TWI353344B - Method for producing copper indium chalcogenides p - Google Patents

Description

1353344 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing a powder, and particularly to a method for producing a CIS (copper indium chalcogenides) powder and a method for producing the same. [Prior Art] In order to solve the problems of energy crisis and environmental pollution caused by overexploitation in recent decades, the development of solar cells has become a major research topic in solving problems such as the energy crisis. Among the CIS-based solar cells derived from the ternary compound of copper indium (CuInSe), the materials commonly used in the p-type semiconductor absorber layer are CuInSe2, Cu(InxGai-x) (SeyS2_y), CuGnxAlbxKSeySa. -y) Wait. These CIS materials are also favored by those skilled in the art because of their high photoelectric efficiency and low material cost.

A method for making a CIS-based powder is disclosed by Claire J. Carmalt et al., J. Mater Chem., 1998, 8(10), 2209-2211. Claire J. Carmalt et al. 'mixed CuBr (0.186 g, 1,30 mmol), InCl3 (0.280 g, 1.30 mmol), Na2Se (2.60 mmol) and C7H8 (20 cm3); another, warmed up and refluxed (about) After 72 hours, the reaction product was allowed to stand and C7H8 was taken to leave a solid reaction product; wherein CuBi was replaced with CuC12 (0.174 g, 1.30 mmol). Further, the solid reaction product is ground and subjected to vacuum drying; finally, 'the solid reaction product is subjected to a calcining process at 500 ° C for 24 hours to form a chalcopyrite crystal phase ( Chalcopyrite phase) CIS powder. 5

Claire J. Carmalt et al. published a method in which a CIS powder of a chalcopyrite crystal phase was obtained not only after calcination at a temperature of 500 ° C for up to 24 hours. In addition, it is worth noting that when a sphalerite phase is present in the CIS powder, it will also affect the photoelectric efficiency of the material itself. However, the X-ray diffraction (XRD) spectrum of this document shows that there are still many diffracted signal peaks of the sphalerite crystal phase which are not desired in this art. Therefore, the CIS-based powder obtained by this method is also limited in the application of solar cells due to its insufficient photoelectric efficiency.

By Bin Li et al., Adv. Mater. 1999, /7, No. 17, 1456-1459, discloses a method for making nanowhiskers and nanoparticles of CuInSe2. By Bin Li et al., were mixed with CuCl2.2H2〇 (〇.221 g, 1.26 mmol), InCl3.4H2O (0.380 g, 1.29 mmol), Se (0.205 g, 2.59 mmol) in an autoclave. The liquid level was about 90% of the aqueous diethylamine (hydrous diethylamine) of the pressure cooker, and the pressure cooker was closed and held at 180 ° C for 15 hours. Further, the pressure cooker is cooled to room temperature, and the precipitate in the pressure cooker is filtered and washed with distilled water and ethanol several times to remove the by-products. Finally, the reaction product is placed in a vacuum environment at 60 ° C. Dry at temperature for 4 hours to obtain CIS powder b

The solvothermal synthesis method used by By Bin Li et al. can obtain a CIS-based powder in the form of a chalcopyrite crystal phase; however, the XRD spectrum shown in the literature shows that this solvothermal synthesis is known. The CIS powder obtained by the method can also be seen in many of the diffracted signal peaks of the 1353344 zinc blende crystal phase which is not desired in this technical field [ie, (10)), (211), and the diffraction surface of Taowan. In addition, since the pressure of the pressure steel is small, the pressure is easy to control, and the pressure of the pressure cooker is more difficult to control; further, in the solvothermal synthesis method, the pressure steel used for sealing the reactants is not provided with a stirrer, Reducing the probability of collision between reactants also relatively reduces the rate of reaction. Therefore, mass production of the CIS-based powder cannot be achieved by the dissolution (four) synthesis method.

As apparent from the above description, the production method of the cis-based powder which has a high crystal phase of the chalcopyrite and the production method thereof are mass-produced, and it is a subject to be solved in the field of research and development of the CIS-based powder. SUMMARY OF THE INVENTION <Summary of the Invention> Conditions for promoting a compound to a crystalline phase, the main determining factor being whether the heat energy provided by the reaction temperature is sufficient for each atom in the compound to occupy its lattice position in the crystal (丨attice site).

