201228930 ， 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種製造IB-IIIA-VIA化合物之万 法’特別是一種利用IB及IIIA族金屬之前驅粉體製造 IB-IIIA-VIA化合物之方法。 【先前技術】 近年來由於受到全球氣候變遷、環境污染問題以及資 满ι a趨短缺的影響，在環保意識高漲與能源危機的警訊下 刺激了太陽光電產業的蓬勃發展。於各種太陽能電池巾，· 由於砸化銅鋼鎵電池(Cu(In，Ga)Se2，CIGS)具備高轉換效 率、穩定性佳、材料成本低、可製成薄膜等優點，因此受 到極大的重視。 CIGS化合物屬於黃銅礦(chaic〇pyrite)結構，其主要由 IB-IIIA-VIA2族化合物所組成’其為一種直接能隙（direct bandgap)半導體材料，可藉由調控組成而改變半導體之能 隙’疋目前常用以作為光吸收層之主要材料。 目前IB-IIIA-VIA化合物通常係利用真空製程來製籲 備，例如共蒸鍍法（Coevaporation)及氣相沉積製程。由於 真空製程具有設備成本較高、材料使用率低且材料之製備 較為繁複等缺點，因此，近年來逐漸朝向採用非真空製程 來製備IB-IIIA-VIA化合物。 另一方面，使用IB與ΙΠΑ族金屬氧化物或氮氧化物 之奈米粉體作為IB-IIIA-VIA化合物的前驅物時，需在硫 化或栖化步驟前，於高溫環境下進行還原反應，以去除氧 111826 4 201228930 及氮。若採用聯胺還原法結合熱處理步驟於製備 IB-IIIA-VIA化合物，則需克服聯胺具有高危險性及不穩定 性等問題。 因此仍需要一種製程簡單，且能有效降低成本之方 法。 【發明内容】 為達成上述及其他目的，本發明提供一種製造 IB-IIIA-VIA化合物之方法，包括：配製含有元素週期表IB • 族及IIIA族金屬陽離子之反應溶液；將還原劑加入該反應 溶液中，使該ΙΒ族及ΙΙΙΑ族金屬陽離子還原成金屬；乾 燥獲得ΙΒ及ΙΙΙΑ族之金屬粉體；以及使用VIA族元素之 蒸氣或直接與VIA族元素混合進行熱處理，形成 IB-IIIA-VIA化合物。本發明方法係在溶液中，利用還原劑 將IB族及IIIA族金屬陽離子還原為金屬，形成具有高活 性之奈米級前驅粉體。該前驅粉體不含氮元素與氧元素， φ 不需要預先進行還原除氧步驟，即可直接進行硒化、硫化 或碲化之熱處理，形成IB-IIIA-VIA化合物，應用於製作 光電材料，不僅可簡化製程，更具有降低生產成本之優點。 本發明又提供一種製造IB及IIIA族金屬粉體之方 法，包括：配製含有元素週期表IB族及IIIA族金屬陽離子 之反應溶液；將還原劑加入該反應溶液中，使該IB族及 ΙΙΙΑ族金屬陽離子還原成金屬；以及乾燥獲得IB及IIIA 族金屬粉體。本發明之方法可在低溫條件下，於溶液中進 行反應，利用還原劑將IB族及IIIA族金屬陽離子還原為 5 111826 201228930 ， 金屬’形成奈米級金屬粉體’所形成之奈米級金屬粉體I 有高活性，且不含氮元素與氧元素’可用作為製造 ΙΒ-ΠΙΑ-VIA化合物之前驅粉體，不但能夠簡化製程降低設 備成本’同時能夠提高原物料的使用率，可應用於製作光 電材料。 【實施方式】 以下藉由特定的具體實例說明實施方式，惟該等實施 例僅為本發明之示例，不應據以侷限本發明之範圍，熟習 此項技藝之人士均可由說明書及後文之申請專利範圍之揭籲 示，根據需要加以適當的變化，而該等變化均含於本發明 之範疇。 本發明製造IB-IIIA-VIA化合物之方法係在溶液中， 利用還原劑將IB族及IIIA族金屬陽離子還原為金屬，形 成奈米級之金屬粉體，再使用VIA族元素之蒸氣或混合 VIA族元素，進行金屬粉體之熱處理，形成IB-IIIA-VIA ,。物。本發明方㈣先將分別含有族及脈族金屬 子之原料溶於水、無機或有機溶射，均句混合形成 2::液後’再進行IB族及ΙΠΑ族金屬離子之還原反應。 ^明枝所使用之金屬㈣频射旨可於溶液中解離出 物二二 之化合物或鹽類，包嶽 族金屬陽離子二 鹽、草㈣或碳酸鹽°該含有 化物、漠化物、實例包括銅、銀或金之氣化物、氣 鹽或碳酸鹽，·麻^肖酸鹽、醋酸鹽、硫酸鹽、草酸 為鋼、銀或金之氯化物或硝酸鹽。該含 6 111826 201228930 有IIIA族金屬陽離子之原料實例包括蝴、紹、嫁、姻或銘 之氟化物、氣化物、溴化物、碘化物、硝酸鹽、醋酸鹽、 硫酸鹽、草酸鹽或碳酸鹽；較佳為爛、铭、嫁、鋼或銘之 氯化物或硝酸鹽。 本發明方法係先將金屬粉體原料溶於水、無機或有機 溶劑，例如乙醇、丙酮、乙二醇等，形成含有m族及ΙΠΑ 族金屬陽離子之反應溶液，再將還原劑加入反應溶液，使 反應溶液中的金屬離子進行還原反應形成金屬、合金或其 籲混合物。該還原劑的實例包括硼氫化物，例如硼氫化鈉 (NaBILO、硼氫化鉀（KBH4)、三乙基硼氫化鈉（NaBEt3H)、 三乙基硼氫化鋰(LiBEt3H);聯氨(N2H4)或有機酸等。該還 原劑可直接添加至含有IB族及IIIA族金屬陽離子之反應 溶液’或以溶液形式添加至反應溶液，使溶液中的IB族及 IIIA族金屬離子同時還原成金屬。該還原反應通常係於〇 至200°C之溫度條件下進行，較佳係於10至100°C之溫度 I 條件下進行，更佳係於15至80°C之條件下進行。本發明 方法之還原反應，壓力條件並無限制，可以在常壓下進行， 亦可加壓幫助反應。 本發明之方法中，可進一步將穩定劑，例如三乙胺 (triethylamine )、乙二胺四乙酸（EDTA)、檸檬酸（citric acid)、抗壞血酸(ascorbic acid)、β-胡蘿蔔素（β-carotene)、 番莊紅素（lycopene)、丁經基茴香醚（butylated hydroxyanisole ， BHA) 、 丁經基曱苯（butylated hydroxytoluene，BHT)或 3,4,5-三經基苯甲酸丙醋（propyl 7 111826 201228930 gaUateS’PG)等，添加至溶液中，避免金屬或合金氧化。 反應溶液中的金屬離子完成還原反應㈣金屬、合金或其 混合㈣’可_離心'或贼的方式，分離並去除溶液' 剩餘的固體經乾燥後，即可獲得金屬粉體、合金粉體或其 可在低溫及空氣條件下，於反應溶液中進 2太還原反應分離並去除溶液’乾燥剩餘固體後即可 ^不米級金屬粉體、合金粉體或其混合物，作為前驅粉 ，。該奈来級前驅粉體具有高活性，且不含氮元素與氧元 =用於製造IB-mA-VIA化合物，不需要預先進行還原 除氧步驟’即可直接進行砸化、硫化、或蹄化反應之熱處 理，形成IB-IIIA-VIA化合物。 於具體實例中’係將該前驅粉體分散於溶劑中，形 成漿料。接著’利用塗佈法或印刷法將漿料施加至基板上， 於非真空魏下，將基板置於包括Μ絲社氣氛中， 進订例如靴、硫化、或雜之Μ理，於絲板上形成 可作為光吸收層之；!謂A_VIA化合物薄膜。通常，該執 處理係於約15〇至_。(：之溫度條件下進行，歷時⑽至 20广時，形成m-mA-VIA化合物薄膜，可應用於cIGS 太陽能電池作為光吸收層。 相較於以往使用IB族與ΠΙΑ族金屬氧化物或氮氧化 物粉，造ΙΒ·ΙΙΙΑ_νΙΑ化合物之方法，本發明方法所利 用之前驅粉體不含氮元素與氧元素，可簡化既往使用金屬 氧化物或氮氧化物，需去除ΙΒ族與ΠΙΑ族氧化物或氮氧 111826 8 201228930 化物之I及氧等元素的額外步驟。本發明方法所使用之前 驅粉體’可直接進行硫化、魏切化之減理，形成 m-mA-VIA化合物。另一方面，本發明方法可避免利用非 真空製程製備！