvent is produced and heated.

  Here, the reducing solvent is a metal hydroxide or metal compound powder of metal oxide (hereinafter referred to as metal compound powder), a simple substance selected from S and Se, or one or more selected from the element group. A compound having a capability of depriving the metal compound of oxygen atoms as a result and producing a chalcogen compound when a compound containing (hereinafter referred to as chalcogen source) coexists in a solvent and heated. As the reducing solvent, those having a boiling point of 200 ° C. or higher are preferable, and those having a boiling point of 220 ° C. or higher are particularly preferable. As will be described later, in order to obtain a chalcogen compound, it is necessary to heat the reducing solvent to 200 ° C. or higher, preferably 220 ° C. or higher. If the boiling point of the reducing solvent is within the above temperature range, the chalcogen is generated under normal pressure. The reaction to obtain the compound can be performed. When the reaction is carried out under pressure, a solvent having a boiling point of less than 200 ° C. can also be used.

  An example of the reducing solvent is an alcohol solvent having a boiling point in the range of 100 ° C to 400 ° C. In order to perform the chalcogenation reaction at normal pressure, the boiling point is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 250 ° C. or higher in consideration of the yield of the chalcogen compound.

Specifically, the reducing solvent includes monohydric alcohol or dihydric alcohol glycol. Examples of the monohydric alcohol include butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, nonyl alcohol, cyclopentanol, benzyl alcohol, and cinnamyl alcohol. Examples of glycol solvents include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, benzpinacol, hydro Benzoyl, cyclopentadiol, cyclohexanediol, cyclohexanediol, glycolic acid amide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monoethyl ether, diethylene glycol dibutyl ether, acetic acid diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, etc. big Intended polyethylene glycol, polyethylene glycol esters, polyethylene glycol ethers. In particular, glycols and diols are preferable because they have two hydroxyl groups and thus have polarity and contribute to the dispersibility of the powder. Examples of such a solvent include —CH 2 —CHOH, or —CHR—CHOH, —CR 1 R 2 —CHOH, ═CHCHOH, ═CRCHOH (R, R 1 , R 2 : side chain) in the molecule. The boiling point of the solvent is at least 100 ° C. or higher. Furthermore, an organic compound having an aldehyde group -CHO has the same effect. For example, as an aliphatic saturated aldehyde, lauric aldehyde, tridecyl aldehyde, myristic aldehyde, capron aldehyde, heptaldehyde, pentadecyl aldehyde, palmitic aldehyde, marga aldehyde. Examples include aliphatic aldehydes such as succindialdehyde, aliphatic unsaturated aldehydes such as crotonaldehyde, and aromatic aldehydes such as benzaldehyde, tolualdehyde, salicylaldehyde, and cinnamaldehyde. And naphthaldehyde, and the heterocyclic aldehyde includes furfural. Examples of amine-based reducing solvents include hexylamine, hebutinamine, octylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dibutylamine, diamylamine, cyclohexylamine, aniline, naphthylamine, and toluidine. is there.

  Further, as the chalcogen source added to the reducing solvent together with the metal compound powder, a simple substance or alloy powder of the element, a hydrogenated chalcogen compound, or an organic metal of the chalcogen element can be used.

  The alloy is an alloy having Se and S as constituent elements.

Typical examples of the hydrogenated chalcogen compound include hydrogen selenide (H 2 Se), hydrogen sulfide (H 2 S), and the like. Generally, as the chalcogen element organic metal, an alkyl selenol, an aryl selenide is used. Nord, dialkyl selenide, diaryl selenide, halogenated alkyl selenide, halogenated aryl selenide, dialkyl selenoxide, diaryl selenoxide, selenone, alkyl selenic acid, aryl selenic acid, selenonic acid, selenoketone, seleno acid, selenophene, etc. There is. For example, typical examples of dialkyl selenium include Se (CH 3 ) 2 , (C 2 H 5 ) 2 Se, (C 4 H 9 ) 2 Se, (C 6 H 13 ) 2 Se, and the like. One or more of these chalcogen-based elements (Se, S), simple substances, alloys, and compounds can be used.

  And the mixed solvent of the said chalcogen source, a metal compound powder, and a reducing solvent is heated at the temperature of 200 to 500 degreeC. Thereby, the chalcogen source, the mixed solvent of the metal compound powder and the reducing solvent are subjected to a chalcogenization reaction, and the chalcogen compound powder can be easily obtained. If the heating temperature (temperature for the chalcogenation reaction: hereinafter, reaction temperature) is low, the formation of the chalcogen compound may not be sufficient, and even if it is 400 ° C. or higher, the production state of the obtained chalcogen compound is greatly changed. Is not seen, Preferably, it is 220 to 400 degreeC, More preferably, it is the range of 250 to 400 degreeC.

In the present embodiment, a reducing solvent having a higher boiling point than ethyl alcohol or the like is heated to the temperature range, so that the solvent acts as a reducing agent to reduce the metal compound powder and reduce Se and S of the chalcogen source. It is considered that the chalcogen compound powder can be easily obtained by reacting the formed metal. Moreover, the particles of the chalcogen compound powder thus prepared have an average particle diameter (D TEM ) of 1 nm to 200 nm, and a powder free from sintering and bonding between particles can be obtained. By adjusting the particle size of the metal compound powder, a chalcogen compound powder having an average particle size (D TEM ) of 1 nm to 60 nm can be obtained.

The chalcogen compound powder obtained in the present embodiment has an X-ray diffraction peak intensity ratio (the highest peak height among the peak intensities of the target chalcogen compound is the highest peak height among the peaks of other substances). (Divided value) is 8 or more, and particles composed of crystals having the target composition are included at a high concentration. By forming a film using this chalcogen compound powder, it is expected to improve the characteristics of CuIn x Ga 1-x Se y S 2-y formed using the powder as a raw material.

The average particle diameter (D TEM ) of the chalcogen compound powder is preferably 1 nm to 60 nm, and more preferably 1 nm to 40 nm, in order to obtain a chalcogen compound film by firing at a lower temperature. If the average particle diameter (D TEM) is 1 nm to 20 nm, it is possible to obtain a film of chalcogen compound even at a firing temperature of about 200 ° C., more preferably. When the average particle size (D TEM ) exceeds 40 nm, a high firing temperature is required. It is difficult to obtain a chalcogen compound powder having an average particle size (D TEM ) of less than 1 nm.

  As will be apparent from the following examples, the higher the heating temperature of the mixed solvent, the better the yield. However, if the mixed solvent (reducing solvent) boils, the chalcogenation reaction proceeds. However, because the reducing solvent thermally decomposes or volatilizes, the reaction becomes unstable. The temperature (heating temperature of the mixed solvent) is lower than the temperature at which the mixed solvent boils. Specifically, the heating temperature of the mixed solvent of the present embodiment is preferably 220 ° C. or higher, and more preferably 250 ° C. or higher, from the viewpoint of the yield of the chalcogen compound. The upper limit temperature of the heating temperature is preferably not higher than the boiling point of the solvent, specifically 400 ° C. or lower.

  During the chalcogenation reaction, water is released due to the reaction, and the reaction easily proceeds by bubbling with nitrogen or argon as a reducing solvent, and tends to be a single phase of the compound containing the target chalcogen element. When the gas flow rate is large, there is a possibility that a chalcogen element having a high vapor pressure is carried out of the system of the chalcogenation reaction, and therefore there is an appropriate amount.

  In addition, after a chalcogen source is added to produce a chalcogen compound powder, a cleaning operation may be performed to remove impurities mixed in when forming the metal hydroxide. In any stage, the reaction impurities can be appropriately removed by washing.

  The order of mixing and adding the metal compound powder, reducing solvent, and chalcogen source is not limited to the above example. That is, in the step of producing a metal hydroxide from a metal salt, a solution obtained by adding a reducing solvent to pure water may be used as a metal salt solution. Further, a high boiling point solvent may be used as a solvent in the step of generating (oxidizing) the metal oxide from the metal hydroxide. Furthermore, a high boiling point solvent may be used as a solvent in the step of generating (oxidizing) the metal oxide from the metal hydroxide, and a reducing solvent may be added when the chalcogen source is added.

Further, the chalcogen source to be added may not be powdery, and for example, a gas such as hydrogen selenide (H 2 Se) may be supplied. As described above, when the metal compound powder and the reducing solvent are mixed and heated, bubbling with nitrogen or the like facilitates the reaction. Therefore, a gasified chalcogen source may be supplied together with the bubbling gas. .