It is worth mentioning that when a plurality of solvents containing anionic and cationic ionic compounds are used, it is sufficient to sufficiently remove anions and metal cations from the plasma compound to form a homogeneous phase (homogeneous). When a precursor containing the precursor of the plasma is used as a chelate solvent; then, the precursor containing the cation/anion is refluxed in a solvent for a predetermined period of time and reacted to form a characteristic chemistry In the process of the agent S compared to the crystal phase, the required reaction energy will decrease relatively. Therefore, the present invention mainly utilizes a solvent having chimerism to capture anions and cations in the starting material to form a homogeneous phase containing the ions and cation precursors of the cation 7 1353344, which are to be embedded in the precursor. Recirculation in a compatible solvent - after a predetermined period of time, a reaction having a predetermined stoichiometric ratio can be formed in the case where the reaction energy is lowered (non-high temperature and high pressure). <Object of the Invention> Therefore, the object of the present invention is to provide a method for producing a powder of a CIS-based powder. Another object of the present invention is to provide a method for producing a CIS dry material. Thus, the method for producing a CIS-based powder of the present invention comprises: mixing a starting material containing Cu, a starting material containing a substance, and a starting material containing M2 in an reaction tank containing an inert gas; a conjugated solvent, such that the chimeric solvent captures the cations and anions of the starting materials in the reaction tank, and forms a homogeneous phase (^, 仏, and 2 precursors.) The precursor of the homogenous phase is further reacted to form a powder containing a chalcopyrite crystal phase after refluxing, wherein Μι is selected from in, Ga, or a combination thereof, and M2 is selected from Se, S, or the like. Further, the method for producing a CIS-based target of the present invention comprises the following steps: (a) filling a mold in a cavity with a CIS-based powder obtained by the above-mentioned production method; (b) The chamber is subjected to a reduced pressure to form a purification chamber; (c) the powder in the chamber is heated to a predetermined temperature and held for a predetermined time; (d) the powder in the purification chamber Applying the body to a predetermined force and holding the predetermined time to cause the CIS powder to pass through the predetermined temperature 8 and pre-dusting force to obtain powder densification energy; and (e) removing the predetermined pressure and introducing an inert gas into the purification chamber to cool the purification chamber. The effect of the present invention is that It is possible to obtain a cIS-based powder having a high chalcopyrite crystal phase under high-temperature and high-pressure production conditions, and to achieve a mass production effect by the production method; and, in addition, a production method of a mass-produced CIS-based powder can be produced. [Embodiment] <Detailed Description of the Invention> The foregoing and other technical contents, features, and effects of the present invention will be described below with reference to a preferred embodiment, nine specific examples, and two A detailed description of the comparative example will be clearly shown. A preferred embodiment of the method for producing a CIS powder of the present invention comprises: mixing a starting material containing Cu in a reaction tank containing an inert gas, containing a starting material of M1, a starting material containing M2 and a chimeric solvent 'so that the chimeric solvent picks up the cation and anion of the starting materials in the reaction tank and forms a homogeneous Phase Cu, and M2 precursors. wherein 'the precursor before the homogeneous phase is agitated and further reacted after reflux to form a powder containing a chalcopyrite crystal phase, which is selected from ιη, Ga' or the like. In a combination, M2 is selected from Se, S, or a combination of 1353344 (ethylenediamine, ED) 'dimethyl formamide (DMF), dimethyl acetamide, Dimethyl sulfoxide (DMSO), N-methyl, N-methylpyrrolidone (NMP), D pyridine, or a combination thereof; suitable for use in the present invention The starting material containing Cu is selected from the group consisting of CuCn, CuC12_2H20, CuS04, or a combination thereof; the starting material containing the oxime suitable for the present invention is selected from the group consisting of InCl3, 4H20, In203, In(N03)3, Ga, GaC 3, or a combination of these; the starting material containing M2 suitable for use in the present invention is selected from the group consisting of Se, Na2Se, S, or a combination thereof; and the inert gas in the reaction tank is selected from N2, Ar, He, or a combination of these. Preferably, the amount of the chimeric solvent is between 50% and 90% of the liquid level of the reaction tank; the reflux temperature in the reaction tank is between 90 ° C and 300 ° C; The reflux time of the reaction tank is between 4 hours and 48 hours. More preferably, the reflux temperature in the reaction tank is between 120 ° C and 300 ° C; and the reflux time of the reaction tank is between 8 hours and 48 hours. More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCl; the starting material is InCl3_4H20 combined with one of Ga; the starting material containing M2 is Se And the Mohr number ratio of CuCl, InCl3'4H2〇, Ga and Se is between 0.90: 0.88: 0.22: 2.20~1.10: 0.72: 0.18: 1.90. More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCl; the starting material containing M is InCl3'4H20; the starting material containing M2 is Se; And the Mohr number ratio of CuCl, InCl3.4H20 and Se is between 0.90: 1.10: 1.90 〜1.10: 0.90: 2.20. 10 1353344 More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCl; the starting material containing M! is a combination of Ιη203 and Ga; the content containing M2 The starting material is Se; and the Mohr number ratio of CuCl, ln203, Ga and Se is between 0.90 : 0.88 : 0.22 : 2.20 〜1.10 : 0.72 : 0.18 : 1_90 . More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCl; the starting material is in combination with one of in(N〇3)3 and Ga; The starting material is Se; and the Mohr number ratio of CuCl, In(N03)3, Ga and Se is between 0.90: 0.88: 0.22: 2.20~1.10: 0.72: 0.18: 1.90. More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCl; the starting material is in combination with one of inci3.4H20 and Ga; the starting material containing M2 Is Na2Se; and CuCl,

