# Patent

## Title
Method for making a chalcopyrite-type compound

## Abstract

A method for making a chalcopyrite-type compound includes: reacting a reaction mixture in a first solvent under reflux condition to form the chalcopyrite-type compound containing M1, M2, and A, in which M1 is selected from Cu, Au, Ag, Na, Li, and K, M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg, and combinations thereof, and A is selected from S, Se, Te, and combinations thereof; filtering the reaction mixture to obtain a crude cake; mixing the crude cake with a second solvent and a powder of a post-treatment material selected from S, Se, Te, and combinations thereof; and heating the mixture under reflux condition.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for making a chalcopyrite-type compound, more particularly to a method involving a post treatment of a crude product of a chalcopyrite-type compound.
2. Description of the Related Art
Chalcopyrite-type compounds, such as CuInSe2, Cu(Inx Ga1-x)(SeyS2-y), and Cu(InxAl1-x)(SeyS2-y), are used in the production of a semiconductor absorption layer of a solar cell due to their high optoelectric efficiency and low cost. The amount of impurities, such as the carbon content, contained in the chalcopyrite-type compound has a significantly adverse effect on the optoelectric efficiency thereof. It is desirable to manufacture a chalcopyrite-type compound having a low impurity content.
Bin Li et al. (Adv. Mater., 1999, 11, No. 17, 1456-1459) disclose a solvothermal synthesis method for making CuInSe2 nano-materials. The method involves reacting a mixture of CuCl2.2H2O, InCl3.4H2O and Se powder in a solvent of ethylenediamine at a temperature of 180° C. for 15 hr to form a precipitate. The precipitate thus formed is rinsed with an aqueous solution containing water and ethanol so as to remove by-product from the precipitate, followed by drying so as to form the chalcopyrite-type compound powder having a structure of a chalcopyrite phase. The chalcopyrite-type compound thus formed has a high carbon impurity content.
U.S. Pat. No. 7,591,990 discloses a process for making a chalcopyrite-type compound of formula M3M1A2, where M1 can be selected from Al3+, Ga3+, In3+, etc., M3 can be selected from Cu+, Ag+, etc., and A can be selected from S, Se, and Te. The process comprises reacting a compound of formula M3X with a compound of formula M2M1A2 in a coordinating solvent so as to form the chalcopyrite-type compound of formula M3M1A2, where X can be a halide and M2 can be Li+, Na+, K+, etc. The reaction product of the chalcopyrite-type compound thus formed also has a relatively high impurity content.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a method for making a chalcopyrite-type compound that can reduce the impurity of the chalcopyrite-type compound.
According to the present invention, a method for making a chalcopyrite-type compound comprises: reacting a reaction mixture in a first solvent under reflux condition to form the chalcopyrite-type compound containing M1, M2, and A, in which M1 is selected from Cu, Au, Ag, Na, Li, and K, M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg, and combinations thereof, and A is selected from S, Se, Te, and combinations thereof; filtering the reaction mixture after the reaction so as to obtain a crude cake of the chalcopyrite-type compound; mixing the crude cake with a second solvent and a powder of a post-treatment material selected from S, Se, Te, and combinations thereof so as to form a treatment mixture; and heating the treatment mixture under reflux condition in a manner to permit the crude cake to undergo a post treatment for removing impurities from the crude cake.



BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become apparent in the following detailed description of the preferred embodiment of this invention, with reference to the accompanying drawings, in which:
FIG. 1 shows an X-ray diffraction pattern of the product (c) of Example 1 before a post treatment in a method of the preferred embodiment according to this invention;
FIG. 2 shows an X-ray diffraction pattern of the product (d) of Example 1 after the post treatment;
FIG. 3 shows an X-ray diffraction pattern of the product (e) of Example 1 after the post treatment and an acid washing;
FIG. 4 shows an X-ray diffraction pattern of the product (f) of Example 2 before a post treatment;
FIG. 5 shows an X-ray diffraction pattern of the product (g) of Example 2 after the post treatment;
FIG. 6 shows an X-ray diffraction pattern of the product (h) of Example 2 after the post treatment and an acid washing;
FIG. 7 shows an X-ray diffraction pattern of the product (i) of Example 3 before a post treatment;
FIG. 8 shows an X-ray diffraction pattern of the product (j) of Example 3 after the post treatment;
FIG. 9 shows an X-ray diffraction pattern of the product (k) of Example 3 after the post treatment and an acid washing;
FIG. 10 shows an X-ray diffraction pattern of the product (l) of Example 4 before a post treatment;
FIG. 11 shows an X-ray diffraction pattern of the product (m) of Example 4 after the post treatment;
FIG. 12 shows an X-ray diffraction pattern of the product (n) of Example 5 before a post treatment;
FIG. 13 shows an X-ray diffraction pattern of the product (o) of Example 5 after the post treatment;
FIG. 14 shows an X-ray diffraction pattern of the product (p) of Example 6 before a post treatment;
FIG. 15 shows an X-ray diffraction pattern of the product (q) of Example 6 after the post treatment;
FIG. 16 shows an X-ray diffraction pattern of the product (r) of Example 7 before a post treatment;
FIG. 17 shows an X-ray diffraction pattern of the product (s) of Example 7 after the post treatment;
FIG. 18 shows an X-ray diffraction pattern of the product (t) of Example 8 before a post treatment;
FIG. 19 shows an X-ray diffraction pattern of the product (u) of Example 8 after the post treatment;
FIG. 20 shows an X-ray diffraction pattern of the product (v) of Comparative Example 1;
FIG. 21 shows an X-ray diffraction pattern of the product (w) of Comparative Example 2; and
FIG. 22 shows an X-ray diffraction pattern of the product (x) of Comparative Example 3.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment of a method for making a chalcopyrite-type compound according to this invention includes: reacting a reaction mixture in a first solvent under reflux condition to form the chalcopyrite-type compound containing M1, M2, and A, in which M1 is selected from Cu, Au, Ag, Na, Li, and K, M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg, and combinations thereof, and A is selected from S, Se, Te, and combinations thereof; filtering the reaction mixture after the reaction so as to obtain a crude cake of the chalcopyrite-type compound; mixing the crude cake with a second solvent and a powder of a post-treatment material selected from S, Se, Te, and combinations thereof so as to form a treatment mixture; and heating the treatment mixture under reflux condition in a manner to permit the crude cake to undergo a post treatment for removing impurities from the crude cake.
The reaction includes at least one first compound and at least one second compound, the first compound containing M1 and A1, the second compound containing M2 and A1, in which A1 is selected from S, Se, Te, Cl−, Br−, I−, OH−, NO3−, SO42−, CH3COO−, acetylacetonate, and combinations of S, Se, and Te; and
wherein, when A1 of the first and second compounds is not S, Se, Te, or the combinations of S, Se, and Te, the reaction mixture further includes a powder of material selected from the group consisting of S, Se, Te, and combinations thereof.
The preferred embodiment further comprises washing the crude cake with a washing solution containing water, alcohol and ketone before mixing with the second solvent and the powder of the post-treatment material for the post treatment, followed by drying the crude cake.
Preferably, the preferred embodiment of this invention further comprises washing the crude cake of the chalcopyrite-type compound with an acid after the post-treatment, followed by a second washing with the washing solution and drying the crude cake.
Suitable examples of the first and second solvents are alkylamines, dimethyl foramide (DMF), N-methylpyrolidone (NMP), methylimidazole, dimethyl sulfoxide (DMSO), oleylamine, glycerol, and ethyleneglycol. In the embodiments of this invention, each of the first and second solvents is independently selected from ethylenediamine and methylimidazole.
Suitable examples of the acid includes nitric acid, hydrochloric acid, citric acid, acetic acid, phosphoric acid, sulfuric acid, and oxalic acid. Preferably, when a strong acid is used, the concentration of the strong acid ranges from 5-10 wt %.
The merits of the method for making the chalcopyrite-type compound of this invention will become apparent with reference to the following Examples and Comparative Examples. The present invention is not restricted to the following Examples.