請A_VIA化合物所需使用之高危險性邀 不穩定之聯胺還原步驟。 、 實施例 實施例1201228930, VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for producing a compound of IB-IIIA-VIA, in particular, a precursor powder using IB and IIIA metals to produce IB-IIIA-VIA Method of compound. [Prior Art] In recent years, due to the global climate change, environmental pollution problems and the shortage of capital, the solar photovoltaic industry has been booming under the warning of high environmental awareness and energy crisis. For various solar cell towels, · Due to the advantages of high conversion efficiency, good stability, low material cost, and the ability to form thin films, the copper-germanium-germanium gallium battery (Cu(In,Ga)Se2, CIGS) has received great attention. . The CIGS compound belongs to the chaic 〇pyrite structure, which is mainly composed of IB-IIIA-VIA2 compound. It is a direct bandgap semiconductor material, which can change the energy gap of the semiconductor by regulating the composition. '疋 is currently used as the main material for the light absorbing layer. Currently, IB-IIIA-VIA compounds are usually prepared by a vacuum process such as coevaporation and vapor deposition processes. Since vacuum processes have disadvantages such as high equipment cost, low material utilization rate, and complicated material preparation, in recent years, IB-IIIA-VIA compounds have been gradually prepared by a non-vacuum process. On the other hand, when using IB and lanthanum metal oxide or oxynitride nanopowder as a precursor of IB-IIIA-VIA compound, it is necessary to carry out the reduction reaction in a high temperature environment before the vulcanization or thawing step. Remove oxygen 111826 4 201228930 and nitrogen. If the hydrazine reduction method combined with the heat treatment step is used to prepare the IB-IIIA-VIA compound, it is necessary to overcome the problems of high risk and instability of the hydrazine. Therefore, there is still a need for a process that is simple in process and can effectively reduce costs. SUMMARY OF THE INVENTION To achieve the above and other objects, the present invention provides a method for producing a compound of IB-IIIA-VIA, comprising: formulating a reaction solution containing a metal cation of Group IB and Group IIIA of the periodic table; adding a reducing agent to the reaction In the solution, the lanthanide and lanthanide metal cations are reduced to a metal; the bismuth and lanthanum metal powders are obtained by drying; and the IB-IIIA-VIA is formed by heat treatment using a group VIA element vapor or directly mixed with a group VIA element. Compound. The method of the present invention reduces the Group IB and Group IIIA metal cations to a metal by a reducing agent in a solution to form a nano-active precursor powder having high activity. The precursor powder does not contain nitrogen element and oxygen element, and φ can be directly subjected to heat treatment of selenization, vulcanization or deuteration without a prior reduction and oxygen removal step to form an IB-IIIA-VIA compound, which is used for the production of photovoltaic materials. It not only simplifies the process, but also has the advantage of reducing production