The Mohr number ratio of InClr4H2〇, Ga and Na2Se is between 0.90: 0.88 : 0.22 : 2.20 〜1·1〇 : 0.72 : 0.18 : 1.90. More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCldHzO; the starting material containing M1 is a combination of InCl3.4H20 and Ga; the starting of Μ2 The substance is se; and the Mohr number ratio of CuC12.2H20, InCl:r4H2〇, Ga and Se is between 0·9〇: 0.88 : 〇·22 · 2·2〇~1·1〇: 0.72 : 0.18 : Between 1.9 baht. More preferably, the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuClr 2 H 2 〇; the starting material containing Μ ι is a combination of InCl 3.4 H 2 〇 and Ga; The starting material is Na2Se; and (: ιι(:12'2Ι12〇, Ιη(:13·4Η20, (the molar ratio of ^^ to Na2Se is between 11 丄0.90: 〇: 〇.22:2_20 ～11 〇: 〇72: 〇i8:i 9〇. β is better i, the chelating solvent is ethylenediamine; the starting material containing a 疋C1 'The starting material of M3 is InCl3. Combination of 4H20 and Ga § 3 The starting material of M2 is Se; and the MoC number of CuC1, InCl3 4H2〇, Ga and 疋)1 is 0.90 : 0.88 : 0.22 : 2.20 〜1.10 : 0.72 :0.18 : 1.90 Between g * 'the eucommence solvent is ethylene diamine; the starting material containing Cu

It is CUCl2.2H2〇; the starting material containing % is inCi3 4H2〇 and ^. The starting material of the a] VI2 is Se; and the Mohr number ratio of CuCl2 2H2〇, nCl3 4H20, Ga and Se is between 〇9〇: 〇88 : 〇2: :2·20 ～0·72 : 0.18: 1.90 between. In another preferred embodiment of the method for fabricating a CIS-based target of the present invention, the method comprises the following steps: (a) filling in a mold in a cavity (not shown), and filling the method as described above. CIS powder;

(b) applying a reduced pressure to the chamber to form a purification chamber; (c) applying a temperature rise to the predetermined temperature of the powder in the chamber for a predetermined period of time; The powder inside is pressurized to a predetermined pressure and held for a predetermined time, so that the CIS-based powder obtains powder densification energy through the predetermined temperature and the predetermined pressure; and (e) removing the predetermined pressure and purifying the An inert gas is introduced into the chamber to cool the purification chamber. It is worth mentioning that 'the step (b) of the present invention is mainly for decompressing the main purpose 12 1353344 is to purify the cavity; when the pressure of the purification chamber is too large In the process of carrying out the steps (C) and (d), an impurity compound which is not desired in the present invention is generated due to an excessive amount of impurities remaining in the purification chamber. Therefore, preferably, the step (b) The pressure of the purification chamber is between 10-2 Torr and 10_5 butyl 0. It is also worth mentioning that the main purpose of the step ((;), (d) of the present invention is to make the CIS powder Producing a densification effect. The target of the present invention

The heating method of the step (4) is determined by the rate of rise of the step (4), that is, the predetermined temperature of the step (4) and the pre-force of the step (4). Therefore, preferably, the heating rate of the (4) (e) is between 2 t/min and H) t/min; and the pressure increasing rate of the step (4) is between 1 MPa/min and 3 MPa/min. between.

