TW201127483A - Fabrication method for IB-IIIA-VIA powder by the sol-gel method - Google Patents

Abstract

The invention provides a fabrication method for IB-IIIA-VIA powder by the sol-gel method, comprising: (a) dissolving a Group IB compound, a Group IIIA compound in an solvent; (b) dissolving an gelation agent in the solvent of the step (a) to form a sol; (c) drying the sol to form a gel; (d) heating the gel to form a precursor powder containing Group IB and IIIA; and (d) subjecting the precursor powder to a thermal process to introduce a Group VIA compound into the precursor powder and to obtain the IB-IIIA-VIA powder.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a semiconductor material, and more particularly to a process for preparing a powder of IB-IIIA-VIA compound by a sol-gel method. [Prior Art] The IB-IIIA-VIA compound has a special energy level (enei>gy gap), which can change the electronic and optical properties of the material by adjusting the ratio of its components. Applied to solar cells. When the IB-IIIA-VIA compound is prepared into a powder type bear, it can be applied to a vacuum process target or a material which can be applied to a coating process. However, the biggest challenge in making the ib_iiia_via compound powder is to prepare a powder that is fine and uniform in particle size. The sol-gel method involves the conversion of the liquid phase (sol) to the solid phase (gel) of the system. In a typical sol-gel method, the raw material of the sol is a solid particle (usually an inorganic metal salt) suspended in a liquid. The reactants undergo a series of hydrolysis, condensation and polymerization to finally condense into a new phase, meaning a gel. The sol-gel method has the advantages of being prepared at a low temperature, high controllability, high product uniformity, and the like, and thus is widely used in various fields such as ceramics, glass, inorganic thin films, aerogels, organic-inorganic composite materials, and the like. . U.S. Patent Publication No. US 2005/0183767 provides a method for preparing a 1% energy battery in a solution form, first taking an organometallic compound containing elements of IB, in a and IA, and mixing the organic metals to form 201127483

An organometallic liquid ink is applied to the substrate, followed by selenization to obtain a m_IIIA_VIA film. However, organometallics are highly toxic and unstable, so the preparation process should be used with care. If the sol-gel method can be incorporated into the method of preparing the IB-IIIA-VIA compound, it should contribute to the provision of minute and uniform powder particles. SUMMARY OF THE INVENTION The present invention provides a method for preparing a bismuth-quinone-VIA compound powder, comprising the steps of: dissolving a steroid and a steroid in a solution of W; (b) Geiati〇ri agent) in the solvent of step (8) to form a sol (sol); (c) drying the sol to obtain a gel; (d) heating the gel to obtain an element containing IB and IIIA elements a precursor powder; and (e) subjecting the precursor powder to a heat treatment process to introduce a VIA group of the precursor powder into the precursor powder to obtain a ΙΒ·ΠΙΑ_νΐΑ compound powder. The above and other objects, features, and advantages of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The method for preparing a -IIIA-VIA compound powder comprises the following steps: &amp; first step (&amp;) dissolving a steroid and a steroid in a solvent, wherein the lanthanum comprises copper (Cu), silver (Ag), gold (Au) ) 201127483 or a combination thereof, and the IB group compound includes an oxide, a nitride, a hydroxide, a sulphate, a sulphate, an acetate, a sulphate, a carbonate, a sulphuric acid, a sulphuric acid, a sulphate, Capric acid, oxalic acid, fillers, such as copper oxide (CuO), copper nitride (Cu(N3)2), copper hydroxide (Cu(OH)2), vaporized copper (CuCl2), silver nitrate (AgN03) , copper nitrate (Cu(N03)2), copper sulfate (CuS04), copper acetate (Cu(CH3COO)2), silver acetate (CH3COOAg), copper carbonate (Cu2C03), copper oxalate (CuC204), gas-acid steel (Cu (C104) 2), copper phosphate (Cu3 (P04) 2), copper lithate (CuSe04) or phosphatized steel (Cu3P). The above Group IIIA includes aluminum (A1), indium (In), gallium (Ga) or a combination thereof, and the Group IIIA compound includes an oxide, a nitride, a hydroxide, a hydroxide, a nitrate, and an acetic acid containing a lanthanum group. , sulphate, carbonate, chlorate, acid, citrate, oxalate or filler, such as indium oxide (ln203), oxidized (Ga203), 匕ϋ (ΙιιΝ), IU 匕 (GaN ), gas indium oxide (In(0H)3), gallium hydroxide (Ga(OH)3), aluminum chloride (A1C13), gasified la(InCl3), chlorinated (GaCl3), nitric acid (L1) (N03) 3), Shi Xiaoximan Steel (Ιη(Ν03)3), gallium nitrate (Ga(N03)3), indium acetate (In(CH3COO)3), aluminum acetate (ai(ch3coo)3), aluminum carbonate ( Ai2(co3)3), aluminum oxalate (Al2(C2〇4)3), gallium acetate (Ga(CH3COO)3), indium sulfate (In2(S04)3), aluminum sulfate (A12(S04)3), sulfuric acid Gallium (Ga2(S04)3), indium sulphate (In(C104)3), gallium chlorate (Ga(C104)3), indium phosphate (ΙηΡ04), gallium phosphate (GaP04), indium selenate (In2(Se) 〇 4) 3), gallium ruthenate (Ga 2 (Se 〇 4) 3), indium (InP) or filled with gallium (GaP). It should be noted here that the selection of the Group IB and Group IIIA compounds is not limited to the above-mentioned compounds, as long as they contain the Group IB and Group IIIA elements. The above solvent may include, in addition to the solvent water, an alcohol, a ketone, an ether, an amine, an acid, a test, or a combination thereof. The above alcohols include decyl alcohol, ethanol, propanol, isopropanol, n-butanol, isoamyl alcohol or ethylene glycol; ketones include acetone, methyl ethyl ketone, decyl isobutyl ketone; ethers include oxime ether, diethyl ether, Methyl ether, diphenyl ether, ethylene glycol oxime ether, ethylene glycol butyl ether or ethylene glycol ethyl ether; amines include ethylene diamine, dimethyl decylamine, triethanolamine or diethanolamine. The above acids include nitric acid, hydrochloric acid, sulfuric acid, acetic acid or pyruvic acid. φ The above bases include sodium hydroxide (NaOH), argon oxide clock (KOH), lithium hydroxide (LiOH), urea (CON2H4), ammonia (NH3), sodium carbonate (Na2C03), sodium hydrogencarbonate (NaHC03) or the above The combination. However, the choice of the solvent is not limited to the above-mentioned alcohols, ketones, ethers, amines, acids, base solvents, and may be any single or mixed solvent capable of dissolving the above compounds. The molar ratio of the above IB compound to the steroid is about (0.7 to 1.4): (0.7 to 1.4), preferably about (0.7 to 1.3): (0.7 to 1.3), and the optimum is about 0.8. ~1.3) : (0.8~1.3). Further, a IA group compound or a VIA group compound may be added to the solvent of the step (a), and the addition of the steroid compound may improve the characteristics of the solar cell. For example, a steroid can be added to increase the photoelectric conversion efficiency of the battery, wherein the lanthanum includes lithium (Li), sodium (Na), potassium (Κ) or a combination thereof, and the steroid compound includes a IA group halide, nitric acid. , acetic acid, sulfuric acid, carbonate or gaseous acid, such as lithium chloride (LiCl), sodium (NaCl), potassium chloride (KC1), lithium nitrate (LiN03), sodium nitrate (NaN03), nitric acid Potassium (KN〇3), lithium acetate (CH3COOLi), sodium acetate (CH3COONa), potassium acetate 201127483 (CH3COOK), sulfuric acid (Li2S〇4), sodium sulfate (Na2S04), sulfuric acid needle (K2S04), lithium carbonate (Li2C03 ), sodium carbonate (Na2C03), carbonic acid clock (K2C03), lithium silicate (LiC103), sodium chlorate (NaC103) or potassium chlorate (KC103). The above Group VIA includes sulfur (S), selenium (Se), tellurium (Te) or a combination thereof, and the Group VIA compound includes oxides, halides, oxyhalides, sulfides, tellurides, amines of Group VIA. a compound, a urea compound, a citrate, a sulphate or a citric acid, such as selenium oxide (Se02), cerium oxide (Te02), sulfuric acid (H2S〇4), selenate (H2Se04), citric acid (H2Te04), sulfurous acid (h2S03), selenite (H2Se03), telluric acid (H2Te03), thiourea (CS(NH2)2), selenourea (CSe(NH2)2), chlorinated stone (SeCI) ), Tetrachloride West (SeCl4), Digassed Hoof (TeCl), Tetrachloride (TeCl4), Bismuth dibromide (SeBr2), Neodymium tetrabromide (SeBr4), Bismuth dibromide (TeBr2) , TeBr4, TeOCl2 or SeS2. The Moir number ratio of the above Group IB compound, Group IIIA compound and Group IA compound is about (0.7 to 1.4): (0.7 to 1.4): (0.005 to 0.2), preferably about (0.7 to 1.3): (0.7 to 1.3) ) : (0.006~0.2), the best is about (0.^.3): (0.8~1.3) : (0.008~0.2). Next, step (b) is carried out by adding a gelation agent to the solvent of the step (a) to form a sol (sol), wherein the gelling agent has two kinds, and the first gelling agent comprises a chelating agent and a polymerization agent. The chelating agent can bond with the metal cation to form a complex to promote the uniformity and reactivity of the metal ion distribution, and the polymerization agent functions to generate a dehydration polymerization reaction with the chelating agent to increase the uniformity of the reaction. . 201127483 The above chelating agents include tartaric acid, oxalic acid, propionic acid, maleic acid, citric acid, pentaethylenehexamine (PEHA), glycidyl methacrylate (GMA). Or ethylenediaminetetraaccetic acid (EDTA), and the polymerization agent is a polyol containing two or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerol, butanediol, butyl alcohol, butyl alcohol, pentane Glycol, glycerol, polyethylene glycol, glycerin, and the like. Another gelling agent is a polymer containing a warp group, and the polymer containing a warp group includes poly (vinyl alchol) and polyvinylpyrrolidine (p〇ly (viny 1 butyral)). Or polyethylene glycol, such polymers can also improve the uniformity of metal ion distribution. Next, the step (4) is performed to dry the sol to obtain a gel (gei), wherein the drying temperature is about 70 ° C to 350 ° C, and the time is about 30 minutes to 8 hours. This step is used to remove excess water to help form a gel. gum. Thereafter, the step (d) is carried out to heat the gel to obtain a precursor powder having a heating temperature of about 200 ° C to 8001 for a period of about 1 hour to 5 hours. This step is for removing excess water and organic matter. Thereafter, the precursor powder is subjected to a heat treatment process in the step (e) to introduce a Group VIA element into the precursor powder to obtain a powder of the IB4IIA-VIA compound. The purpose of the heat treatment process is to improve the powder properties and to make the powder more uniform in its morphology. The above-mentioned via family and its compounds are as described above and will not be described again. The heat treatment process can be divided into two processes, the first process includes mixing the VIA powder and the precursor powder to obtain a mixed powder; and placing the mixed powder in a gas atmosphere for heat treatment, wherein the VIA powder 201127483 and the precursor powder The molar ratio is about (0.01 to 20): 1 ' is preferably about (0.5 to 10): 1, more preferably about (1 to 4): 1. The above gas atmosphere includes a gas containing a Group VIA element such as hydrogen selenide (H2Se), hydrogen sulfide (H2S), ruthenium (Se) vapor, sulfur (S) vapor, ruthenium (Te) vapor or a combination thereof. In addition, the gas atmosphere includes other gases such as nitrogen (N2), hydrogen (H2), argon (Ar), carbon monoxide (CO), carbon dioxide (C02), ammonia (NH3), monooxide (NO), oxygen. (〇2), air or a combination of the above. The second