  If a pressurizing apparatus is used for the chalcogenation reaction, a reducing solvent having a boiling point at normal pressure lower than 200 ° C. can be used.

  In the present embodiment, when the solid content concentration in the liquid of the metal compound at the start of the chalcogenization reaction in the present embodiment is thin, it is easy to disperse and there is little aggregation, but the production amount per reaction decreases, and conversely between the obtained chalcogen compound particles Therefore, the solid content concentration of the metal compound at the start of the chalcogenization reaction is preferably in the range of 0.1% by mass to 50% by mass. More preferably, it is the range of 0.1 mass%-10 mass%.

  In addition, the amount of chalcogen source added during the chalcogen reaction can be equal to or greater than the amount of the metal compound. When the chalcogenation reaction temperature is high, the chalcogen source may evaporate out of the reaction system before the chalcogenation reaction is completed, but by adding more than the equivalent amount, the loss due to the evaporation can be compensated. . Even when added in excess of the equivalent amount, the surplus chalcogen source is lost from the mixed solvent by evaporation after the chalcogen reaction, so the amount of chalcogen source added, the temperature of the chalcogenization reaction, the time, etc. may be adjusted as appropriate. Since it is uneconomical to add the chalcogen source excessively, it is preferable to add 1 to 1.3 times the equivalent amount.

  In the present embodiment, hereinafter, “addition in excess” means adding an amount of more than 1 time and not more than 1.5 times the equivalent.

  The thus produced chalcogen compound powder can be dispersed in a target solvent by a solvent substitution method. At this time, a surfactant can be attached to the particle surface so that the solvent can be easily replaced, and the surfactant can be easily dispersed in the target solvent.

Specifically, the surfactant is not limited to the type of anionic, cationic, nonionic, etc., by controlling the pH in the solvent to charge the particle surface to the positive or negative side, By selecting a surfactant having a charge on the opposite side to the polarity of the charged state, the surfactant can be adsorbed appropriately. Specifically, when the pH is controlled to be on the acidic side, the particle surface tends to be positively charged, and in this case, organic molecules having a functional group such as COO- and SO3- are easily adsorbed. . There are those having functional groups such as sulfone groups and sulfino groups that are easily dissociated in a solvent and easily become anions, but those such as R 1 R 2 SO 2 that do not dissociate and are involved in the polarity of the molecule But it is effective for dispersion. Conversely, when the pH of the solvent is changed to the alkaline side, those having amino groups such as —NH 2 and —NRH are easily adsorbed, and the surfactant should be selected according to the charged state of the particle surface. Is desirable. In some cases, if -OH is present on the surface of the particle, it may be chemically bonded by ester bonding with the carboxyl group of the surfactant. Alternatively, a coupling agent such as Si, Al, or Ti can be used when the impurity concentration does not matter.

  Hereinafter, the embodiment will be described in detail with reference to FIGS. In the following examples, even if there is a difference between the elemental composition ratio of each element of the obtained chalcogen compound and the elemental composition ratio intended to be generated, if the difference is 5% or less, it will be generated. And may be expressed by the molecular formula of the intended elemental composition ratio.

In Example 1, propylene glycol as a solvent in producing metal oxides from metal hydroxide: using (Propyleneglycol PEG), was synthesized CuIn 0.7 Ga 0.3 Se 2. A 250 ml flask is prepared by dissolving 0.01 mol of copper nitrate, 0.007 mol of indium nitrate, and 0.003 mol of gallium nitrate in 200 ml of pure water so that the composition of Cu, In, and Ga is 1: 0.7: 0.3. Put in. Subsequently, in a state where the wings having a diameter of 5 cm were rotated and stirred in the flask at 300 rpm, a 1N solution of sodium hydroxide was added dropwise to neutralize, and the addition was terminated at pH 8.5 to co-precipitate the metal hydroxide. Product was produced. Then, after filtering using Nutsche to obtain a cake, the cake was redispersed with pure water, and the filtration was further repeated, so that the electrical conductivity of the filtrate was 10 −2 Sm −1 or less. At this time, since the copper hydroxide was dissolved when the pH approached 7, the pH was kept at about 7.5. The metal hydroxide cake was then vacuum dried at 90 ° C.

  As a result of observing the form of the metal compound (hydroxide) with TEM, it was a form in which very fine particles were aggregated.

  5 g of this dried metal hydroxide was put into a 250 ml three-necked flask, and further added to 75 g of propylene glycol (PEG), and a feather having a diameter of 5 cm was rotated at 300 rpm and stirred. Thereafter, nitrogen was bubbled at 100 ml / min. In this state, a sample of a metal compound was produced by heating at the 10 kinds of oxidation heating temperatures shown in FIG.

FIG. 2 shows the particle diameters of the metal compounds of Sample 1 to Sample 10 (average particle diameter (D 50 ) (mass 50% particle diameter) measured with a laser type measuring device) prepared at each heating temperature (oxidation heating temperature), And the result of having confirmed the production | generation state of the compound is shown. Here, the particle size was measured using a particle size distribution measuring device by laser scattering, and the formation state of the compound was confirmed from the peak position and height of X-ray diffraction with respect to the approximate ratio of copper hydroxide / copper oxide. . As a result, it was found that when the oxidation heating temperature is 120 ° C. or higher, particles having a particle size of 3 μm or less and mainly oxides can be obtained. Since a particle size distribution measuring device using laser scattering is used for the particle size, primary particles and secondary particles in which primary particles are aggregated are simultaneously measured.

In FIG. 2, the case where the average particle diameter (D 50 ) measured using a particle size distribution measuring device by laser scattering is 2 μm or less is evaluated as ◯, the case where it exceeds 2 μm and 3 μm or less is evaluated as Δ, and the case where it exceeds 3 μm is evaluated as ×. .

From FIG. 2, it can be seen that the higher the oxidation heating temperature, the smaller the average particle diameter (D 50 ), and the dispersion proceeds. As a result of confirming the primary particle size of the copper compound by TEM observation, when the oxidation heating temperature is 150 ° C. or higher, the primary particle size is about 30 nm, and the primary particles are very fine, and are aggregated. It has become. Conversely, when the oxidation heating temperature is as low as 110 ° C. or lower, the copper oxide ratio is low and the secondary particle size is large. From this result, in order to obtain metal compound particles mainly composed of a metal oxide having a small secondary particle size, it is preferable that the oxidation heating temperature is high. When the metal is copper, gallium, and indium, the oxidation heating temperature is 120 ° C. or higher. Is preferred.

Next, Se powder (chalcogen source) so that the atomic ratio of Cu to Se (Cu: Se) is 1: 2.2 with respect to the mixed solvent containing the metal compound treated at the oxidation heating temperature of 250 ° C. ) Was added in excess to obtain a mixed solvent. Subsequently, the solvent in the 250 ml three-necked flask was stirred by rotating a feather having a diameter of 5 cm at 300 rpm, and nitrogen was bubbled at 100 ml / min. In this state, the mixed solvent was heated at 10 reaction temperatures shown in FIG. 3 between 150 ° C. and 300 ° C. for 10 hours to try to produce a chalcogen compound. The produced chalcogen compound was dispersed in ethanol, and then washing for filtration was repeated until the filtrate had a conductivity of 10 −1 Sm −1 or less, followed by drying in the air at room temperature. The chalcogen compound thus obtained was evaluated as follows.

The result is shown in FIG. In FIG. 3, the crystal analysis is performed mainly by an X-ray analyzer (X-Ray Diffractometer, hereinafter referred to as XRD, RAD-rX manufactured by Rigaku Corporation), and the chalcogen compound (CuIn 0.7 Ga 0.3 Se) is obtained for samples 1 to 10. investigated the generation state of the two), it was investigated reaction temperature of chalcogenide reaction necessary to generate the chalcogen compound. At this time, X-ray diffraction was measured under the condition of 50 kV and 100 mA, and the peak intensity ratio was determined. As described above, the peak intensity ratio is a value obtained by dividing the highest peak height among the peak intensities of the target chalcogen compound by the highest peak height among the peaks of other substances. If the peak intensity ratio was 8 or more, it was determined that the target chalcogen compound was obtained in high purity (containing particles having a crystal having the target composition at a high concentration), and indicated by ○ in FIG. . Furthermore, when the peak intensity ratio was 15 or more, it was determined that a single-phase target product was obtained. If the peak intensity ratio was 5 or more, it was determined that a substance having a high content of the target chalcogen compound was obtained, and the result is shown by Δ in FIG. When the peak intensity ratio was less than 5, the content of the target chalcogen compound was determined to be low, and indicated by x. The evaluation criteria are the same in the following examples.