Further, in the method of producing the dry material of the present invention, the CIS tantalum powder is allowed to pass through a mechanism of diffusion f sintering to generate densification mainly by the energy generated by the temperature and the house force. It is worth mentioning here that 'when the predetermined temperature of the steps (4), (4), the predetermined pressure or the predetermined time is insufficient, the structure of the finally produced dry material will be too loose; otherwise, when the step (4) is pre-(4) Force or shape „overcutting, not only for the powder:: no substantial contribution will also cause unnecessary production costs; here more mu when the final step of the step (4) is made by the phase change “ht. Oh, it will make the most unwilling male (four) s u°n) and generate the 500T of the invention: ~8〇(Τ(^π. J疋前疋疋度疋 between 18〇Mp 1, the predetermined fort of step (4) The force is between 60 MPa and a. 'The steps (4) and (4) are expected to be between i hours and 8 13 1353344 hours. It is worth mentioning that the target of the present invention is mainly produced by the method. The energy generated by the temperature and pressure causes the CIS-based powder to be densified; therefore, when the predetermined temperature approaches the above-defined 5 〇〇 〇, it can be supplemented by raising the predetermined pressure to form a densification. Energy 1. Specific Example 1 A specific example of a method for producing a CIS-based powder of the present invention In the crucible, the inert gas in the reaction tank is N2; the chimeric solvent is DMF in a volume of 12 〇〇ml; the starting material containing Cxi is CuCi; the starting material containing ruthenium is InCl3.4H2 〇 One of the combinations of Ga; the starting material containing hydrazine is &amp;; the stirring rate is 300 rpm; the reflux temperature and the reflux time are respectively 丨 艽 and 48 hours. Further, in this specific example 1, DMF is in the reaction. The liquid level in the tank is about 60%; the molar ratio of Cua, InCI3.4H2〇, Ga and Se is ! : 〇8 .0.2 . 2 ' and the amount of CuCl, InCl3.4H20, Ga and Se is 102.96 respectively. g, 243_36g, 14.56g and 164.32 g. The CIS-based powder obtained by the specific example 1 of the present invention is a CuIn〇.8Ga〇.2Se2 powder having a weight of about 339 77 g and an average particle diameter of about i 〜5 μηη. 1. The analysis data of the XRD spectrum of the CIS-based powder obtained by the specific example of the present invention shows that the specific example is only about 65. There is a weak (4〇〇) and 71° respectively. (316) The crystallite phase of the sphalerite crystal phase is diffracted with a signal peak. Obviously, the invention can be fabricated at a process temperature of 18 〇 A large amount of high-purity CIS-based powder of a chalcopyrite crystal phase. <Specific Example 2> 14 1353344 One of the methods for producing a CIS-based powder of the present invention is substantially the same as the specific example 1, and the difference is only The starting material containing cerium is InCl3.4H2 〇; and the molar ratio of CuC 卜 InCI3, 4H20 to Se is 1.2. Further, in this specific example 2, the use of CuCl, InCl3.4H20 and Se with a file was 102.96 g, 304·2 g and 164.32 g. The CIS-based powder obtained by the specific example 2 of the present invention is a culnse 2 powder having a weight of about 349. denier and an average particle diameter of about 1 μm to 5 μm. φ Referring to Fig. 2, the analysis data of the XRD spectrum of the CIS-based powder obtained in the specific example 2 of the present invention shows that the specific example 2 is only about 65. At 71 and 82, respectively, there are weak (400), (316) and (424) crystal planes of the dilute zinc diurnal day diffraction signal peak. Obviously, the present invention can produce a large amount of high-purity chalcopyrite crystal phase powder under the degree of the system: Specific Example 3> One of the methods for producing the cis-based powder of the present invention is substantially It is the same as the specific example 1, except that the starting material of the containing is a combination of 1 and &amp; and Ml, In2〇3, and the molar ratio to Se is 1: 08.09.,, , ..0.2 · 2. Further, in this specific example 3, the amounts of CuC, 3, and Se were 102.96 g, 229.63 g, and 14.56 g J g28, respectively. The CIS powder obtained in the specific example 3 of the present invention was about 339.47 g by weight. And the average particle size and CUIn0.8Ga0 2Se2 powder of about 1 μπι to 5 Pm. XRD^H3' The analysis data of the cerium of the CIS-based powder obtained in the specific example 3 of the present invention shows that the specific example 3 is only about Η. 15

Uy3344 71 and 82 respectively have weak (_), (316) and (424) crystal planes = sphalerite crystal phase diffraction signal ♦. Obviously, the present invention is at (10). The process of c can produce a large amount of high-purity chalcopyrite crystal phase (3) powder &lt; specific example 4&gt;

One of the specific examples of the method for producing the cis-based powder of the present invention is substantially the same as the specific example. The difference is only that the starting material containing M1 is _〇3)3 and is combined with it; and CuC1; The molar ratio of in(N〇3)3, G^Se is 疋1 · G.8 : G.2 : 2. Further, in this specific example 4, the amounts of CuCl Ιπ(Ν〇3)3, Ga and Se were ι〇2 % g, (10) 6 g 6 g and 164.32 g, respectively. The cIS-based powder obtained by the specific example 4 of the present invention is a CuIn〇.8Ga().2Se2 powder having a weight of about 339.77 g and an average particle diameter of about _~5 _. Figure 4 is a specific example 4 of the present invention. The analysis data of the XRD spectrum of the obtained (3)-based powder showed that the specific example 4 was only about 65.