Example 1 (E1)
Preparation of In2Se3 
4000 ml of ethylenediamine was added into a reactor. 302.5 g of Se powder was added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes. 750.5 g of InCl3.4H2O was slowly added into the reactor with stirring. The mixture in the reactor was stirred for 20 minutes before heating and was heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 30 hrs. The mixture was filtered to obtain a crude cake of In2Se3 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L (Liter) of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A yellow powder (product (a)) of In2Se3 having a composition of 42.63 at % In and 57.37 at % Se was obtained. Elemental analysis shows that the yellow powder contains an impurity of 4.81 wt % of carbon.
Preparation of Cu2Se
5500 ml of ethylenediamine was added into a reactor. 231 g of Se powder was added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes. 580 g of CuCl was slowly added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 24 hrs. The mixture was filtered to obtain a crude cake of Cu2Se after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A dark blue powder (product (b)) of Cu2Se having a composition of 63.82 at % Cu and 36.18 at % Se was obtained. Elemental analysis shows that the dark blue powder contains an impurity of 0.1 wt % of carbon.
Preparation of Ternary Compound CuInSe2 
9000 ml of ethylenediamine was added into a reactor. 600 g of product (a) and 260 g of product (b) were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 30 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (c)) of CuInSe2 having a composition of 25.43 at % Cu, 26.68 at % In and 47.89 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 1.536 wt % of carbon. FIG. 1 shows the X-ray diffraction (XRD) pattern of the black powder (product (c)).
Removal of Impurity from Product (c)
6000 ml of ethylenediamine was added into a reactor. 730 g of product (c) and 44 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 40 hrs for conducting a post treatment of the product (c) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInSe2 after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (d)) of CuInSe2 having a composition of 25.44 at % Cu, 26.67 at % In, and 47.88 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.877 wt % of carbon. FIG. 2 shows the X-ray diffraction (XRD) pattern of the black powder (product (d)).
The post treatment of product (c) permits a significant reduction of the carbon content of the CuInSe2 product from 1.536 wt % (product (c)) to 0.877 wt % (product (d)).
Removal of Impurity from Product (d)
5400 ml of 5% nitric acid was added into a reactor. 650 g of product (d) was added into the reactor with stirring. The mixture was subsequently heated to 45° C. with stirring for 4 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 after the treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (e)) of CuInSe2 having a composition of 26.29 at % Cu, 25.45 at % In, and 48.26 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.713 wt % of carbon. FIG. 3 shows the X-ray diffraction (XRD) pattern of the black powder (product (e)).
Example 2 (E2)
Preparation of Quarternary Compound CuInGaSe2 
350 ml of ethylenediamine was added into a reactor. 6 g of product (a), 11.95 g of product (b) and 1.31 g Ga2Se3 were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 50 hrs. The mixture was filtered to obtain a crude cake of CuInGaSe2 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (f)) of CuInGaSe2 having a composition of 24.4 at % Cu, 21.6 at % In, 6.48 at % Ga, and 47.52 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 1.332 wt % of carbon. FIG. 4 shows the X-ray diffraction (XRD) pattern of the black powder (product (f)).
Removal of Impurity from Product (f)
200 ml of ethylenediamine was added into a reactor. 15 g of product (f) and 0.9 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 98 hrs for conducting a post treatment of the product (f) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInGaSe2 after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (g)) of CuInGaSe2 having a composition of 23.5 at % Cu, 22.28 at % In, 6.49 at % Ga, and 47.73 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.65 wt % of carbon. FIG. 5 shows the X-ray diffraction (XRD) pattern of the black powder (product (g)).
Removal of Impurity from Product (g)
85 ml of 5% nitric acid was added into a reactor. 10 g of product (g) was added into the reactor with stirring. The mixture was subsequently heated to 45° C. with stirring for 4 hrs. The mixture was filtered to obtain a crude cake of CuInGaSe2 after the treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (h)) of CuInGaSe2 having a composition of 23.9 at % Cu, 22.23 at % In, 6.55 at % Ga, and 47.32 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.511 wt % of carbon. FIG. 6 shows the X-ray diffraction (XRD) pattern of the black powder (product (h)).
Example 3 (E3)
Preparation of Five-Element Compound CuInGaSeS