  As a result, it was found that a reaction temperature of at least 220 ° C. or higher is required for the chalcogenation reaction in order to produce a highly pure chalcogen compound.

Moreover, as a result of investigating the particle size of the chalcogen compound powder prepared in Sample 8, Sample 9, and Sample 10 with TEM, the average particle size (D TEM ) was 10 nm to 15 nm. The average particle diameter (D TEM ) was obtained by taking a TEM image with JEM-2010 manufactured by JEOL Ltd. at a magnification of 100,000 times, measuring the particle diameter of any 100 particles among all particles, and calculating the average Value.

  Some of the obtained chalcogen compounds were subjected to composition analysis by fluorescent X-rays. X-ray fluorescence analysis was performed using JSX-3201 manufactured by JEOL Ltd.

  FIG. 4 shows the analysis results, and Samples 8, 9, and 10 are shown in terms of atomic ratios of constituent elements. According to this, it was confirmed that the chalcogen compound close | similar to the target composition ratio (Cu: In: Ga: Se = 1: 0.7: 0.3: 2) was obtained.

FIG. 5 is a graph showing the X-ray diffraction results of the obtained chalcogen compound (sample 10), in which the vertical axis represents peak intensity [cps] and the horizontal axis represents diffraction angle (2θ) [°]. According to this, no peaks other than the peak indicating CuIn 0.7 Ga 0.3 Se 2 were observed. In addition, it turns out that the peak in the range of 20 degrees-25 degrees recognized in FIG. 5 originates in the adhesive material of a measurement jig | tool.

  In Example 2, the test was performed in the same manner as in Example 1 except that the amount of Se powder (chalcogen source) to be added was 1: 2 in terms of the atomic ratio of Cu to Se (Cu: Se).

  FIG. 6 shows the evaluation results of Sample 1 to Sample 10 prepared at each oxidation heating temperature. The same result as in Example 1 was obtained.

FIG. 7 shows the evaluation results of the products obtained by the chalcogenation reaction by the same X-ray diffraction evaluation method as in Example 1 for Sample 1 to Sample 10. As a result, it was confirmed that CuIn 0.7 Ga 0.3 Se 2 was obtained. It was found that a reaction temperature of at least 220 ° C. or higher was required during the chalcogenation reaction in order to produce a high-purity chalcogen compound (CuIn 0.7 Ga 0.3 Se 2 ). In Sample 8, the sample 9, as a result of the particle size of the chalcogen compound powder prepared was examined by TEM in the sample 10, both the average particle diameter (D TEM) was 7Nm~12nm.

  FIG. 8 shows the result of fluorescent X-ray analysis by the same method as in Example 1. From these, it was confirmed that the chalcogen compounds close to the target composition ratio (Cu: In: Ga: Se = 1: 0.7: 0.3: 2) were obtained for samples 8, 9, and 10. It was done.

In the synthesis of CuIn 0.7 Ga 0.3 Se 2 of Example 2, SeS (SeS powder to be added (chalcogen source) as a chalcogen source was added in an atomic ratio of Cu: Se: S of 1 with respect to Cu). : 1: 1). Other conditions were the same.

FIG. 9 shows the evaluation results of the products obtained by the chalcogenation reaction by the same X-ray diffraction evaluation method as in Example 1 for Sample 1 to Sample 10. From the evaluation result of X-ray diffraction, it was confirmed that CuIn 0.7 Ga 0.3 SeS was obtained. In order to produce a high-purity chalcogen compound (CuIn 0.7 Ga 0.3 SeS), it has been found that a reaction temperature of at least 220 ° C. or higher is required during the chalcogenation reaction. Moreover, as a result of investigating the particle size of the chalcogen compound powder prepared in Sample 8, Sample 9, and Sample 10 with TEM, the average particle size (D TEM ) was 12 nm to 20 nm.

  FIG. 10 shows the results of fluorescent X-ray analysis of samples 9, 10, and 11 by the same method as in Example 1. From these, the chalcogen compounds close to the target composition ratio (Cu: In: Ga: S: Se = 1: 0.7: 0.3: 1: 1) were obtained for Samples 9, 10, and 11. That was confirmed.

Using a reducing solvent in generating a metal hydroxide from Example 4, a metal salt, was synthesized CuIn 0.7 Ga 0.3 Se 2. Purely 0.01 mol of copper chloride, 0.007 mol of indium chloride and 0.003 mol of gallium chloride so that the atomic ratio of Cu, In, and Ga (Cu: In: Ga) is 1: 0.7: 0.3. 50 ml of water and 100 g of TEG (reducing solvent) were dissolved in a mixed solution, and the solution was put into a 250 ml flask. Subsequently, while stirring and rotating a feather having a diameter of 5 cm at 300 rpm, a 1N solution of sodium hydroxide was added dropwise to neutralize, and the addition was terminated at a pH of 8.5. A precipitate was formed. Next, while rotating and stirring the wings having a diameter of 5 cm at 300 rpm, nitrogen was bubbled at 100 ml / min, and Se powder (chalcogen source) so that the atomic ratio of Cu to Se (Cu: Se) was 1: 2.5. ) Was added in excess to obtain a mixed solvent. In this state, the mixed solvent was heated for 10 hours at 10 reaction temperatures shown in FIG. 11 at 150 ° C. to 300 ° C. to try to produce a chalcogen compound. Thereafter, the mixed solvent containing the reaction product is filtered using a Nutsche, and then the cake is redispersed with pure water, and the filtration is further repeated until the filtrate has a conductivity of 10 −1 Sm −1 or less. The cake obtained was vacuum-dried to obtain chalcogen compound powder (sample 1 to sample 10). This powder was evaluated in the same manner as in Example 1.

FIG. 11 shows the evaluation results obtained by evaluating the samples 1 to 10 (products obtained by the chalcogenation reaction) obtained above by the same X-ray diffraction as in Example 1. From the evaluation result of X-ray diffraction, it was confirmed that CuIn 0.7 Ga 0.3 Se 2 was obtained. It was found that a reaction temperature of at least 220 ° C. or higher was required during the chalcogenation reaction in order to produce a high-purity chalcogen compound (CuIn 0.7 Ga 0.3 Se 2 ). Moreover, as a result of investigating the particle size of the chalcogen compound powder prepared in Sample 8, Sample 9, and Sample 10 with TEM, the average particle size (D TEM ) was 7 nm to 13 nm.

  FIG. 12 shows the X-ray fluorescence analysis results of Sample 9, Sample 10, and Sample 11 by the same method as in Example 1. As a result, a chalcogen compound close to the target composition ratio (Cu: In: Ga: Se = 1: 0.7: 0.3: 2) was obtained for Sample 9, Sample 10, and Sample 11. ,confirmed.

In Example 5, the synthesis of CuIn 0.9 Ga 0.1 Se 2 was performed. Copper, 0.01 mol, indium chloride, 0.009 mol and gallium chloride, 0.001 mol were made of metal so that the atomic ratio of Cu, In, and Ga (Cu: In: Ga) was 1: 0.9: 0.1. The test was conducted in the same manner as in Example 4 except that it was used as a source and the Se powder was added excessively so that the atomic ratio of Cu to Se (Cu: Se) was 1: 2.3. It was.

FIG. 13 shows the evaluation results obtained by evaluating the samples 1 to 10 (products obtained by the chalcogenation reaction) obtained above by the same X-ray diffraction as in Example 1. From the evaluation result of X-ray diffraction, it was confirmed that CuIn 0.9 Ga 0.1 Se 2 was obtained. To produce high purity chalcogenide (CuIn 0.9 Ga 0.1 Se 2) , at least 220 ° C. or higher reaction temperature was found to be required during chalcogenide reaction. Moreover, as a result of investigating the particle size of the chalcogen compound powder prepared in Sample 8, Sample 9, and Sample 10 with TEM, the average particle size (D TEM ) was 8 nm to 13 nm.

  FIG. 14 shows the X-ray fluorescence analysis results for Sample 9, Sample 10, and Sample 11 by the same method as in Example 1. As a result, a chalcogen compound close to the target composition ratio (Cu: In: Ga: Se = 1: 0.9: 0.1: 2) was obtained for Sample 9, Sample 10, and Sample 11. ,confirmed.