At 71 and 82°, there are diffractive (trans), (316) and (424) crystal planes respectively. Obviously, the present invention is just. (3) powder of a chalcopyrite crystal phase having a purity of $1 and a purity of the chalcopyrite crystal phase. Specific Example 5> One of the methods for producing the CIS-based powder of the present invention is substantially the only one. Same as the specific example 1, the difference is only that the % of the starting material 疋NazSe, and the Moir number ratio of Cua, InC13, 4H2〇, and ^ is 9 0.88 . 0.22 . In addition, in this specific example $, Cua, 16 1353344

The amounts of InCl3.4H2 〇, Ga and Na2Se were 92 §, Μ 7 〇 g, 16.02 g and 286 g, respectively. The cis-based powder obtained by the specific example 5 of the present invention is a CuIn〇.8Ga().2Se2 powder having a weight of about 360.54 g and an average particle diameter of about i to 5%. Referring to Fig. 5, the analysis data of the XRD spectrum of the as-based powder obtained in the specific example 5 of the present invention shows that the specific example 5 has weak (400) and (3) respectively at about 7 Γ.丨6) The sphalerite crystal phase of the isomorphous plane is diffracted by the signal peak. Obviously, the present invention can produce a large amount of high purity chalcogenide crystal phase CIS powder at a process temperature of 18 Torr. &lt;Specific Example 6&gt; One of the methods for producing the CIS-based powder of the present invention is substantially the same as the specific example 1, except that the Cu-containing starting material 疋CuC12.2H2〇; and CuC12 The molar ratio of .2H20, InCl3.4H20, Ga and Se is 1: 0.8 : 0.2 : 2. Further, in this specific example 6,

The amounts of CuC12.2H2〇, inci3.4H20, Ga and Se were 177 32 〇 , 243.36 g, 14.56 g and 164.32 g, respectively. The CIS-based powder obtained in the specific example 6 of the present invention is a CuIn0.8Ga0.2Se2 powder having a weight of about 339.77 g and an average particle diameter of about ληη to $μπι. Referring to Fig. 6, the analysis data of the XRD spectrum of the CIS-based powder obtained in the specific example 6 of the present invention shows that the specific example 6 exhibits only weak (4〇〇) and (about) respectively. 316) Sphalerite crystal phase diffraction signal peak of isomorphous crystal "Obviously, the present invention can produce a CIS powder of a large-scale and purely chalcopyrite crystal phase at a process temperature of 180 ° C. In addition, a mold (not shown) in the cavity is filled with about 80 g of CuIn〇_8Ga〇_2Se2 powder prepared by the specific example 6 17 1353344; further, at 5 ° C/min. The CuIn〇.8Ga〇.2Se2 powder is heated and the vacuum is evacuated; the vacuum in the cavity is about 2〇χΙ〇-3 T〇rr (about 1 hour). And in the cavity ^Ar, and respectively boosting and heating the Cuin〇sGa〇2Se2 powder at the same heating rate and a rate of increase of 1,7 MPa/min to the predetermined pressure and the predetermined temperature (about duration) 15 hours wide Finally, after about 4 hours of holding and holding the temperature, the predetermined pressure is removed and naturally cooled in the atmosphere T of Ar to produce a CIS-based target. In this specific example 6, the CIS-based target The appearance is a disk shape with a diameter and a thickness of about 3 inches (4) and 3 mm, respectively; the predetermined degrees are 15 〇]^^ and 780. 〇., pre-twist/blood