350 ml of ethylenediamine was added into a reactor. 6 g of product (b), 8.35 g of In2S3, and 1.31 g Ga2Se3 were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 50 hrs. The mixture was filtered to obtain a crude cake of CuInGaSeS after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (i)) of CuInGaSeS having a composition of 25.4 at % Cu, 19.68 at % In, 6.82 at % Ga, 18.1 at % Se, and 30 at % S was obtained. Elemental analysis shows that the black powder contains an impurity of 0.928 wt % of carbon. FIG. 7 shows the X-ray diffraction (XRD) pattern of the black powder (product (i)).
Removal of Impurity from Product (i)
200 ml of ethylenediamine was added into a reactor. 13 g of product (i) and 0.9 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 48 hrs for conducting a post treatment of the product (i) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInGaSeS after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (j)) of CuInGaSeS having a composition of 24.9 at % Cu, 20.1 at % In, 6.7 at % Ga, 18.5 at % Se, and 29.8 at % S was obtained. Elemental analysis shows that the black powder contains an impurity of 0.522 wt % of carbon. FIG. 8 shows the X-ray diffraction (XRD) pattern of the black powder (product (j)).
Removal of Impurity from Product (j)
100 ml of 5% nitric acid was added into a reactor. 12 g of product (j) was added into the reactor with stirring. The mixture was subsequently heated to 48° C. with stirring for 4 hrs. The mixture was filtered to obtain a crude cake of CuInGaSeS after the treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (k)) of CuInGaSeS having a composition of 24.83 at % Cu, 19.82 at % In, 6.75 at % Ga, 17.41 at % Se, and 31.19 at % S was obtained. Elemental analysis shows that the black powder contains an impurity of 0.331 wt % of carbon. FIG. 9 shows the X-ray diffraction (XRD) pattern of the black powder (product (k)).
Example 4 (E4)
Preparation of Ternary Compound CuInSe2 
600 ml of ethylenediamine was added into a reactor. 18.75 g of Se powder was added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes. 76.24 g of InCl3. 4H2O was added into the reactor with stirring. The mixture was stirred for 20 minutes. 22.64 g of CuCl was added into the reactor with stirring. The mixture was stirred for 20 minutes before heating and was subsequently heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 50 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (l)) of CuInSe2 having a composition of 22.49 at % Cu, 28.99 at % In and 48.51 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 9.216 wt % of carbon. FIG. 10 shows the X-ray diffraction (XRD) pattern of the black powder (product (l)).
Removal of Impurity from Product (l)
600 ml of ethylenediamine was added into a reactor. 50 g of product (l) and 1.37 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 40 hrs for conducting a post treatment of the product (l) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInSe2 after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (m)) of CuInSe2 having a composition of 22.54 at % Cu, 28.31 at % In, and 49.15 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 1.055 wt % of carbon. FIG. 11 shows the X-ray diffraction (XRD) pattern of the black powder (product (m)).
The post treatment of product (l) permits a significant reduction of the carbon content of the CuInSe2 product from 9.216 wt % (product (l)) to 1.055 wt % (product (m)).
Example 5 (E5)
Preparation of Ternary Compound CuInSe2 
170 ml of N-methylimidazole was added into a reactor. 16.6 g of InCl3 was added into the reactor with stirring. 18.7 g of Na2Se powder was slowly added into the reactor with stirring to form a first mixture. 90 ml of N-methylimidazole was added into a second reactor. 7.4 g of CuCl was added into the second reactor with stirring to form a second mixture. The first mixture was cooled to about 3° C., followed by slowly adding the second mixture into the first mixture with stirring while the temperature remained below 5° C. for reaction to take place. The reaction lasted for about 12 hrs. The reaction mixture was filtered to obtain a crude cake of CuInSe2 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (n)) of CuInSe2 having a composition of 26.02 at % Cu, 26.34 at % In and 47.64 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 4.322 wt % of carbon. FIG. 12 shows the X-ray diffraction (XRD) pattern of the black powder (product (n)).
Removal of Impurity from Product (n)
80 ml of ethylenediamine was added into a reactor. 9 g of product (n) and 0.25 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 45 hrs for conducting a post treatment of the product (n) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInSe2 after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (o)) of CuInSe2 having a composition of 25.68 at % Cu, 26.13 at % In, and 48.19 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.912 wt % of carbon. FIG. 13 shows the X-ray diffraction (XRD) pattern of the black powder (product (o)).
The post treatment of product (n) permits a significant reduction of the carbon content of the CuInSe2 product from 4.322 wt % (product (n)) to 0.912 wt % (product (o)).
Example 6 (E6)
Preparation of Quarternary Compound CuInGaSe2 