heat treatment process comprises subjecting the precursor powder to a heat treatment process in a gas atmosphere containing VIA, wherein the gas atmosphere of the Group VIA is the same as described above and will not be described herein. Regardless of the first or second heat treatment process, the process temperature is about 300 ° C to 900 ° C, and the time is about 1 hour to 24 hours. It should be noted here that the preparation process of the above steps (a) to (c) can be carried out under normal room temperature and atmospheric environment without additional control of the atmosphere, temperature, humidity and pressure of the process. Compared with the conventional alloy preparation method, the invention has the advantages of preparing the IB-IIIA-VIA compound powder by the sol-gel method, that the metal ions are uniformly distributed in the solution, the process temperature is low, and the preparation time is short. Compared with the prior art (US 2005/0183767), using organometallic as a starting material, the Group IB or IIIA compound of the step (a) of the present invention is not only non-toxic, but also has high chemical stability, and the preparation cost is low, and Conducive to industrial applications.

The powder of the IB-IIIA-VIA compound obtained by the present invention was confirmed by X-ray diffraction pattern analysis to be a crystal structure of chalcopyrite. In addition, it is known by scanning electron microscopy (SEM) that the particle size is about 〇·〇1~3 μιη′, preferably about 〇.〇1~〇.1 μιη, and the obtained ib-IIIA-VIA 201127483 The compound powder has a spherical structure and has a multi-ply-dimension surface type, and a chalcopyrite powder having a multi-dimensional surface state can obtain a relatively uniform coated surface in a subsequent coating process. In summary, the present invention utilizes a sol-gel method to prepare a powder of a compound of Β·ΠΙΑ-νΐΑ, which is uniformly distributed in a sol solution by a gelling agent, and is dried to form a gel, and then combined with subsequent heat treatment. The process is to obtain a small and uniform powder. The powder of 1B-IIIA-VIA compound produced by the above process can be used as a target for a vacuum process, wherein the vacuum process includes evaporation or sputtering. In addition, after the above-mentioned ΙΒ-ΙΠΑ-VIA compound powder is mixed into a slurry, it can be used as a raw material of a coating process, wherein the coating process includes spin coating, bar coating, Dip coating, roll coating, spray coating, gravure coating, ink jet printing, slit coating (slot) Coating) or blade coating. Furthermore, the IB_IIIA_VIA compound powder can also be used as a solar cell (Solar Cell) ® light absorbing material. [Examples] Example 1 Aqueous solution, mixture. According to the chemical composition ratio of CUInSe2, 'first add citric acid as a chelating agent' to prepare a mixed mixture of CuCl2 and InCl3, and then add ethylene glycol as a poly-polymer, and dry to obtain a gelatinous product, and the aqueous solution is stirred evenly, 201127483 The gelatinous product was heated in a 400 ° C oven for three hours to remove organic matter to obtain a precursor, and the precursor was ball-milled with an excess of selenium powder so that the ratio of &amp; to (CU++In3+) was L1. :1, and then heated at 500 ° C for one hour under a nitrogen-hydrogen reducing atmosphere to obtain a desired CuInSe 2 powder. The first picture is the X-ray diffraction analysis of the powder. The figure shows that the powder has three main diffraction peaks (112), (204)/(220) and (312)/(116), ^ (204) and (220) are the diffraction peaks at the same position, and (312) and (116) are also the same diffraction peaks as the ICDD card number 895646, which is a chalcopyrite structure. Example 2 According to the chemical composition ratio of CuIn0 5Ga0.5Se2, an aqueous solution of CuCl2, InCl3, Ga(N03)3 and Se02i