Referring to Fig. 7', the XRD spectrum of the m-based dry material obtained by the powder of the specific example 6 of the present invention shows that the three major diffraction signal peaks of the tree of the specific example 6 are (1) 2), (2G4/22G, respectively). And (312)# crystal plane, it is apparent that (4) of the specific example 6 of the present invention is a high-purity chalcopyrite crystal phase (10). (IV) One of the methods for producing the as-based powder of the present invention is substantially the same as Specific example 6, the difference is only in 疋a χτ 〇, the S has M2 starting material 疋Na2Se; and CuC12.2H20, Incir4H nr 尔 曰L曰3 4H2〇, Ga and Na2Se Mo: number ratio 疋1 :〇.8:〇.2:2. Further, in this specific example 7, CuC12.2H2〇, InCl3.4H2〇, Ga and 190.55 g, 219.〇2 13 1〇, 2: the amount of the road is “g and the average particle diameter is about 18 1353344 〜 CuIn〇.sGa〇.2Se2 powder of 5. Referring to Fig. 8, the analysis data of the XRD spectrum of the cis-based powder obtained in the specific example 7 of the present invention shows that the specific example 7 is only at = and 7r respectively. A sphalerite crystal phase diffracted bee with a weak (400) and (316) crystal plane appears. Obviously, the present invention can produce a large amount of high-purity chalcopyrite at a process temperature of 18 Qt. Crystalline CIS powder. <Specific Example 8> One of the methods for producing the CIS powder of the present invention is substantially the same as the specific example 1, except that the fungicidal solvent is about a volume. 1200 ml of ethylenediamine (ED) Q The CIS-based powder obtained by the specific example 8 of the present invention is a CuIn®.8Ga〇.2Se2 powder having a weight of about 339 77 g and an average particle diameter of about i 〜. The analysis data of the XRD spectrum of the CIS-based powder obtained in the specific example 8 of the present invention shows that the specific example 8 is only about 65. Diffraction signal peaks of the zinc blende crystal phase with weak (400), (316) and (424) crystal planes appearing at 82. Obviously, the present invention can be fabricated under 18 (rc process pulse) A cis-based powder of a large amount of high-purity chalcopyrite crystal phase &lt;Specific Example 9&gt; One of the methods for producing the CIS-based powder of the present invention is substantially the same as the specific example 8, except that The starting material containing Cu is CUC12.2H20; and CuCl2.2H2〇, Ιηα3.ο, and the amount used are 177.32 g, 243.36 g, 14 56 § and 164 32 g, respectively. According to the specific example 9 of the present invention The obtained CIS-based powder is cUIn&quot;Ga having a weight of about 349·44 g and 19 average: diameter about i _~5 μηη. As a powder. &gt; Figure 10 shows the CIS system obtained by the specific example 9 of the present invention. The analysis data of the powder 71.% D曰 shows that the specific example 9 has only a weak (4〇〇), (316) and (424) crystal planes of sphalerite at about 65 ′′ 82. The crystal phase diffracts the signal peak. Obviously, the present invention can produce a large amount of high-purity chalcopyrite phase CIS powder at the process temperature of i8()t. : Comparative Example &gt;

β is used to compare with a specific example of the present invention - a 1 to 2, which is substantially the same as the specific example! The difference is only in the comparative example. 2 is the use of tetrahydrofuran (tetrahydrofuran, chemical formula is c4H80, THF for short) and mouse imitation (chi〇r〇f〇rm, chemical formula is c, etc.) Solvents that are not devastating. 2. Looking at Figures 11 to 12, the analytical data of the XRD spectra of these comparative examples are obscure. 'These comparative examples cannot be used because of the solvent without post-coherence.

Effectively from the starting materials (ie, CuC1, InCl3.4H2〇, and (4) to grab their cations and get away from the early .mi ^ ions, therefore, at 18 (TC reflux temperature can not directly react to form a yellow-rich CIS powder of copper ore crystal phase, and 26.6.45 in κ n~12, 盥so C.# 未能 未能 未能 未能 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 112 The three major diffraction signals of the isomorphic plane. The differences between the comparative examples and the specific examples of the present invention are simply summarized in the following table. 20 1353344

The present invention utilizes a chimeric solvent to capture a cation and an anion in the starting material in a process of mixing the starting material and the solvent to form a precursor in a homogeneous phase. And at a reflux temperature below the boiling point of the chimeric solvent (18 (rc) in each embodiment of the invention, the precursor is directly reacted to form a CIS system rich in chalcopyrite crystal phase Further, the method for producing a CIS-based powder of the present invention is also capable of producing a large amount of CIS-based powders due to the use of a chiral solvent; therefore, the CIS-based powder obtained by the method for producing a CIS S powder of the present invention It is more advanced to make a target for the sputtering system through the process of powder metaIlurgy to facilitate the development of the solar cell industry.