170 ml of N-methylimidazole was added into a reactor. 14.6 g of InCl3 and 1.58 g of GaCl3 were added into the reactor with stirring. 18.7 g of Na2Se powder was slowly added into the reactor with stirring to form a first mixture. 90 ml of N-methylimidazole was added into a second reactor. 7.4 g of CuCl was added into the second reactor with stirring to form a second mixture. The first mixture was cooled to about 3° C., followed by slowly adding the second mixture into the first mixture with stirring while the temperature remained below 5° C. for reaction to take place. The reaction lasted for about 12 hrs. The reaction mixture was filtered to obtain a crude cake of CuInGaSe2 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (p)) of CuInGaSe2 having a composition of 19.4 at % Cu, 21.72 at % In, 7.28 at % Ga, and 51.6 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 4.339 wt % of carbon. FIG. 14 shows the X-ray diffraction (XRD) pattern of the black powder (product (p)).
Removal of Impurity from Product (p)
105 ml of ethylenediamine was added into a reactor. 12 g of product (p) and 0.33 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 40 hrs for conducting a post treatment of the product (p) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInGaSe2 after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (q)) of CuInGaSe2 having a composition of 18.42 at % Cu, 22.25 at % In, 7.41 at % Ga, and 51.92 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.872 wt % of carbon. FIG. 15 shows the X-ray diffraction (XRD) pattern of the black powder (product (q)).
The post treatment of product (p) permits a significant reduction of the carbon content of the product CuInGaSe2 from 4.339 wt % (product (p)) to 0.872 wt % (product (q)).
Example 7 (E7)
Preparation of Five-Element Compound CuInGaSeS
170 ml of N-methylimidazole was added into a reactor. 14.6 g of InCl3 and 1.58 g of GaCl3 were added into the reactor with stirring. 9.37 g of Na2Se powder and 5.85 g of Na2S were slowly added into the reactor with stirring to form a first mixture. 90 ml of N-methylimidazole was added into a second reactor. 7.4 g of CuCl was added into the second reactor with stirring to form a second mixture. The first mixture was cooled to about 3° C., followed by slowly adding the second mixture into the first mixture with stirring while the temperature remained below 5° C. for reaction to take place. The reaction lasted for about 12 hrs. The reaction mixture was filtered to obtain a crude cake of CuInGaSeS after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (r)) of CuInGaSeS having a composition of 24.64 at % Cu, 22.1 at % In, 6.98 at % Ga, 25.88 at % Se, and 20.4 at % S was obtained. Elemental analysis shows that the black powder contains an impurity of 2.936 wt % of carbon. FIG. 16 shows the X-ray diffraction (XRD) pattern of the black powder (product (r)).
Removal of Impurity from Product (r)
90 ml of ethylenediamine was added into a reactor. 10 g of product (r) and 0.28 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring for 40 hrs for conducting a post treatment of the product (r) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInGaSeS after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 2 L of ethanol and 2 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (s)) of CuInGaSeS having a composition of 24.25 at % Cu, 22.1 at % In, 7.11 at % Ga, 26.37 at % Se, and 19.38 at % S was obtained. Elemental analysis shows that the black powder contains an impurity of 0.917 wt % of carbon. FIG. 17 shows the X-ray diffraction (XRD) pattern of the black powder (product (s)).
The post treatment of product (r) permits a significant reduction of the carbon content of the product CuInGaSeS from 2.936 wt % (product (r)) to 0.917 wt % (product (s)).
Example 8 (E8)
Preparation of Five-Element Compound CuInSe2 
150 ml of ethylenediamine was added into a reactor. 2.63 g of Se powder was added into the reactor under stirring. The mixture in the reactor was stirred for 5 minutes. 10.05 g of In(NO3)3 was added into the reactor under stirring. The mixture was stirred for 15 minutes. 6.9 g of Cu(NO3)2 was added into the reactor under stirring. The mixture was stirred for 10 minutes and was subsequently heated to a boiling point thereof. The reaction of the mixture was lasted under reflux condition for 45 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 after the reaction was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (t)) of CuInSe2 having a composition of 25.72 at % Cu, 26.83 at % In and 47.45 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 3.255 wt % of carbon. FIG. 18 shows the X-ray diffraction (XRD) pattern of the black powder (product (t)).
Removal of Impurity from Product (t)
80 ml of ethylenediamine was added into a reactor. 10 g of product (t) and 0.28 g of Se powder were added into the reactor under stirring. The mixture in the reactor was stirred for 3 minutes before heating and was subsequently heated to its boiling point under stirring for 45 hrs for conducting a post treatment of the product (t) of the mixture under reflux condition. The mixture was filtered to obtain a crude cake of CuInSe2 after the post treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (u)) of CuInSe2 having a composition of 25.64 at % Cu, 26.72 at % In, and 47.64 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 0.912 wt % of carbon. FIG. 19 shows the X-ray diffraction (XRD) pattern of the black powder (product (u)).