was added, and 5 mol% of NaC1 was added to the aqueous solution, and oxalic acid was first added as a chelating agent and then added. Glycerin is used as a polymerization agent. After the aqueous solution was stirred uniformly, it was dried to obtain a gel-like product, and the gelled product was heated in an oven at 500 ° C for three hours to remove the organic matter to obtain a precursor, and then the precursor was subjected to a nitrogen-hydrogen reducing atmosphere. The heat of 〇〇c is heated for thirty minutes to obtain the desired CuIn〇5G() 5Se2 powder. The powder has three major diffraction peaks (112), (204)/(220) and (312)/(116) after X-ray diffraction pattern analysis, which conforms to ICDE) card number 4〇1488 map 'this The powder is a chalcopyrite structure. Example 3 According to the chemical composition ratio of CuIn0.7Ga0.3Se2, an aqueous solution of CuCl2, InCl3 201127483 and Ga(N〇3)3 was added, and ethylenediamineteraacetic acid (EDTA) was added as a chelating agent, and then added. Propylene glycol is used as a polymerization agent. After the aqueous solution is uniformly mixed, it is dried to obtain a gelatinous product, and the dried gelatinous product is heated in a 550 〇c oven for one hour to remove the organic matter to obtain the other precursor, and then the precursor and the excess are added. The tortoise powder is ball-milled and mixed so that the molar ratio of Se to (Cu++In3++Ga3+) is 1.5:1, and then heated at 550 ° C for 30 minutes under a nitrogen-containing reducing atmosphere containing a code gas. %% of CuIn〇.7Ga〇_3Se2 powder is required. The powder has three main diffraction peaks (112), (2〇4)/(220) and (312)/(116) after X-ray diffraction pattern analysis, among which (2〇4) and (22) 〇) is the diffraction peak of the same position, and (312) and (116) are also the diffraction peaks at the same position, which conforms to the ICDD card number 351102 map, and the powder is a chalcopyrite structure. Example 4 Proton Cui jAlSe2 chemical composition ratio 'Equipped with an aqueous solution of CuCl2 and Α1(Ν〇3)3, and added 10 mol% of NaC1 in an aqueous solution, and then added polyvinyl alcohol (polyvinyl Alcoho pvA) as The gelling agent is stirred uniformly to obtain a gelatinous product, and the dried gelatinous product is heated in an oven at 350 ° C for three hours to remove the organic matter to obtain a precursor, and then the precursor and excess The selenium powder and the sulfur powder are ball-milled and mixed so that the molar ratio of (Se+S) to (Cu++In3++Ga3+) is 2:1, and then heated at 450 ° C for one hour under a nitrogen-hydrogen reducing atmosphere. The desired CuAl(Se,S)2 powder can be obtained. 201127483 This powder has two main diffraction peaks (112), (204) and (312) after X-ray diffraction pattern analysis. It conforms to the ICDd card number 75〇1〇1 map. This powder is chalcopyrite. structure. Example 5 According to the ratio of the chemical composition of Cu0.8GaSe2, a solution of CuCl2, Ga(N03)3^, and HJeO3/tCi was added, and tartaric acid was first added as a chelating agent and then butanediol was added as a polymerization agent. After the aqueous solution was stirred uniformly, it was dried to obtain a gel-like product, and the product was heated in a Wc furnace for one hour to remove the organic matter to obtain a precursor, and then the precursor was subjected to a nitrogen-hydrogen reducing atmosphere at 5 〇〇〇C. After heating for one hour, the desired cuGaSe2 powder can be obtained. Μ This powder has five major diffractions of (112), (220), (204) and (312), (116) after X-ray diffraction pattern analysis. The peak is in accordance with the ICDD card number 81〇9〇3 map, and the powder is a yellow steel ore structure. Example 6 According to the chemical composition ratio of AglnuSes, the water/gluten solution of AgN03 and In(N〇3)3 is added to the aggregate. Ethylene glycol (p〇lyethyiene giyC〇i, peg) is used as