The value of the cIS system generated from the specific example 丨~9 of the present invention is about 350 g. Although the reaction tank 21 1353344 used in the specific examples is laboratory-specific and has a volume of 2000 ml. Reaction tank; however, the reaction tank used in the production of the CIS powder according to the method of producing the CIS powder of the present invention [i.e., chemical reflux synthesis method] is replaced by a mass production type reaction. In the case of the groove, the amount of the Cis-based powder is not only relatively increased; in addition, in the production process, the process temperature is easy to control; in addition, compared with the solvothermal synthesis method, the present invention can also Stirring action to increase the reaction rate; therefore, it is more conducive to the development of solar cell related industries. In summary, the method for producing a CIS-based powder of the present invention and the method for producing the same, can produce a high-purity CIS powder of a high-purity chalcopyrite crystal phase without requiring high-temperature and high-pressure production conditions. The CIS-based powder obtained by the mass production method can assist in the development of the solar cell-related industry by the production of the target, and indeed achieves the object of the present invention. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are modified. All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an XRD spectrum showing the crystal phase of a specific example 1 of the method for producing a CIS powder of the present invention; and Fig. 2 is an XRD spectrum showing the production of the as-based powder of the present invention. One of the methods is the crystal phase of the specific example 2; Fig. 3 is a diagram showing the crystal phase of the specific example 3 of the method for producing the powder of the invention (3); 22 1353344 Fig. 4 is an XRD spectrum, illustrating The crystal phase of the specific example 4 of the method for producing a CIS-based powder; FIG. 5 is an XRD spectrum, illustrating a crystal phase of a specific example 5 of the method for producing a CIS-based powder of the present invention; and FIG. 6 is an XRD spectrum. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 7 is a view showing a crystal phase of a specific example 6 of the method for producing a CIS powder of the present invention; Fig. 7 is an XRD spectrum chart for explaining a target made of a CIS powder obtained by the specific example 6 of the present invention. Fig. 8 is an XRD spectrum showing the crystal phase of a specific example 7 of the method for producing a CIS powder of the present invention; and Fig. 9 is an XRD spectrum showing one of the methods for producing the CIS powder of the present invention. The crystal phase of the specific example 8; FIG. 10 is an XRD spectrum chart illustrating the method for producing the CIS powder of the present invention. Figure 9 is an XRD spectrum illustrating the crystal phase of Comparative Example 1 used in comparison with the specific examples of the present invention; and Figure 12 is an XRD spectrum showing The crystal phase of Comparative Example 2 is compared with each of the specific examples of the present invention. 23 1353344 [Description of main component symbols] None

twenty four

Claims (1)