In Example 6 was synthesized CuIn 0.5 Ga 0.5 Se 2. Copper mol 0.01 mol, indium chloride 0.005 mol and gallium chloride 0.005 mol were metal so that the atomic ratio of Cu, In, and Ga (Cu: In: Ga) was 1: 0.5: 0.5. The test was conducted in the same manner as in Example 4 except that it was used as a source and excessively added Se powder so that the atomic ratio of Cu to Se (Cu: Se) was 1: 2.2. It was.

FIG. 15 shows the results of evaluating the samples 1 to 10 (products obtained by the chalcogenation reaction) obtained as described above by the same X-ray diffraction as in Example 1. From the X-ray diffraction evaluation results, it was confirmed that CuIn 0.5 Ga 0.5 Se 2 was obtained. It was found that a reaction temperature of at least 220 ° C. or higher was required during the chalcogenation reaction in order to produce a high-purity chalcogen compound (CuIn 0.5 Ga 0.5 Se 2 ). Moreover, as a result of investigating the particle size of the chalcogen compound powder prepared in Sample 8, Sample 9, and Sample 10 with TEM, the average particle size (D TEM ) was 8 nm to 13 nm.

  FIG. 16 shows the fluorescent X-ray analysis results for Sample 9, Sample 10, and Sample 11 by the same method as in Example 1. As a result, a chalcogen compound close to the target composition ratio (Cu: In: Ga: Se = 1: 0.5: 0.5: 2) was obtained for Sample 9, Sample 10, and Sample 11. ,confirmed.

FIG. 17 is a graph showing the X-ray diffraction result of the obtained chalcogen compound (sample 9), in which the vertical axis represents peak intensity [cps] and the horizontal axis represents diffraction angle (2θ) [°]. According to this, no peaks other than the peak indicating CuIn 0.5 Ga 0.5 Se 2 were observed.

In Example 7 was synthesized CuIn 0.1 Ga 0.9 Se 2. Copper mol 0.01 mol, indium chloride 0.001 mol, and gallium chloride 0.009 mol are metal so that the atomic ratio of Cu, In, and Ga (Cu: In: Ga) is 1: 0.1: 0.9. The test was conducted in the same manner as in Example 4 except that it was used as a source and that Se powder was added excessively so that the atomic ratio of Cu to Se (Cu: Se) was 1: 2.4. It was.

FIG. 18 shows the results of evaluating the samples 1 to 11 (products obtained by the chalcogenation reaction) obtained as described above by the same X-ray diffraction as in Example 1. From the evaluation results of the X-ray diffraction, it was confirmed that CuIn 0.1 Ga 0.9 Se 2 was obtained. It was found that a reaction temperature of at least 220 ° C. or higher was required during the chalcogenation reaction in order to produce a high-purity chalcogen compound (CuIn 0.1 Ga 0.9 Se 2 ). Moreover, as a result of investigating the particle size of the chalcogen compound powder produced in Sample 6 to Sample 11 with TEM, the average particle size (D TEM ) was 8 nm to 26 nm.

  FIG. 19 shows the result of fluorescent X-ray analysis of Sample 9, Sample 10, and Sample 11 by the same method as in Example 1. As a result, a chalcogen compound close to the target composition ratio (Cu: In: Ga: Se = 1: 0.1: 0.9: 2) was obtained for Sample 9, Sample 10, and Sample 11. ,confirmed.

Figure 20, in Example 7, the chalcogen compound created in the sample 6 to sample 11 CuIn 0.1 Ga 0.9 Se 2 is generated, the result of measuring the crystallite diameter using an X-ray diffraction method Indicated. As a result, these crystallite diameters were 5 nm to 24 nm. The crystallite diameter D was determined using the Scherrer equation. First, Scherrer's formula is expressed by the following general formula.

D = K · λ / βcos θ (1)
In the above formula, K: Scherrer constant, D: crystallite diameter, λ: measured X-ray wavelength, β: half width of peak obtained by X-ray diffraction, and θ: Bragg angle of diffraction line. If K adopts a value of 0.94 and the X-ray tube uses Cu, the equation (1) can be rewritten as the following equation.

D = 0.94 × 1.5405 / βcos θ (2)
The crystallite diameter D calculated by the equation (2) is a value shown in FIG.

In Example 8, CuIn 0.5 Ga 0.5 S 2 was synthesized. 30 ml of 0.01 mol of copper chloride, 0.005 mol of indium chloride and 0.005 mol of gallium chloride so that the atomic ratio of Cu, In and Ga (Cu: In: Ga) is 1: 0.5: 0.5. Was dissolved in a mixed solvent of 100 g of TEG and 100 g of TEG, and this solution was put into a 250 ml flask. Subsequently, while stirring and rotating a feather having a diameter of 5 cm at 300 rpm, the flask was neutralized by dropping a 1N solution of sodium hydroxide to finish the pH at 7.9, and a hydroxide coprecipitate was produced. did. Thereafter, a mixed gas of hydrogen sulfide and nitrogen in a volume ratio of 1: 1 was bubbled into the mixed solvent in which the coprecipitate was generated at 200 ml / min. In this state, the temperature was raised to 120 ° C. and held for 2 hours, and then the temperature was raised to 1 ° C./min to the reaction temperature (150 ° C. to 330 ° C.) shown in FIG. Samples 1 to 12 having different reaction temperatures were prepared. Thereafter, the mixed solvent containing the reaction product is filtered using a Nutsche, and then the cake is redispersed with pure water, and the filtration is further repeated until the filtrate has a conductivity of 10 −1 Sm −1 or less. The cake obtained was vacuum-dried to obtain a chalcogen compound powder. This chalcogen compound powder was evaluated in the same manner as in Example 7.

FIG. 21 shows the result. From this, it was found that a reaction temperature of at least 220 ° C. or higher is necessary for the chalcogenation reaction. Moreover, as a result of investigating the particle size of the chalcogen compound powder produced in Sample 7 to Sample 12 with TEM, the average particle size (D TEM ) was about 12 nm to 60 nm.

FIG. 22 shows the results of evaluating the crystallite diameter D of the chalcogen compounds prepared in Sample 7 to Sample 12 in which CuIn 0.5 Ga 0.5 S 2 was generated in Example 8. The crystallite diameter D was calculated by the same method as in Example 7. As a result, the crystallite diameter D was 14 nm to 45 nm.

  As described above, in Examples 1 to 8, the chalcogen compound powder obtained by the production method in which a metal salt is used as a starting material and produced via a metal hydroxide or metal oxide has been described. Chalcogen compound powder can also be produced (without producing metal hydroxide or metal oxide).

  With reference to FIGS. 23 to 42, the chalcogen compound obtained by another production method will be described in detail. FIG. 23 is a flowchart showing another method for producing the chalcogen compound powder of this embodiment.

  Another method for producing the chalcogen compound powder of the present embodiment is one selected from an element group of one or more metal salts, a high boiling point solvent, sulfur (S), selenium (Se), and tellurium (Te). A step of producing a mixed solvent containing the compound (single or) composed of the above, and a step of heating the mixed solvent at a temperature of 170 ° C. to 500 ° C. By this method, a chalcogen compound powder having an average particle size of 40 nm or less can be obtained.

  Here, a compound composed of one or more selected from the element group of sulfur (S), selenium (Se), and tellurium (Te) (or a simple substance) is hereinafter referred to as a chalcogen source. As will be described in detail later, the high boiling point solvent in other production methods refers to a solvent having a boiling point of 170 ° C. or higher at normal pressure.

  Specifically, a metal salt is mixed as a starting material in a high boiling point solvent, and heated in a state where a chalcogen source is added to the high boiling point solvent to produce a predetermined chalcogen compound. Various chalcogen compound powders can be obtained by selecting the type of metal salt and chalcogen source to be used.

  The metal salt is preferably dissolved in the solvent when added to the solvent and heated. When the metal salt does not dissolve at all in the solvent, it is difficult to obtain a chalcogen compound. As a method for adding the metal salt and chalcogen source contained in the mixed solvent to the high boiling point solvent, the metal salt and the chalcogen source can be added to the high boiling point solvent before or during heating. Further, the chalcogen source can be added to the high boiling point solvent to which the metal salt has been added during heating, and the metal salt can be added to the high boiling point solvent to which the chalcogen source has been added. Furthermore, a metal salt is added to a high boiling point solvent to form a first solution, a chalcogen source is added to another high boiling point solvent to form a second solution, and these are mixed to obtain a mixed solvent. Is also possible. The heating in this case may be performed before or after the mixed solvent is generated.