costs. The invention further provides a method for manufacturing IB and IIIA metal powder, comprising: preparing a reaction solution containing a metal cation of Group IB and Group IIIA of the periodic table; adding a reducing agent to the reaction solution to make the IB group and the steroid Reduction of the metal cation to the metal; and drying to obtain the IB and IIIA metal powder. The method of the invention can carry out the reaction in a solution under low temperature conditions, and reduces the IB group and the IIIA metal cation to 5 111826 201228930 by using a reducing agent, and the nano-metal formed by the metal 'forming a nano-sized metal powder' Powder I has high activity and contains no nitrogen and oxygen. It can be used as a precursor powder for the manufacture of ΙΒ-ΠΙΑ-VIA compounds, which not only simplifies the process and reduces equipment costs, but also improves the utilization rate of raw materials. Making photovoltaic materials. The embodiments are described below by way of specific examples, but the examples are only examples of the invention, and should not be construed as limiting the scope of the invention, and those skilled in the art can The disclosure of the scope of the patent application is subject to appropriate changes as needed, and such variations are intended to be included within the scope of the invention. The method for producing the IB-IIIA-VIA compound of the present invention is a solution in which a metal hydride of a Group IB and a Group IIIA metal is reduced to a metal by a reducing agent to form a metal powder of a nanometer type, and a vapor of the VIA group element or a mixed VIA is used. The group element is subjected to heat treatment of the metal powder to form IB-IIIA-VIA. Things. The present invention (4) first dissolves the raw materials containing the family and the pulsed metal in water, inorganic or organic, and uniformly mixes them to form a 2:: liquid, and then carries out a reduction reaction of the IB and lanthanum metal ions. ^The metal used in the Mingzhi (4) is a compound or salt that can dissociate the second compound in the solution, the metal salt of the cation metal salt, the grass (four) or the carbonate. The compound, the desert compound, examples include copper. , silver or gold gasification, gas salt or carbonate, · methic acid, acetate, sulfate, oxalic acid is steel, silver or gold chloride or nitrate. Examples of raw materials containing Group IIIA metal cations including 6 111826 201228930 include fluoride, vapor, bromide, iodide, nitrate, acetate, sulfate, oxalate or carbonate Salt; preferably chloride, nitrate, or sulphur, steel, or salt. The method of the invention first dissolves the metal powder raw material in water, an inorganic or organic solvent, such as ethanol, acetone, ethylene glycol, etc., to form a reaction solution containing a metal cation of the m group and the lanthanum, and then adds the reducing agent to the reaction solution. The metal ions in the reaction solution are subjected to a reduction reaction to form a metal, an alloy or a mixture thereof. Examples of the reducing agent include borohydrides such as sodium borohydride (NaBILO, potassium borohydride (KBH4), sodium triethylborohydride (NaBEt3H), lithium triethylborohydride (LiBEt3H); hydrazine (N2H4) or An organic acid, etc. The reducing agent may be directly added to a reaction solution containing a Group IB and a Group IIIA metal cation or added to the reaction solution as a solution to simultaneously reduce the Group IB and Group IIIA metal ions in the solution to a metal. The reaction is usually carried out at a temperature of from 200 ° C to 200 ° C, preferably at a temperature of from 10 to 100 ° C, more preferably from 15 to 80 ° C. Reduction of the process of the invention The reaction and the pressure conditions are not limited, and may be carried out under normal pressure, or may be pressurized to assist the reaction. In the method of the present invention, a stabilizer such as triethylamine or ethylenediaminetetraacetic acid (EDTA) may be further added. , citric acid, ascorbic acid, β-carotene, lycopene, butylated hydroxyanisole (BHA), butylated hydroxytoluene , BHT) or 3,4,5-tri-propylbenzoic acid propyl vinegar (propyl 7 111826 201228930 gaUateS'PG), etc., added to the solution to avoid oxidation of the metal or alloy. The metal ions in the reaction solution complete the reduction reaction (4) metal , alloy or its mixture (4) 'can be centrifuged' or thief's way, separate and remove the solution' After the remaining solids are dried, the metal powder, alloy powder or its reaction can be obtained under low temperature and air conditions. In the solution, the second reduction reaction is separated and the solution is removed. After drying the remaining solid, the non-meter metal powder, the alloy powder or a mixture thereof can be used as a precursor powder, and the nano-precursor powder has high activity, and Nitrogen-free element and oxygen element = used in the manufacture of IB-mA-VIA compound, can be directly subjected to heat treatment of deuteration, vulcanization, or hoofing reaction without prior reduction and desulfurization step to form IB-IIIA-VIA compound In a specific example, the precursor powder is dispersed in a solvent to form a slurry. Then, the slurry is applied to the substrate by a coating method or a printing method, and the substrate is placed under a non-vacuum. Silk community atmosphere In the process of ordering, for example, boots, vulcanization, or miscellaneous treatment, it can be formed on the silk plate as a light absorbing layer; !; A_VIA compound film. Usually, the treatment is about 15 〇 to _. Under the conditions, the film of m-mA-VIA compound is formed over a period of time (10) to 20, which can be applied to a cIGS solar cell as a light absorbing layer. Compared with the conventional IB group and lanthanum metal oxide or oxynitride powder, The method for producing ΙΒ·ΙΙΙΑ_νΙΑ compound, the precursor powder used in the method of the invention does not contain nitrogen element and oxygen element, can simplify the previous use of metal oxide or nitrogen oxide, and needs to remove lanthanum and lanthanum oxide or oxynitride 111826 8 201228930 Additional steps for elements such as I and oxygen. The powder-pulverized body used in the method of the present invention can be directly subjected to reduction by vulcanization and Wei-cutting to form a m-mA-VIA compound. On the other hand, the process of the invention avoids the use of non-vacuum process preparation! The high risk of the A_VIA compound is required to invite an unstable hydrazine reduction step. Embodiments Embodiment 1