Comparative Example 1 (CE1)
Preparation of Ternary Compound CuInSe2 
700 ml of ethylenediamine was added into a reactor. 12 g of Cu2Se, 27.2 g of In2Se3 and 2.38 g of Se powder were added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 55 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 with a relatively large amount of a red fine powder after the reaction was completed and the mixture was cooled. The particle size of the red fine powder was relatively small, which made the filtration of the reaction product and separation of the red fine powder from the crude cake difficult.
The crude cake was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (v)) of CuInSe2 having a composition of 24.48 at % Cu, 26.8 at % In and 48.72 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 2.239 wt % of carbon. FIG. 20 shows the X-ray diffraction (XRD) pattern of the black powder (product (v)).
Comparative Example 2 (CE2)
Preparation of Ternary Compound CuInSe2 
600 ml of ethylenediamine was added into a reactor. 46.3 g of Se powder was added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes. 76.24 g of InCl3.4H2O was added into the reactor with stirring. The mixture was stirred for 20 minutes. 22.64 g of CuCl was added into the reactor with stirring. The mixture was stirred for 20 minutes before heating and was subsequently heated to a boiling point thereof with stirring for reaction of the mixture to take place. The reaction of the mixture lasted under reflux condition for 50 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 with a relatively large amount of a red fine powder after the reaction was completed and the mixture was cooled. The particle size of the red fine powder was relatively small, which made the filtration of the reaction product and separation of the red fine powder from the crude cake difficult. The crude cake was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (w)) of CuInSe2 having a composition of 24.37 at % Cu, 28.19 at % In and 47.44 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 8.526 wt % of carbon. FIG. 21 shows the X-ray diffraction (XRD) pattern of the black powder (product (w)).
Comparative Example 3 (CE3)
Blank Test: Treating CuInSe2 without Using Se Powder
130 ml of ethylenediamine was added into a reactor. 20 g of CuInSe2 with a carbon content of 1.841 wt % was added into the reactor with stirring. The mixture in the reactor was stirred for 5 minutes before heating and was subsequently heated to its boiling point with stirring under reflux condition for 55 hrs. The mixture was filtered to obtain a crude cake of CuInSe2 after the treatment was completed and the mixture was cooled. The crude cake was washed with a solution containing a large amount of water, 1 L of ethanol and 1 L of acetone, followed by drying at a temperature of 150° C. A black powder (product (x)) of CuInSe2 having a composition of 26.71 at % Cu, 25.59 at % In, and 47.7 at % Se was obtained. Elemental analysis shows that the black powder contains an impurity of 2.012 wt % of carbon.
FIG. 22 shows the X-ray diffraction (XRD) pattern of the black powder (product (x)).
Comparative Example 1 differs from Example 1 in that an additional amount of the Se powder was added in the reaction mixture of Cu2Se and In2Se3 for Comparative Example 1. The results show that the black powder (product (v)) of Comparative Example 1 has a carbon content higher than that obtained before post treatment, i.e., the product (c) of Example 1 and much higher than that obtained after post treatment, i.e., the product (d) of Example 1, which demonstrates that adding an additional amount of the Se powder in the reaction mixture cannot achieve the carbon reduction effect of the post treatment carried out in Example 1.
Comparative Example 2 differs from Example 4 in that an excessive amount of the Se powder was added in the reaction mixture of Cu2Se and In2Se3 for Comparative Example 2. The results show that the black powder (product (w)) of Comparative Example 2 has a carbon content slightly less than that obtained before post treatment, i.e., the product (l) of Example 4 and much higher than that obtained after post treatment, i.e., the product (m) of Example 4, which demonstrates that adding an excessive amount of the Se powder in the reaction mixture cannot achieve the carbon reduction effect of the post treatment carried out in Example 4.
Comparative Example 3 differs from the previous Examples 1 and 4 in that the post treatment of CuInSe2 was carried out without the use of the Se powder for Comparative Example 3. The results show that the carbon content of the black powder (product (x)) of Comparative Example 3 is increased after the post treatment, which demonstrates that reduction of the carbon content cannot be achieved without the use of the Se powder in the post treatment.
With the invention thus explained, it is apparent that various modifications and variations can be made without departing from the spirit of the present invention. It is therefore intended that the invention be limited only as recited in the appended claims.