As a metal salt used as a starting material, for example, as a metal halide salt, cupric chloride (CuCl 2 ), cadmium chloride (CdCl 3 ), indium chloride (InCl 3 ), gallium chloride, zinc chloride, tin chloride, bromide Typical examples include metal chlorides such as copper (CuBr 2 ) and copper iodide (CuI 2 ), metal bromides, metal iodides, metal fluorides, cupric nitrate (Cu (NO 3 ) 2 ), nitric acid Examples include indium, gallium nitrate, zinc nitrate, tin nitrate, and nitrate. These salts may contain water of crystallization. Further, the metal salt to be added may be a powder or a dissolved state.

  The metal element contained in the metal salt includes at least one of 3d and 4f transition metal elements, group III metal elements, and group VI metal elements. 3d and 4f transition metal elements include iron (Fe), cobalt (Co), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), cadmium (Cd), and zinc (Zn). , Titanium (Ti), vanadium (V), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy) , Erbium (Er), and ytterbium (Yb). Examples of Group III metal elements include aluminum (Al), gallium (Ga), thallium (Tl), and indium (In). In addition, examples of the Group VI metal element include tin (Sn) and lead (Pb).

When the chalcogen compound to be obtained is a compound containing a plurality of metal elements, the metal salt may have the same metal element ratio as that of the chalcogen compound. Specifically, for example, when CuInSe 2 is manufactured, a copper salt and an indium salt may be used as raw materials so that the atomic ratio of copper (Cu) and indium (In) is 1: 1.

  As the high boiling point solvent, those having a boiling point of 170 ° C. or higher at normal pressure are preferable, and those having a boiling point of 220 ° C. or higher are particularly preferable. As will be described later, in order to obtain a chalcogen compound, it is necessary to heat the high boiling point solvent to 170 ° C. or higher, preferably 220 ° C. or higher. The reaction to obtain the compound can be performed. When the reaction is carried out under pressure, a solvent having a boiling point of less than 170 ° C. can also be used. Hereinafter, unless otherwise specified, the temperature is a temperature under normal pressure.

  Since the high boiling point solvent is required to have the ability to dissolve the metal salt, an example of the high boiling point solvent is an alcohol solvent having a boiling point in the range of 100 ° C to 400 ° C. In order to carry out the chalcogenation reaction at normal pressure, the boiling point is preferably 170 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 250 ° C. or higher in consideration of the yield of the chalcogen compound.

Specifically, the high boiling point solvent includes monohydric alcohol or dihydric alcohol glycol. Examples of the monohydric alcohol include butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, nonyl alcohol, cyclopentanol, benzyl alcohol, and cinnamyl alcohol. Examples of glycol solvents include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, benzpinacol, hydro Benzoyl, cyclopentadiol, cyclohexanediol, cyclohexanediol, glycolic acid amide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monoethyl ether, diethylene glycol dibutyl ether, acetic acid diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, etc. big Intended polyethylene glycol, polyethylene glycol esters, polyethylene glycol ethers. In particular, glycols and diols are preferable because they have two hydroxyl groups and thus have polarity and contribute to the dispersibility of the powder. Examples of such a solvent include —CH 2 —CHOH, or —CHR—CHOH, —CR 1 R 2 —CHOH, ═CHCHOH, ═CRCHOH (R, R 1 , R 2 : side chain) in the molecule. The boiling point of the solvent is at least 100 ° C. or higher. Furthermore, an organic compound having an aldehyde group -CHO has the same effect. For example, as an aliphatic saturated aldehyde, lauric aldehyde, tridecyl aldehyde, myristic aldehyde, capron aldehyde, heptaldehyde, pentadecyl aldehyde, palmitic aldehyde, marga aldehyde. Examples include aliphatic aldehydes such as succindialdehyde, aliphatic unsaturated aldehydes such as crotonaldehyde, and aromatic aldehydes such as benzaldehyde, tolualdehyde, salicylaldehyde, and cinnamaldehyde. And naphthaldehyde, and the heterocyclic aldehyde includes furfural. Examples of amine-based high-boiling solvents include hexylamine, hebutinamine, octylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, dibutylamine, diamylamine, cyclohexylamine, aniline, naphthylamine, and toluidine. is there.

  Tetraethylene glycol and triethylene glycol are particularly suitable because of their high boiling point and cost and operability.

  Further, as a simple substance selected from the element group of S, Se, Te, or a compound containing one or more selected from these element groups (hereinafter referred to as a chalcogen source), which is added to the high boiling point solvent together with the metal salt powder. Can be an alloy powder of an element group, a hydrogenated chalcogen compound, or an organic metal of a chalcogen element.

  An alloy is an alloy having two or more elements selected from the group consisting of Se, Te, and S as constituent elements.

Representative examples of the hydrogenated chalcogen compound include hydrogen selenide (H 2 Se), hydrogen sulfide (H 2 S), hydrogen telluride (H 2 Te), and the like. Is alkyl selenol, aryl selenol, dialkyl selenide, diaryl selenide, halogenated alkyl selenide, halogenated aryl selenide, dialkyl selenoxide, diaryl selenoxide, selenone, alkyl selenic acid, aryl selenic acid, selenonic acid , Selenoketone, selenoic acid, selenophene, and the like. For example, typical examples of dialkyl selenium include Se (CH 3 ) 2 , (C 2 H 5 ) 2 Se, (C 4 H 9 ) 2 Se, (C 6 H 13 ) 2 Se, and the like. One or more of these chalcogen-based elements (Se, S, Te), simple substances, alloys and compounds can be used.

  And the mixed solvent of the said chalcogen source, a metal salt, and a high boiling point solvent is heated at the temperature of 170 to 500 degreeC. Thereby, the chalcogen source, the mixed solvent of the metal salt and the high boiling point solvent are subjected to a chalcogenation reaction, and the chalcogen compound powder can be easily obtained. If the heating temperature of the mixed solvent (temperature for the chalcogenation reaction: hereinafter, reaction temperature) is low, the formation of the chalcogen compound may not be sufficient. Since no change is observed, it is preferably 170 ° C. to 400 ° C. (however, in the case of Se compound, 220 ° C. to 400 ° C.), more preferably 250 ° C. to 400 ° C.

  Although the detailed reaction mechanism is not clarified in the production method of the present embodiment, a high-boiling solvent having a higher boiling point than that of ethyl alcohol or the like is used in the above temperature range (170 ° C. to 500 ° C., and Se is contained in the chalcogen source). Is heated to 220 ° C. to 500 ° C.) so that the chalcogen source is dissolved in the solvent, and the Se, Te, S of the chalcogen source and the metal of the metal salt dissolved in the solvent are reacted. Thus, it is considered that the chalcogen compound powder can be easily obtained. Further, the particles of the chalcogen compound powder thus prepared have a particle diameter of 1 nm to 40 nm, and a powder having no sintering or bonding between particles is obtained.

  As is apparent from the following examples, good results can be obtained when the heating temperature of the mixed solvent is a certain temperature or higher. However, if the mixed solvent is heated to a high temperature until boiling, the chalcogenation reaction proceeds, but the mixed solvent (high boiling point solvent) is thermally decomposed or evaporated, resulting in an unstable reaction. Therefore, the heating temperature (reaction temperature) of the mixed solvent is lower than the temperature at which the mixed solvent boils. Specifically, the heating temperature (reaction temperature) of the mixed solvent of this embodiment is preferably 220 ° C. or higher, and more preferably 250 ° C. or higher, from the viewpoint of the yield of the chalcogen compound. The upper limit temperature of the reaction temperature is preferably not higher than the boiling point of the solvent, specifically 500 ° C. or lower.

For example, according to this embodiment, an example of obtaining a CuInSe-based chalcogen compound is as follows. Cu (NO 3 ) 2 and In (NO 3 ) 3 are mixed with a high boiling point solvent, and the metal Se powder is added to the solvent and heated to 220 ° C. to 400 ° C. Thereby, a reaction for generating a chalcogen compound (hereinafter, chalcogenation reaction) is remarkably accelerated, and a CuInSe-based compound is easily formed.