依CuInSe2成分比例，將CuCl2和inCl3溶於乙二醇（E 中配製金屬離子溶液。接著，將過量删氫化鈉(ν_德 於乙二醇中形成爛氫化鈉溶液，再將該棚氫化鈉溶液加入 金屬離子/合液中。均勻混合後，加入穩定劑三乙胺，於室 溫條件下進行還原反應，歷時3G分鐘。反應完成後，分離 並去除溶液，獲得合金/金屬粉體，所得之合金/金屬粉體 以/酉精清洗’乾燥後’獲得前驅粉體。經X-ray繞射圖譜 分析’其結果如第丨圖所示，顯示具有CuIn及Cn2In合 ^ 金化合物。 將所得之前驅粉體於含有硒蒸氣之還原氣氛下，以 450 C之溫度條件進行煆燒，歷時0.5小時，完成硒化反應 後’獲得化合物樣品1。 經X-ray繞射圖譜分析，其結果如第2圖所示，顯示 化合物樣品1具有（112)、（204)/(220)、與（312)/(116)三支 主要繞射鋒，其中（2〇4)與(22〇)為同位置之繞射鋒’（312) 與（116)亦為同位置之繞射鋒，符合ICDD卡編號35-1102 圖譜，確認為黃鋼礦相晶體結構。 9 111826 201228930 實施例2 依AgIn〇.8S17成分比例，將Ag(N03)2和ιη(Ν〇3)3溶於 乙二醇（EG)中配製金屬離子溶液。接著’將過量硼氫化納 (NaBILO溶於乙二醇（EG)中形成硼氫化鈉溶液，再將該蝴 氫化鈉溶液加入金屬離子溶液中，其中NaBH4為 ([Ag2+]+[In3+])的3倍。均勻混合後，加入穩定劑三乙胺， 於30°C之溫度條件下進行還原反應，歷時1〇分鐘。反應 完成後’分離並去除溶液，獲得合金/金屬粉體，所得之合 金/金屬粉體以酒精清洗，乾燥後，獲得前驅粉體。 孀 將所得之前驅粉體於含有硫蒸氣之還原氣氛下，以 200°C之溫度條件進行煆燒，歷時3小時，完成硫化反應 後，獲得化合物樣品2。 經X-ray繞射圖譜分析’其結果顯示化合物樣品2具 有（112)、（220)、（204)、（312)與（116)/(215)等主要繞射鋒二 其中（116)與(215)為同位置之繞射鋒，確定為黃銅礦相晶體 結構。 實施例3 # 依Cu0.8GaSei·9成分比例，將叫恥^和仏(助3)3溶 於乙一醇(EG)中配製金屬離子溶液。接著，將過量蝴氫化 納（NaBH4)溶於乙二醇(EG)中形成硼氫化納溶液，再將該 硼氫化鈉溶液加入金屬離子溶液中，其中NaBH4為 (lCu2+]+[Ga3+])的0.2倍。均勻混合後，進行還原反應，歷 時60分鐘。反應完成後，分離並去除溶液，獲得合金/金 屬粉體，所得之合金/金屬粉體以酒精清洗，乾燥後，再將 111826 10 201228930 其配製成漿料，利用塗佈法塗佈成薄膜，並於含有栖蒸氣 之還原氣氛下，以600°C之溫度條件進行煆燒，歷時1〇小 時’完成硒化反應後’獲得薄膜樣品3。 經X-ray繞射圖譜分析，其結果顯示薄膜樣品3具有 (112)、（220)、（204)、（312)與（116)/(303)等主要繞射鋒，其 中（116)與（303)為同位置之繞射鋒，確定為黃銅礦相晶體鈐 構。 實施例4 • 依CuAlSe2成分比例’將CuCl2和AICI3溶於去離子 水中配製金屬離子水相溶液。接著，將過量硼氫化納 (NaBILO溶於去離子水中形成硼氫化鈉水溶液，再將該硼 氫化鈉水溶液加入金屬離子水相溶液中，其中NaBH4為 ([Cu^+fAl3"])的〇·5倍。均勻混合後，進行還原反應，歷 時120分鐘。反應完成後，分離並去除溶液，獲得合金/ 金屬粉體’所得之合金/金屬粉體以酒精清洗，乾燥後獲得 φ 前驅粉體。 將所得之前驅粉體於含有硒蒸氣之還原氣氛下，以 350°C之溫度條件進行煆燒，歷時oj小時，完成硒化反應 後’獲得化合物樣品4。 經X-ray繞射圖譜分析，其結果顯示化合物樣品4具 有（112)、（220)、（204)、（312)與（116)等主要繞射鋒，確定 譜，確定為黃銅礦相晶體結構。 實施例5 依 CuIni.2Se2 3 成分比例，將 Cu(N〇3)2 和 ln(N〇3)3 溶 111826 11 201228930 於去離子水中配製金屬離子溶液。接著，將過量硼氫化鈉 (NaBH4)溶於去離子水中形成棚氫化鈉水溶液，再將該硼 氫化鈉水溶液加入金屬離子溶液中。均勻混合後，進行還 原反應’歷時0.5分鐘。反應完成後，分離並去除溶液， 獲得Culn、Cujn合金與in金屬粉體，所得之合金及金屬 粉體以酒精清洗，乾燥後，再將其配製成漿料，利用刮刀 (doctor-blade)塗佈成薄膜’並於含有砸蒸氣之還原氣氛 T ’以220C之溫度條件進行煆燒，歷時8小時，完成石西 化反應後’獲得薄膜樣品5。 φ 經X-ray繞射圖譜分析，其結果顯示薄膜樣品5具有 (112)、（204)/(220)、與（312)/(116)三支主要繞射鋒，其中（2〇4) 與（220)為同位置之繞射鋒，（312)與（116)亦為同位置之繞 射鋒’確定為黃鋼礦相晶體結構。 實施例6 依CuInSe2成分比例，將CuCl2和inCi3溶於去離子水 中配製金屬離子水相溶液。接著，將過量抗壞企酸鈉鹽 (sodium ascorbic acid)溶於去離子水中形成抗壞血酸鈉鹽籲 水溶液，再將該抗壞血酸鈉鹽水溶液加入金屬離子水相溶 液中，其中抗壞血酸鈉鹽為（[Cu2+]+[In3+])的3〇倍。均勾 混合後’進行還原反應，歷時3G分鐘。反應完成後，分離 並去除溶液，獲得合金/金屬粉體，所得之合金/金屬粉體 以酒精清洗，乾燥後，獲得前驅粉體。 將所得之前驅粉體於含有硒蒸氣之還原氣氛下，以 180°C之溫度條件進行煆燒，歷時5小時，完成砸化反應 111826 12 201228930 後’即可獲得化合物樣品6。 經X-ray繞射圖譜分析，其結果顯示化合物樣品6具 有（112)、（204)/(220)、與（312)/(116)三支主要繞射鋒，其 中（204)與（220)為同位置之繞射鋒，（312)與（116)亦為同位 置之繞射鋒，確定為黃銅礦相晶體結構。 實施例7 依CuInSez成分比例，將CuCl2和InCl3溶於去離子水 中配製金屬離子水相溶液。接著，將過量硼氫化鈉（NaBH4) Φ ’谷於去離子水中形成删氫化納水溶液，再將該棚氫化鈉水 >谷液加入金屬離子水相溶液中。均勻混合後，進行還原反 應，歷時30分鐘。反應完成後，分離並去除溶液，獲得合 金/金屬粉體，所得之合金/金屬粉體以酒精清洗，乾燥後 獲得前驅粉體。接著，所得到之沉澱粉體與過量Se粉以球 磨均勻混合，其中[Se2·]為（[Cu2+]+[In3+])的2倍，再於H2/N2 氣氛中’於400°C之溫度條件下進行熱處理，歷時0.5小 φ 時，反應完成後，獲得化合物樣品7。 經X-ray繞射圖譜分析，其結果顯示化合物樣品7具 有（112)、（204)/(220)、與（312)/(116)三支主要繞射鋒，其 中（204)與（220)為同位置之繞射鋒，（312)與（116)亦為同位 置之繞射鋒，確定為黃銅礦相晶體結構。 