## Claims

1. A method for making a chalcopyrite-type compound, comprising:
reacting a reaction mixture in a first solvent under reflux condition to form the chalcopyrite-type compound containing M1, M2, and A, in which M1 is selected from Cu, Au, Ag, Na, Li, and K, M2 is selected from In, Ga, Al, Ti, Zn, Cd, Sn, Mg, and combinations thereof, and A is selected from S, Se, Te, and combinations thereof;
filtering the reaction mixture after the reaction so as to obtain a crude cake of the chalcopyrite-type compound;
mixing the crude cake with a second solvent and a powder of a post-treatment material selected from S, Se, Te, and combinations thereof so as to form a treatment mixture; and
heating the treatment mixture under reflux condition in a manner to permit the crude cake to undergo a post treatment for removing impurities from the crude cake.

2. The method of claim 1, wherein each of the first and second solvents is independently selected from alkylamine, dimethyl foramide, N-methylpyrolidone, methylimidazole, dimethyl sulfoxide, oleyamine, glycerol, and ethyleneglycol.

3. The method of claim 2, wherein each of the first and second solvents is independently selected from the group consisting of ethylenediamine and methylimidazole.

4. The method of claim 1, further comprising washing the crude cake with a washing solution containing water, alcohol and ketone before the post-treatment.

5. The method of claim 1, further comprising filtering the treatment mixture after the post-treatment to obtain a treated crude cake, followed by washing the treated crude cake with a washing solution containing water, alcohol and ketone.

6. The method of claim 5, further comprising washing the treated crude cake with an acid.

7. The method of claim 1, wherein the reaction mixture includes at least one first compound and at least one second compound, the first compound containing M1 and A1, the second compound containing M2 and A1, in which A1 is selected from S, Se, Te, Cl−, Br−, I−, OH−, NO3−, SO42−, CH3COO−, acetylacetonate, and combinations of S, Se, and Te; and
wherein, when A1 of the first and second compounds is Cl−, Br−, I−, OH−, NO3−, SO42−, CH3COO−, acetylacetonate, the reaction mixture further includes a powder of material selected from the group consisting of S, Se, Te, and combinations thereof.

8. The method of claim 7, wherein the reaction mixture includes Cu2Se and In2Se3.

9. The method of claim 7, wherein the reaction mixture includes Cu2Se, In2Se3 and Ga2Se3.

10. The method of claim 7, wherein the reaction mixture includes Cu2Se, In2S3, and Ga2Se3.

11. The method of claim 7, wherein the reaction mixture includes Se, InCl3.4H2O, and CuCl.

12. The method of claim 7, wherein the reaction mixture includes InCl3, Na2Se, and CuCl.

13. The method of claim 7, wherein the reaction mixture includes InCl3, GaCl3, Na2Se, and CuCl.