  In such a reaction, the same effect was obtained when the reaction was carried out using other chalcogen elements. More specifically, other CdSe series, CuInGaSe series, copper selenide (CuSe) series, tellurium selenide (TeSe) series, zinc selenide (ZnSe) series, gallium selenide (GaSe) series, indium selenide (InSe). ), Cobalt selenide (CoSe), samarium selenide (SmSe), manganese selenide (MnSe), tin selenide (SnSe), cerium selenide (CeSe), etc. Effects can be obtained. Fe, Co, Cu, Cr, Mn, Ni, Cd, Zn, Ti, V, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Al, Ga, Tl, and InSn and The same effect can be obtained in Pb in the chalcogenation reaction.

  The reaction proceeds easily by bubbling nitrogen or argon into a high boiling point solvent. If the gas flow rate is large, chalcogen elements having a high vapor pressure may be carried out of the chalcogenation reaction system, and therefore there is an appropriate amount of gas flow for bubbling.

Further, the chalcogen source to be added may not be powdery, and for example, a gas such as hydrogen selenide (H 2 Se) may be supplied. As described above, when the metal salt powder and the high-boiling solvent are mixed and heated, bubbling with nitrogen or the like facilitates the reaction. Therefore, a gasified chalcogen source may be supplied together with this bubbling gas. .

  If a pressurizer is used for the chalcogenation reaction, a solvent having a boiling point at normal pressure lower than 170 ° C. can be used.

  The solid concentration in the metal salt solution at the start of the chalcogenation reaction in this production method is the same as in the production methods used in Examples 1 to 8. That is, the solid content concentration of the metal salt at the start of the chalcogenation reaction is preferably in the range of 0.1% by mass to 50% by mass. More preferably, it is the range of 0.1 mass%-10 mass%.

  The amount of chalcogen source added during the chalcogen reaction is the same as in the production methods used in Examples 1 to 8, and it is preferable to add 1 to 1.3 times the equivalent.

  In the present embodiment, hereinafter, “addition in excess” means adding an amount of more than 1 time and not more than 1.5 times the equivalent. In addition, the atomic ratio of the metal of the obtained chalcogen compound to Se, S, Te depends on the atomic ratio of the chalcogen source to the metal contained in the metal salt added, the temperature and time of the chalcogenization reaction, the gas flow rate of bubbling, etc. It is possible to control.

  Specifically, in the following cases, the atomic ratio of Se, S, and Te to the metal in the obtained chalcogen compound increases.

  First, when the chalcogen source atomic ratio to be added to the metal contained in the metal salt to be added is high, second, when the chalcogenation reaction temperature is low, and third, the chalcogenation reaction time is short In the fourth case, the bubbling gas flow rate is small. In particular, in the second to fourth cases, loss due to evaporation can be reduced.

  The thus produced chalcogen compound powder can be dispersed in a target solvent by a solvent substitution method. At this time, a surfactant can be attached to the particle surface so that the solvent can be easily replaced, and the surfactant can be easily dispersed in the target solvent.

  Specifically, it is the same as the manufacturing method used in Example 1 to Example 8, and the description is omitted.

  Hereinafter, the embodiment will be described in detail with reference to FIGS. In the following examples, even if there is a difference between the elemental composition ratio of each element of the obtained chalcogen compound and the elemental composition ratio intended to be generated, if the difference is 5% or less, it will be generated. And may be expressed by the molecular formula of the intended elemental composition ratio.

(Example of synthesizing CuSe particles)
A solution prepared by dissolving 0.01 mol of copper nitrate in 100 mL of tetraethylene glycol was placed in a 250 mL flask. Here, Se powder was added as a chalcogen source to obtain a mixed solvent. The amount of Se powder added was such that the atomic ratio of Cu to Se (Cu: Se) was 1: 1.1. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 300 rpm with a blade having a diameter of 5 cm.

Next, the mixed solvent in this state was heated to 10 kinds of reaction temperatures between 150 ° C. and 300 ° C. shown in FIG. The reaction temperature was maintained for 5 hours, and a reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder subjected to cleaning by repeated washing and filtration with isopropyl alcohol to a conductivity of the filtrate and 10 -1 Sm -1 or less, then dried in vacuo at 60 ° C..

  FIG. 24 mainly performs crystal analysis using an X-ray analyzer (X-Ray Diffractometer, hereinafter referred to as XRD, RAD-rX manufactured by Rigaku Corporation), and examines the generation state of a chalcogen compound (CuSe) for Sample 1 to Sample 10, The result of having investigated the reaction temperature of the chalcogenation reaction required for the production | generation of a chalcogen compound is shown.

  At this time, X-ray diffraction was measured under the condition of 50 kV and 100 mA, and the highest peak height among the peak intensities of the target chalcogen compound was divided by the highest peak height among the peak intensities of other substances. The value (hereinafter, peak intensity ratio) was determined. If the peak intensity ratio was 15 or more, it was determined that the target chalcogen compound was obtained with high purity (a single phase of the target product was obtained), and indicated by ○ in FIG. If the peak intensity ratio was 5 or more, it was determined that a substance having a high content of the target chalcogen compound was obtained, and the result is indicated by Δ in FIG. When the peak intensity ratio was less than 5, the content of the target chalcogen compound was determined to be low, and indicated by x. This evaluation criterion is the same in the other examples. As a result, it was found that a reaction temperature of at least 220 ° C. or higher is required for the chalcogenation reaction in order to produce a highly pure chalcogen compound.

  Moreover, as a result of investigating the particle size of the chalcogen compound powder prepared in Sample 8, Sample 9, and Sample 10 with TEM, the average particle size (DTEM) was 16 nm to 22 nm. DTEM photographed the TEM image with JEM-2010 manufactured by JEOL Ltd. at a magnification of 100,000 times, and measured the particle diameter of 100 particles out of all the particles to obtain the average value.

  FIG. 25 shows the result of compositional analysis by fluorescent X-ray for some of the obtained chalcogen compounds. X-ray fluorescence analysis was performed using JSX-3201 manufactured by JEOL Ltd. as an apparatus.

  In FIG. 25, the analysis results of Samples 8, 9, and 10 are shown as atomic ratios of constituent elements. According to this, it was confirmed that a chalcogen compound close to the target composition ratio (Cu: Se = 1: 1) was obtained.

  FIG. 26 is a graph showing an X-ray diffraction result of the obtained chalcogen compound, and is an analysis result of Sample 8. The vertical axis is the peak intensity [cps], and the horizontal axis is the diffraction angle (2θ) [°].

  Referring to FIG. 26, in sample 8, no peak other than the peak indicating CuSe was observed.

  In Example 9, each chloride of Fe, Co, Cr, Mn, Ni, Zn, Ti, V, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, and Yb instead of copper nitrate Using (metal salt), the other conditions were the same, and an attempt was made to produce a chalcogen compound. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound.

  As a result, when the temperature of the chalcogenation reaction is 220 ° C. or more, the peak intensity ratio is 15 or more, and the atomic ratio of the metal element to Se (metal element: Se) is 1: 0.95 to 1: 1.05. A chalcogen compound was obtained. The obtained chalcogen compound powder had a TEM particle size of less than 40 nm.

In Example 9, the same method was used except that (C 2 H 5 ) 2 Se was used instead of Se powder. As a result, the chalcogenization reaction temperature was set to 220 ° C. or higher, whereby the peak intensity ratio was Was a chalcogen compound having an atomic ratio of metal element to Se (metal element: Se) of 1: 1.00 to 1: 1.05. The obtained chalcogen compound powder had a TEM particle size of 15 nm to 20 nm.

  Example 9 is the same as Example 9 except that Se powder is not added and the bubbling gas is changed from 100 mL / min of nitrogen gas to 200 mL / min of nitrogen and selenium hydride gas mixed at a volume ratio of 1: 1. The test was carried out by the method.

  As a result, by setting the chalcogenation reaction temperature to 220 ° C. or higher, the peak intensity ratio is 15 or higher, and the atomic ratio of metal element to Se (metal element: Se) is from 1: 1.06 to 1: 1.12. A chalcogen compound was obtained. The obtained chalcogen compound powder had a TEM particle size of 20 nm or less.

(Example in which Example 9 and Se addition method are different)
A solution prepared by dissolving 0.01 mol of copper nitrate in 100 mL of triethylene glycol was placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 300 rpm with a blade having a diameter of 5 cm. Next, in this state, each of Sample 1 to Sample 8 was heated to eight kinds of reaction temperatures between 150 ° C. and 240 ° C. shown in FIG. 24 to obtain a first solution. Separately, selenium powder having an atomic ratio of Cu to Se (Cu: Se) of 1: 1.1 was added to 100 mL of triethylene glycol in a 250 mL Erlenmeyer flask to produce a second solution, The solution of 2 was heated to 220 ° C. The second solution was added at 5 mL / min to a triethylene glycol solution (first solution) in which copper nitrate was dissolved to obtain a mixed solvent. The reaction temperature was maintained for 5 hours, and a reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C.