【圖式簡單說明】 第1圖係本發明實施例1所形成之前驅粉體之X_ray 繞射圖譜；以及 第2圖係本發明實施例1所形成之化合物樣品1之 13 111826 201228930 X-ray繞射圖譜。 【主要元件符號說明】According to the proportion of CuInSe2 component, CuCl2 and inCl3 are dissolved in ethylene glycol (E to prepare a metal ion solution. Then, sodium hydride is formed in excess of sodium hydride, and sodium hydride sodium is formed in ethylene glycol. The solution is added to the metal ion/liquid mixture, and after uniformly mixing, the stabilizer triethylamine is added, and the reduction reaction is carried out at room temperature for 3 G minutes. After the reaction is completed, the solution is separated and removed to obtain an alloy/metal powder. The alloy/metal powder was cleaned by '酉 dry' to obtain the precursor powder. The X-ray diffraction pattern analysis was carried out. The results are shown in the figure, which shows CuIn and Cn2In alloy compounds. The precursor powder was calcined under a reducing atmosphere containing selenium vapor at a temperature of 450 C for 0.5 hour, and after completion of the selenization reaction, 'Compound Sample 1 was obtained. After X-ray diffraction pattern analysis, the results were as follows. As shown in Fig. 2, it is shown that compound sample 1 has three main diffraction fronts of (112), (204)/(220), and (312)/(116), of which (2〇4) and (22〇) are The same position of the diffraction front '(312) and (116) are also in the same position The diffraction front conforms to the ICDD card number 35-1102 map and is confirmed to be the crystal structure of the yellow steel ore phase. 9 111826 201228930 Example 2 According to the ratio of AgIn〇.8S17 composition, Ag(N03)2 and ιη(Ν〇3)3 Dissolve in ethylene glycol (EG) to prepare metal ion solution. Then 'excess sodium borohydride (NaBILO dissolved in ethylene glycol (EG) to form sodium borohydride solution, then add the butterfly sodium hydride solution to metal ion solution , wherein NaBH4 is 3 times of ([Ag2+]+[In3+]). After homogeneous mixing, the stabilizer triethylamine is added, and the reduction reaction is carried out at a temperature of 30 ° C for 1 minute. After the completion of the reaction, the separation is carried out. And removing the solution to obtain an alloy/metal powder, and the obtained alloy/metal powder is washed with alcohol and dried to obtain a precursor powder. The obtained precursor powder is subjected to a reducing atmosphere containing sulfur vapor at 200 ° C. The temperature was subjected to calcination for 3 hours, and after the completion of the sulfurization reaction, the compound sample 2 was obtained. The X-ray diffraction pattern analysis showed that the compound sample 2 had (112), (220), (204), 312) and (116) / (215) and other major diffraction front two 116) The diffraction front at the same position as (215) is determined to be a chalcopyrite phase crystal structure. Example 3 # According to the ratio of Cu0.8GaSei·9 composition, it is called 耻^ and 仏(助3)3 dissolved in A metal ion solution is prepared in an alcohol (EG). Then, an excess of hydrogen halide (NaBH4) is dissolved in ethylene glycol (EG) to form a sodium borohydride solution, and the sodium borohydride solution is added to the metal ion solution, wherein