1353344 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Mixing a starting material containing cu, a starting material containing the starting material, a starting material containing M2, and a chimeric solvent in a reaction tank containing an inert gas to make the chimeric solvent in the reaction tank Grasing the cations and anions of the starting materials, and forming a homogenous phase containing cu, hydrazine, and M2 precursors; wherein, before the homogeneous phase, the reactants are further reacted to form yellow a powder of a copper ore phase, Μι is selected from In ', or a combination thereof, Μ2 is selected from Se, s, or a combination thereof; the chimeric solvent is selected from the group consisting of ethylenediamine and diterpene Mercaptoamine or a combination thereof; the starting material containing Cu is selected from the group consisting of cuci, CUC12.2H2, CuSQ4, or the like; the starting material containing 胄% is selected from the group consisting of InClr4H2〇 , In2〇3, In(N〇3)3, Ga, GaCi3, or a combination thereof; and the inclusion m2 is selected from the starting material, Na2Se, S, or such - A New together. 2. The method for producing a CIS-based powder according to the above application, wherein the chimeric solvent is dimethylformamide; the starting material containing Cu is CuCl; The substance is a combination of InCi3 4h2〇 and ^; the starting material containing % is Se; the Mohr concentration of CuC1, InClr4H20 'Ga and Se is between 〇9〇: 〇88 : 0·22 · 2·20 〜 1.1〇: 0.72 : 〇18: 丄9〇. 3. According to the application of the scope of the patent application (10), the method of making powder 25 1353344 | ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ On the 6th of the month, 'the chimeric solvent B _ tian * β (1) 疋-methyl carbamide; the starting material containing Cu is CuCI; the starting material containing λ Λ a 丄〆 3 is inCl3 .4H2〇; the starting material containing M2 is Se. . The molar concentration of cut, Coa, inci3.4H20 and Se is 0.90 : l 1 〇. 1 〇nt Λ Λ ΛΛ ηυ · 1.90 ~ι · ι〇: 〇90 : 2_20 between. 4. The method for producing a cis-based powder according to the above-mentioned Patent No. 4, wherein the chimeric solvent is dimethyl ketone; the Cu-containing The starting material is CuCl; the starting material containing Μι is 1〇2〇3 and is combined with one; the starting material containing M2 is Se; the molar concentration of CuCb In2〇3, Ga and Se is于〇9〇: 〇88 : 〇22 : 2 2〇~n 〇·72 : 0.18 : 1.90. 5. The method according to claim 1, wherein the chimeric solvent is dimethylformamide; the starting material containing CU is CuCl; The starting material is ιη(Ν〇3)3 combined with one of Ga; the starting material containing M2 is Se; the molar concentration of CuC1, In(N〇3)3, Ga and Se is 〇9〇: 0 88: 0 22: 2.20~ 1.10 : 0.72 : 0.18 : 1.90. 6. The method for producing a CIS powder according to the scope of the patent application of the invention, wherein the chimeric solvent is dimethyl decylamine; the starting material containing Cu is CuCl; The starting material is a combination of InCl3.4H2〇 and Ga; the starting material containing M2 is Na2Se; the Mohr concentration of CuCl, InClr4H2〇, Ga and Na2Se is between ο.%: 〇88:0.22: 2.20 〜1.1 〇: 0.72 : 〇· 18 : 1.90. 7. Preparation method of CIs powder according to item 1 of the patent application scope S 26 1353344 - Supplementary application of han·line version 丨 097103740, replacement of the instructions without correction after the correction page Correction date: 100 years October 6th, wherein the chimeric solvent is dimethylformamide; the starting material containing cu is ChC12.2H2〇; the starting material containing Μι is a combination of one of InCldHA and Ga; The starting material containing cerium is: CuC12.2H20, InCl3-4H2 〇, Mo and Se molar concentration is between 0.90:0·88: 0·22: 2.20 〜M0 : 〇72 : 〇18 :丄9〇' 〇8. The method for producing a CIS-based powder according to claim 1, wherein the chimeric solvent is dimethyl oxime; the starting material containing Cu is CuC12.2H2〇; the starting material containing ruthenium is a combination of InClr4H2 〇 and Ga; the starting material containing μ is: he is; CuClr2H20 'InCl3.4H20, the molar concentration of Ga and Na2Se is between 0.90 : 0.88 : 〇 '22 : 2.20 ~ 1.10 : 〇 · 72 : 0.18 : 1.90 between. 9. The method according to the invention of claim 3, wherein the chimeric solvent is ethylenediamine; the starting material containing Cu 疋CuCl '6 Hai contains a starting material of μ丨It is a group of InCl3.4H2 〇 and Ga, the starting material containing M2 is Se; the Mohr concentration of CuCl, InCl3.4H20, Ga and Se is 0.90 : 0.88 : 0.22 : 2.20~ - 1.1〇· 0.72: 0.18: 1·9〇. , 10. According to the scope of the 4 patents! The method for producing a cis-based powder according to the invention: wherein the chimeric solvent is ethylenediamine; the starting material containing Cu is CuCl2 2H2 〇, and the starting material containing M ΐ is ΐηΐ ΐ3.4Η2 The combination of 〇 and Ga 'The starting material containing M2 is Se; cuci2.2H20 '27 I unlined version] Patent No. 097103740 is applied for continuation. Replacement of the monthly case, correction of the unlined specification page replacement page correction period: 100 years October 6曰InCl3-4H2〇' Ga M Se έΑ The Mohr concentration is between 0.90 : 0.88 : 〇·22:2·20 ~1·10:0·7^0·18:1·90. U. The method for producing a powder according to item (3) of claim i wherein the inert gas in the reaction tank is selected from the group consisting of N2, Ar, He, or a combination thereof; the chimeric solvent The amount used is between 5 〇 Q / 〇 ~ 90% of the liquid level of the reaction tank. 12. The method for producing a CIS-based powder according to the above-mentioned claim, wherein the reflux temperature in the reaction tank is between 9 〇〇c and 3 〇 (rc, and the reflux of the 5 liter reaction tank) The time is between 4 hours and 48 hours. 13. A method for producing a CIS target, comprising the following steps: (a) filling a mold in a cavity as claimed in the first to the twentieth The CIS powder obtained by the method of any one of the items; (b) applying a pressure to the cavity under a pressure of between 10 2 Torr and 1 〇 -5 T rr to form a purification chamber (c) applying the temperature of the powder in the chamber to a predetermined temperature and holding the temperature for a predetermined time 'where' the temperature increase rate is between 2. (: /min~1 〇°C/min The predetermined temperature is between 5 〇〇 ° c and 800. (: between and the predetermined time is between 1 hour and 8 hours; (d) the powder in the purification chamber is boosted up to one The predetermined pressure is held for a predetermined period of time to cause the CIS-based powder to obtain powder densification energy via the predetermined temperature and a predetermined pressure, wherein the pressure-up rate Between 1 MPa/min and 3 MPa/min, the predetermined pressure is between 60 MPa and 180 MPa and the predetermined time is S 28 1353344 4 Patent application No. 097103740 After the unlined specification replacement page correction date: 100 years October 6 曰 - between 1 hour and 8 hours; and (e) remove the predetermined pressure and introduce inert gas into the purification chamber to cool the Purify the cavity. 29