  As a result of performing the same evaluation as in Example 9 on the obtained chalcogen compound powder, the reaction temperature was 220 ° C. or higher, the peak intensity ratio was 15 or higher, 240 ° C. or higher, and the peak intensity ratio was 30 or higher. The result was the same as in Example 9.

  As a result of the composition analysis by fluorescent X-rays for Samples 7 and 8, the atomic ratio of Cu to Se (Cu: Se) was 1: 1.03 to 1: 1.05. The TEM average particle size was 15 nm to 18 nm.

(Example in which the metal salt addition method is different from Example 9)
To synthesize CuSe particles, 100 mL of tetraethylene glycol was placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 300 rpm with a feather having a diameter of 5 cm. Next, it heated to 250 degreeC in this state, and temperature was hold | maintained. Here, an amount of Se powder in which the atomic ratio (Cu: Se) of Cu and Se contained in copper nitrate to be added later is 1: 1.1 is added to heated tetraethylene glycol, and the second solution is added. Got.

Thereafter, the temperature of tetraethylene glycol (second solution) in which Se powder was added to four types of temperatures between 220 ° C. and 300 ° C. shown in FIG. Separately, a liquid (first solution) prepared by dissolving 0.01 mol of copper nitrate in 100 mL of tetraethylene glycol was prepared, and added to tetraethylene glycol (second solution) to which Se powder was added at 5 mL / min, and mixed. A solvent was obtained. After the addition, the adjusted temperature was maintained for 5 hours, and a reaction (chalcogenization reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

  FIG. 27 is a table showing the results of examining the production state of the chalcogen compound (CuSe) and the reaction temperature. The reaction temperature was 220 ° C. or higher, and the peak intensity ratio was 30 or higher. Moreover, as a result of the composition analysis by fluorescent X-rays for Samples 1 and 4, the atomic ratio of Cu to Se (Cu: Se) was 1: 1.01 to 1: 1.04. The TEM average particle size was 15 nm to 20 nm.

In Example 9 was conducted to synthesize CuSe particles but, in the present embodiment was synthesized Cu 0.8 In 1.0 Se 2.1 with chalcopyrite crystal structure. A 250 ml flask is prepared by dissolving 0.008 mol of copper nitrate and 0.01 mol of indium nitrate in 100 mL of tetraethylene glycol so that the atomic ratio of Cu and In (Cu: In) is 0.8: 1.0. I put it in. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 300 rpm with a feather having a diameter of 5 cm.

Next, in this state, each of samples 1 to 10 was heated to 10 kinds of reaction temperatures between 150 ° C. and 300 ° C. shown in FIG. An amount of Se powder having an atomic ratio of Cu to Se (Cu: Se) of 1: 2.1 was added to 100 mL of the above tetraethylene glycol in a 250 mL Erlenmeyer flask to obtain a mixed solvent. The reaction temperature was maintained for 5 hours, and a reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

FIG. 28 is a table showing the results of examining the production state of the chalcogen compound (Cu 0.8 In 1.0 Se 2.1 ) and the reaction temperature, and FIG. 29 shows the composition analysis by fluorescent X-rays. FIG. 30 is a graph showing the results, and FIG. 30 is a graph showing the X-ray diffraction results of the chalcogen compound of Sample 8.

As a result, it was found that a high-purity Cu 0.8 In 1.0 Se 2.1 powder can be obtained by setting the chalcogenation reaction temperature to 220 ° C. or higher (FIG. 28). As a result of examining the particle sizes of Samples 8, 9, and 10 by TEM, the TEM average particle size was 13 nm to 18 nm. Samples 8, 9, and 10 were subjected to compositional analysis using fluorescent X-rays. As a result, it was found that crystal powders close to the target composition ratio were generated (FIG. 29). Furthermore, with reference to FIG. 30, the peak of Cu 0.8 In 1.0 Se 2.1 crystal having the target chalcopyrite type crystal structure was confirmed in Sample 8. From this result, it can be seen that a single-phase composition of Cu 0.8 In 1.0 Se 2.1 having a chalcopyrite type crystal structure is obtained.

In Example 12, Cu 0.9 In 1.0 Se 2.1 particles were synthesized. In this example, Cu 0.9 In 0.5 Ga 0.5 Se having a chalcopyrite crystal structure was used. A synthesis of 2.07 was performed. Add 0.009 mol of copper nitrate and 0.005 mol of indium nitrate and 0.005 mol of gallium nitrate so that the atomic ratio of Cu, In, and Ga (Cu: In: Ga) is 0.9: 0.5: 0.5. A first solution dissolved in 100 mL of triethylene glycol was placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 300 rpm with a feather having a diameter of 5 cm.

Next, in this state, each of samples 1 to 10 was heated to 10 kinds of reaction temperatures between 150 ° C. and 300 ° C. shown in FIG. Here, a second solution in which an amount of Se powder having an atomic ratio of Cu to Se (Cu: Se) of 1: 2.15 was added to 100 mL of tetraethylene glycol and heated to 230 ° C. was separately prepared. The second solution containing Se was added to the first solution containing the metal salt at 10 mL / min to obtain a mixed solvent. Thereafter, the temperature of the mixed solvent was adjusted to be the above reaction temperature, this reaction temperature was maintained for 5 hours, and the reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

FIG. 31 is a table showing the formation state of the chalcogen compound (Cu 0.9 In 0.5 Ga 0.5 Se 2.07 ) and the results of examining the reaction temperature, and FIG. 32 shows the composition by fluorescent X-rays. FIG. 33 is a table showing the results of analysis, and FIG. 33 is a graph showing the X-ray diffraction results of the chalcogen compound of Sample 8.

As a result, it was found that high-purity Cu 0.9 In 0.5 Ga 0.5 Se 2.07 powder can be obtained by setting the chalcogenation reaction temperature to 220 ° C. or higher (FIG. 31). Moreover, as a result of investigating the particle size of Samples 8, 9, and 10 by TEM, the TEM average particle size was 20 nm to 25 nm. As a result of the compositional analysis by fluorescent X-rays for Samples 8, 9, and 10, it was found that crystal powder close to the target composition ratio was generated (FIG. 32). Further, with reference to FIG. 33, the peak of Cu 0.9 In 0.5 Ga 0.5 Se 2.07 crystal having the target chalcopyrite type crystal structure was confirmed in Sample 8. From this result, it can be seen that a single-phase composition of Cu 0.9 In 0.5 Ga 0.5 Se 2.07 having a chalcopyrite type crystal structure is obtained.

In this example, Cu 1.0 In 0.7 Ga 0.3 Se 2.0 having a chalcopyrite crystal structure was synthesized. 0.010 mol of copper chloride, 0.007 mol of indium chloride and 0.003 mol of gallium chloride so that the composition of Cu, In, and Ga is 1.0: 0.7: 0.3 by atomic ratio (Cu: In: Ga). Was dissolved in 100 mL of triethylene glycol and placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 600 rpm with a feather having a diameter of 5 cm.

Next, in this state, each of samples 1 to 10 was heated to 10 kinds of reaction temperatures between 150 ° C. and 300 ° C. shown in FIG. Here, a second solution in which an amount of Se powder having an atomic ratio of Cu to Se (Cu: Se) of 1: 2.05 was added to 100 mL of tetraethylene glycol and heated to 270 ° C. was separately prepared. The liquid containing Se (second solution) was added to the liquid containing metal salt (first solution) at 50 mL / min to obtain a mixed solvent. Thereafter, the temperature of the mixed solvent was adjusted to be the above reaction temperature, this reaction temperature was maintained for 5 hours, and the reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

FIG. 34 is a table showing the results of examining the production state of the chalcogen compound (Cu 1.0 In 0.7 Ga 0.3 Se 2.0 ) and the reaction temperature, and FIG. 35 shows the composition by fluorescent X-rays. FIG. 36 is a table showing the results of analysis, and FIG. 36 is a graph showing the X-ray diffraction results of the chalcogen compound of Sample 8.