NaBH4 It is 0.2 times that of (lCu2+)+[Ga3+]). After homogeneous mixing, the reduction reaction was carried out for 60 minutes. After the reaction is completed, the solution is separated and removed to obtain an alloy/metal powder, and the obtained alloy/metal powder is washed with alcohol, dried, and then formulated into a slurry by 111826 10 201228930, and coated into a film by coating. And calcining at a temperature of 600 ° C under a reducing atmosphere containing the invading vapor, and obtaining a film sample 3 after completion of the selenization reaction for 1 hour. The X-ray diffraction pattern analysis shows that the film sample 3 has major diffraction fronts such as (112), (220), (204), (312) and (116)/(303), among which (116) and (303) is the diffraction front of the same position, which is determined to be a chalcopyrite phase crystal structure. Example 4 • A metal ion aqueous phase solution was prepared by dissolving CuCl2 and AICI3 in deionized water according to the ratio of CuAlSe2 composition. Next, excess sodium borohydride (NaBILO is dissolved in deionized water to form an aqueous solution of sodium borohydride, and the aqueous sodium borohydride solution is added to the metal ion aqueous phase solution, wherein NaBH4 is ([Cu^+fAl3"]) After 5 times of uniform mixing, the reduction reaction was carried out for 120 minutes. After the completion of the reaction, the solution was separated and the solution was removed to obtain an alloy/metal powder obtained by alloy/metal powder, which was washed with alcohol and dried to obtain a φ precursor powder. The obtained precursor powder was calcined under a reducing atmosphere containing selenium vapor at a temperature of 350 ° C for a period of oj, and after completion of the selenization reaction, 'Compound Sample 4 was obtained. X-ray diffraction pattern analysis, The results show that the compound sample 4 has major diffraction fronts such as (112), (220), (204), (312) and (116), and the spectrum is determined to be determined to be a chalcopyrite phase crystal structure. Example 5 According to CuIni. 2Se2 3 composition ratio, Cu(N〇3)2 and ln(N〇3)3 dissolved 111826 11 201228930 to prepare metal ion solution in deionized water. Then, excess sodium borohydride (NaBH4) was dissolved in deionized water to form Sodium hydride aqueous solution The aqueous solution of sodium borohydride is added to the metal ion solution. After homogeneous mixing, the reduction reaction is carried out for 0.5 minutes. After the reaction is completed, the solution is separated and removed to obtain Culn, Cujn alloy and in metal powder, and the obtained alloy and metal are obtained. The powder is washed with alcohol, dried, and then formulated into a slurry, which is coated into a film by a doctor-blade and simmered at a temperature of 220 C in a reducing atmosphere T' containing hydrazine vapor. After 8 hours, the stone sample was obtained and the film sample 5 was obtained. φ was analyzed by X-ray diffraction pattern, and the results showed that the film sample 5 had (112), (204)/(220), and (312)/(116 Three major diffraction fronts, in which (2〇4) and (220) are the same position of the diffraction front, and (312) and (116) are also the same position of the diffraction front' determined as the yellow steel ore phase crystal structure Example 6 According to the ratio of CuInSe2 component, CuCl2 and inCi3 were dissolved in deionized water to prepare a metal ion aqueous phase solution. Then, excess sodium ascorbic acid was dissolved in deionized water to form sodium ascorbate. Aqueous solution, then the anti-scurvy The sodium salt aqueous solution is added to the metal ion aqueous phase solution, wherein the sodium ascorbate salt is 3 times of ([Cu2+]+[In3+]). After the mixture is mixed, the reduction reaction is carried out for 3G minutes. After the reaction is completed, the separation and removal are performed. The solution is obtained as an alloy/metal powder, and the obtained alloy/metal powder is washed with alcohol and dried to obtain a precursor powder. The obtained precursor powder is subjected to a reducing atmosphere containing selenium vapor at a temperature of 180 ° C. The calcination was carried out for 5 hours, and after completion of the deuteration reaction 111826 12 201228930, compound sample 6 was obtained. By X-ray diffraction pattern analysis, the results show that compound sample 6 has three main diffraction fronts (112), (204)/(220), and (312)/(116), of which (204) and (220) ) is the diffraction front of the same position, and (312) and (116) are also the diffraction fronts of the same position, which are determined to be the chalcopyrite phase crystal structure. Example 7 A metal ion aqueous phase solution was prepared by dissolving CuCl2 and InCl3 in deionized water according to the ratio of CuInSez composition. Next, an excess of sodium borohydride (NaBH4) Φ ' valley was added to deionized water to form an aqueous solution of sodium hydride, and the shed sodium hydride water > gluten solution was added to the metal ion aqueous phase solution. After homogeneous mixing, the reduction reaction was carried out for 30 minutes. After the completion of the reaction, the solution was separated and removed to obtain an alloy/metal powder, and the obtained alloy/metal powder was washed with alcohol and dried to obtain a precursor powder. Then, the obtained precipitated powder and the excess Se powder are uniformly mixed by ball milling, wherein [Se2·] is twice the ([Cu2+]+[In3+]), and then in the H2/N2 atmosphere, the temperature is at 400 °C. The heat treatment was carried out under the conditions, and when 0.5 φ was passed, the compound sample 7 was obtained after completion of the reaction. X-ray diffraction pattern analysis showed that compound sample 7 had three main diffraction fronts (112), (204)/(220), and (312)/(116), of which (204) and (220) ) is the diffraction front of the same position, and (312) and (116) are also the diffraction fronts of the same position, which are determined to be the chalcopyrite phase crystal structure. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an X-ray diffraction pattern of a precursor powder formed in Example 1 of the present invention; and FIG. 2 is a sample 1 of a compound formed in Embodiment 1 of the present invention. 13 111826 201228930 X-ray Diffraction map. [Main component symbol description]