a gelling agent. After the aqueous solution is stirred uniformly, it is dried to obtain a gelatinous product, which is heated in a furnace at 4 ° C. The organic matter was removed for three hours to obtain the precursor. The ballast and the excess selenium powder were ball-milled to make the Mohr number ratio of Se to (Ag++In3+) 3:1, and then the hydrogen reduction of the selenium-containing gas. Heat at 550 ° C for 18 hours to obtain the desired Aginise 2 201127483 powder. This powder is X-ray After the spectroscopic analysis, there are three main diffraction peaks (112), (204) and (312), which are in accordance with the ICDD card number 7501 18, which is a chalcopyrite structure. Although the present invention has several comparisons The preferred embodiments are disclosed above, but are not intended to limit the invention, and any one of ordinary skill in the art can make any changes and modifications without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

15 201127483 [Simple description of the drawing] Fig. 1 is an X-ray diffraction pattern' for explaining the structure of the brass stone powder of the present invention. [Main component symbol description]

16

Claims (1)

201127483 VII. Patent application scope: 1. A method for preparing IB-IIIA-VIA compound powder by sol-gel method, comprising the following steps: (a) dissolving a group IB compound and a group IIIA compound in a solvent; Adding a gelation agent to the solvent of step (a) to form a sol; (c) drying the sol to obtain a gel; (d) heating the gel to obtain a gel a precursor powder containing IB and a lanthanum element; and (e) a heat treatment process for the precursor powder to introduce a Group VIA element into the precursor powder to obtain a powder of the IB-IIIA-VIA compound. 2. The method for preparing a powder of IB-IIIA-VIA compound by a sol-gel method as described in claim 1, wherein the molar ratio of the group IB compound to the group IIIA compound is about (0.7 to 1.4): (0.7~1.4). 3. A method for preparing a powder of IB-IIIA-VIA compound by a sol-gel method as described in claim 1, wherein the solvent comprises water, an alcohol φ, a ketone, an ether, an amine, an acid, A base or a combination of the above. 4. A method of preparing a powder of IB_IIIA-VIA compound by a sol-gel method as described in claim 1, wherein step (a) further comprises mixing a compound of Group IA or a compound of Group VIA in the solvent. 5. A method of preparing a powder of IB-IIIA-VIA compound by a sol-gel method as described in claim 1, wherein the gelling agent comprises a chelating agent and a polymerization agent. 6. A method for preparing a powder of IB-IIIA-VIA compound by a sol-gel method as described in claim 5, wherein the chelating agent comprises tartar 17 201127483 acid, oxalic acid, propionic acid, maleic acid , citric acid, pentaethylene hexamine (PEHA), glycidyl methacrylate (GMA) or ethylenediaminetetraaccetic acid (EDTA). 7. A method of preparing a powder of IB-ΠΙΑ-VIA compound by a sol-gel method as described in claim 5, wherein the polymerization agent comprises a polyol having two or more hydroxyl groups. 8. A method of preparing a powder of IB-IIIA-VIA compound by a sol-gel method as described in claim 1, wherein the gelling agent comprises a polymer containing a hydroxyl group. 9. The method of preparing a powder of IB-IIIA-VIA compound by a sol-gel method according to claim 1, wherein the heat treatment process comprises the steps of: mixing a powder containing a group VIA with the powder of the precursor to obtain Mixing the powder; and subjecting the mixed powder to a gas atmosphere for heat treatment. 10. The method for preparing a powder of IB-IIIA-VIA compound by a sol-gel method as described in claim 1, wherein the heat treatment process comprises the step of: placing the precursor powder in a gas containing a VIA gas atmosphere The heat treatment process is carried out.