As a result, it was found that by setting the chalcogenation reaction temperature to 220 ° C. or higher, high-purity Cu 1.0 In 0.7 Ga 0.3 Se 2.0 powder can be obtained (FIG. 34). As a result of examining the particle sizes of Samples 8, 9, and 10 with TEM, the TEM average particle size was 15 to 20 nm. Samples 8, 9, and 10 were subjected to compositional analysis using fluorescent X-rays, and as a result, it was found that crystal powder having a target composition ratio was generated (FIG. 35). Referring to FIG. 36, the peak of Cu 1.0 In 0.7 Ga 0.3 Se 2.0 crystal having the target chalcopyrite type crystal structure was confirmed in Sample 8. From this result, it can be seen that a single-phase composition Cu 1.0 In 0.7 Ga 0.3 Se 2.0 having a chalcopyrite type crystal structure is obtained.

In this example, Cu 1.0 In 0.7 Ga 0.3 S 2.0 having a chalcopyrite crystal structure was synthesized. 0.010 mol of copper chloride, 0.007 mol of indium chloride, 0.003 mol of gallium chloride so that the atomic ratio of Cu, In, and Ga (Cu: In: Ga) is 1.0: 0.7: 0.3 Was dissolved in 100 mL of triethylene glycol (first solution) and placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 600 rpm with a feather having a diameter of 5 cm.

Next, in this state, each of samples 1 to 10 was heated to 10 kinds of reaction temperatures between 150 ° C. and 300 ° C. shown in FIG. A liquid (second solution) prepared by adding S powder in an amount of Cu: S atomic ratio (Cu: S) of 1: 2.05 to 100 mL of tetraethylene glycol and heating to 270 ° C. is prepared separately. did. The liquid containing S (second solution) was added to the liquid containing metal salt (first solution) at 50 mL / min to obtain a mixed solvent. Thereafter, the temperature of the mixed solvent was adjusted to be the above reaction temperature, this reaction temperature was maintained for 5 hours, and the reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

FIG. 37 is a table showing the results of examining the production state of the chalcogen compound (Cu 1.0 In 0.7 Ga 0.3 S 2.0 ) and the reaction temperature, and FIG. 38 shows the composition by fluorescent X-rays. It is a table | surface which shows the result of having analyzed.

As a result, it was found that a high-purity Cu 1.0 In 0.7 Ga 0.3 S 2.0 powder can be obtained by setting the chalcogenation reaction temperature to 180 ° C. or higher (FIG. 37). When the chalcogen source was S, a high-purity chalcogen compound could be obtained even when the chalcogenation reaction temperature was low, compared to the case of Se. This is presumed to be due to the lower melting point of sulfur compared to selenium.

  As a result of examining the particle sizes of Samples 8, 9, and 10 with TEM, the TEM average particle size was 15 to 20 nm. Samples 8, 9, and 10 were subjected to compositional analysis by fluorescent X-ray, and as a result, it was found that crystal powder close to the target composition ratio was generated (FIG. 38).

(Reference example)
By the above production method, Cu 1.0 Zn 0.9 Sn 0.1 S 2.0 having a chalcopyrite crystal structure was synthesized. 0.010 mol of copper chloride, 0.009 mol of zinc chloride, 0.001 mol of tin chloride so that the composition of Cu, Zn, and Sn is 1.0: 0.9: 0.1 in terms of atomic ratio (Cu: Zn: Sn) Was dissolved in 100 mL of triethylene glycol (first solution) and placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 600 rpm with a feather having a diameter of 5 cm.

Next, in this state, each of samples 1 to 10 was heated to 10 kinds of temperatures between 150 ° C. and 300 ° C. shown in FIG. A solution (second solution) prepared by adding S powder in an amount of Cu: S atomic ratio (Cu: S) of 1: 2.05 to 100 mL of tetraethylene glycol and heating to 200 ° C. is prepared separately. did. The liquid containing S (second solution) was added to the liquid containing metal salt (first solution) at 50 mL / min to obtain a mixed solvent. Thereafter, the temperature of the mixed solvent was adjusted to be the above reaction temperature, this reaction temperature was maintained for 5 hours, and the reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

FIG. 39 is a table showing the formation state of the chalcogen compound (Cu 1.0 Zn 0.9 Sn 0.1 S 2.0 ) and the results of examining the reaction temperature. FIG. 40 shows the composition by fluorescent X-rays. It is a table | surface which shows the result of having analyzed.

As a result, it was found that high-purity Cu 1.0 Zn 0.9 Sn 0.1 S 2.0 powder was obtained by setting the chalcogenation reaction temperature to 180 ° C. or higher (FIG. 39). When the chalcogen source was S, a high-purity chalcogen compound could be obtained even when the chalcogenation reaction temperature was low, compared to the case of Se. As a result of examining the particle sizes of Samples 8, 9, and 10 with TEM, the TEM average particle size was 15 to 20 nm. Samples 8, 9, and 10 were subjected to compositional analysis using fluorescent X-rays, and as a result, it was found that crystal powder having a target composition ratio was generated (FIG. 40).

(Reference example)
The above manufacturing method, was synthesized Cu 1.0 Zn 0.9 Sn 0.1 S 0.5 Se 1.5 with chalcopyrite crystal structure. 0.010 mol of copper chloride, 0.009 mol of zinc chloride, 0.001 mol of tin chloride so that the composition of Cu, Zn, and Sn is 1.0: 0.9: 0.1 in terms of atomic ratio (Cu: Zn: Sn) Was dissolved in 100 mL of triethylene glycol (first solution) and placed in a 250 mL flask. Subsequently, nitrogen was bubbled at 100 ml / min while stirring the inside of the flask at 600 rpm with a feather having a diameter of 5 cm.

Next, in this state, each of samples 1 to 10 was heated to 10 kinds of reaction temperatures between 150 ° C. and 300 ° C. shown in FIG. Here, an amount of S powder in which the atomic ratio of Cu and S (Cu: S) is 1: 0.5 and an amount of Se powder in which the atomic ratio of Cu and Se (Cu: Se) is 1: 1.5. Was added to 100 mL of tetraethylene glycol and heated to 240 ° C. (second solution). The second solution containing S and Se was added to the liquid containing the metal salt (first solution) at 50 mL / min to obtain a mixed solvent. Thereafter, the temperature of the mixed solvent was adjusted to be the above reaction temperature, this reaction temperature was maintained for 5 hours, and the reaction (chalcogenation reaction) was performed to obtain a chalcogen compound powder. The obtained chalcogen compound powder was repeatedly washed with isopropyl alcohol and filtered to make the filtrate have a conductivity of 10 −1 Sm −1 or less, and then vacuum dried at 60 ° C. Evaluation similar to Example 9 was performed with respect to the obtained chalcogen compound powder.

FIG. 41 is a table showing the formation state of the chalcogen compound (Cu 1.0 Zn 0.9 Sn 0.1 S 0.5 Se 1.5 ) and the results of examining the reaction temperature, and FIG. It is a table | surface which shows the result of having performed the composition analysis by X-ray | X_line.

As a result, it was found that a high-purity Cu 1.0 Zn 0.9 Sn 0.1 S 0.5 Se 1.5 powder can be obtained by setting the chalcogenation reaction temperature to 220 ° C. or more (FIG. 41). ). As a result of examining the particle sizes of Samples 8, 9, and 10 with TEM, the TEM average particle size was 15 to 20 nm. Samples 8, 9, and 10 were subjected to compositional analysis using fluorescent X-rays, and as a result, it was found that crystal powder having a target composition ratio was generated (FIG. 42).

Claims (5)

  1. Average particle diameter (D TEM ) represented by the general formula CuIn x Ga 1-x Se y S 2-y (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 2) and measured by transmission electron microscope observation Is a chalcogen compound powder characterized in that it is 1 nm to 60 nm.
  2. The chalcogen compound powder according to claim 1, wherein the chalcogen compound powder has a general formula CuIn x Ga 1-x Se 2 (where 0.1 ≦ x ≦ 0.9).
  3. The chalcogen compound powder according to claim 1, wherein the average particle diameter (D TEM ) is 20 nm or less.
  4.   X-ray diffraction peak intensity ratio (the value obtained by dividing the highest peak height of the peak intensity of the desired chalcogen compound by the highest peak height of the peaks of other substances) is 8 or more. The chalcogen compound powder according to any one of claims 1 to 3, wherein the chalcogen compound powder is characterized.
  5.   The chalcogen compound powder according to claim 4, wherein the X-ray diffraction peak intensity ratio is 15 or more.
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