201021906 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種太％能電池的製造方法，尤其是製造 銅銦鎵硒溶膠凝膠溶液的方法。 【先前技術】 隨著石化能源的逐漸枯竭，尋求穩定可靠的替代能源 ❹ 已是本世紀所有人類要面對的最大生存課題，而包括生質 能源、地熱能源、風力能源、核能的各種能源，在來源可 靠度、使用安全性、環境保護的考慮下，皆比不上取自太 陽光輻射的太陽能，因為在地球表面上皆能接收到太陽 光，且使用過程中只是將光能轉換成電能，而沒有任何污 染性的物質產生，因此太陽能是目前最為潔淨的替代能源。 太陽能電池係將太陽光之光能轉換成方便使用之電能 Ο 的裝置’在眾多太陽能電池中，銅銦鎵砸 (Copper/Indium/Gallium/Selenium，CIGS)太陽能電池由 於向吸光率與光電轉換效率的優異性能而漸漸獲得重視。 CIGS太陽能電池係由銅銦硒 (Copper/Indium/Selenium，CIS)太陽能電池演進而來。cis 太％能電池主要包括CuInSe2，係屬於直接遷移性半導體， 尤其吸光係數極高，CulnSe2的禁止帶幅(Eg)為leV，小於 最適用於太陽電池的1.4-1.5eV，因此與Eg=1.6eV的 201021906201021906 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing a solar cell, in particular, a method for producing a copper indium gallium selenide sol gel solution. [Prior Art] With the gradual depletion of petrochemical energy, the search for stable and reliable alternative energy sources is the biggest survival problem for all human beings in this century, including biomass energy, geothermal energy, wind energy, and nuclear energy. In terms of source reliability, safety of use, and environmental protection, it is not comparable to solar energy taken from solar radiation, because it can receive sunlight on the surface of the earth, and only converts light energy into electrical energy during use. Without any polluting substances, solar energy is currently the cleanest alternative energy source. Solar cells are devices that convert the light energy of sunlight into convenient power devices. In many solar cells, Copper/Indium/Gallium/Selenium (CIGS) solar cells have high absorbance and photoelectric conversion efficiency. The excellent performance has gradually gained attention. The CIGS solar cell evolved from a copper indium selenide (Copper/Indium/Selenium, CIS) solar cell. The cis too% energy battery mainly includes CuInSe2, which belongs to direct migration semiconductors, especially the absorption coefficient is very high. The forbidden band width (Eg) of CulnSe2 is leV, which is less than 1.4-1.5eV most suitable for solar cells, so Eg=1.6 eV's 201021906
CuGaSe2較高帶幅材料形成cu(InGa)Se2,亦即所謂的CIGS 混晶材料，以改善此一缺點。CiGS太陽能電池的光電效率 最高可達19%而模組的光電效率亦可達13%，且隨著錮鎵 含量的不同，光吸收範圍可從1〇2#至1.68^，因高達 1〇5cm1的吸光效率’所以厚度只需不到1 ，便有99%以 上的光子被吸收。 參閱第一圖，習用技術的CIGS太陽能電池之示意圖。 如第一圖所示’ CIGS太陽能電池1 一般包括玻璃基板1〇、 背面電極層20、CIGS吸光層30、緩衝層40以及透明電極 層50’其中背面電極層2〇係用以導電，一般是使用鉬金屬， CIGS吸光層30係p型半導體層，最主要的作用是吸光，緩 衝層40通常是使用硫倾(CdS)，以形成n型半導體， 而透明電極層50主要氧化雜(Aluminum Zinc Oxide ’ AZO)、氧化鋅銦（Indium Zinc㈣如，IZ〇)或氧化 錫銦（IndiumTin 〇xide，⑽，具有高透光性以及導電性。 太陽光L如箭頭方向所示係由上而下射入nGS太陽能電池 1 ’穿透過透明電極層50以及緩衝層4〇而到達CIGS吸光 曰30 :呈CIGS吸光層3〇吸收後產生具電位能量的電洞電 子對’並分別由透明電極層50與背面電極層20傳導至外 部而提供電能。 201021906 參閱第二圖’習用技術的CIGS太陽能電池之製造流程 圖。如第二圖所示，首先在步驟S10中，使用金屬鉬靶材， 以磁控濺射法在玻璃基板上沉積出厚度約丨咖的背面電極 層’接著在步驟S20中，利用適當方法在背面電極層上沉 積出厚度約2醒的CIGS吸光層，並進入步驟S30，使用化 學水浴法(Chemical Bath Deposition，CBD)，在 CIGS 吸 光層上形成緩衝層，通常是CdS，最後進入步驟S4G，以錢 鑛法或化學氣相沉積法，在緩衝層上形成透明電極，藉以 形成第一圖的CIGS太陽能電池之結構。 CIGS吸光層的製造方法包括蒸鍍法、濺鍍法、電化學沉積 法比及墨印法（Ink Coating) ’其中蒸鍍法、濺鍍法以及電 化學沉積法需要一系列的真空製程，造成硬體投資與製造 成本均相當高昂，而墨印法係由ISET公司（Internati〇nal Solar Electric Technology, Inc.)所開發的非真空技術， 利用奈米技術先備製奈米級金屬粉末或氧化物粉末，經適 畲溶劑混合後製成漿料，再以類似油墨製程（Ink Process) 將漿料配置在鉬金屬層上而形成CIGS吸光層，可大幅降低 製造成本。 然而，習用技術的缺點為’墨印法所需的奈米級金屬 粉末或氧化物粉末不容易製造，且製成漿料所需的溶劑也 不容易調配，使得墨印法缺乏來源穩定且可靠度高的原料。 201021906 因此，需要一種金屬粉末與溶劑之混合漿料的製造方 法’利用適當的混合製程，使不同的金屬粉末以及溶劑充 分均勻混合，以解決習用技術的缺點。 【發明内容】 本發明之主要目的在提供一種溶膠凝膠溶液的製造方 法’利用預先混合製程’將包含銅、姻、錄與砸的化合物 φ 混合成金屬化合物混合物，將稀釋劑加入分散劑中形成稀 釋分散劑，將黏著劑、流平劑以及穩定劑混合成穩定黏著 劑’將防凍劑與延遲凝結劑混合成防凍凝結劑，將還原劑、 金屬絡合劑以及提煉金屬溶劑混合成金屬還原劑，接著混 合金屬化合物混合物、稀釋分散劑、穩定黏著劑、防珠凝 結劑以及金屬還原劑，並進行加熱授拌，再進行降溫挽拌， 最後經冷卻而形成溶膠凝膠(Sol-Gel)溶液，供墨印法在位 〇 於玻璃基板上的金屬薄膜層上，形成CIGS太陽能電池的 CIGS吸光層。 因此，藉由本發明所提供的方法，可提供具適當金屬 比例的溶膠凝膠溶液給供墨印法，以形成所需的cigs吸光 層，因此能解決上述習知技術的所有缺點。 【實施方式】 以下配合圖式及元件符號對本發明之實施方式做更詳 細的說明，俾使熟習該項技藝者在研讀本說明書後能據以 201021906 實施。 參閱第三圖，本發明CIGS太陽能電池之溶膠凝膠溶液 的製造方法流程圖。如第三圖所示，首先由步驟S110開始， 在步驟S110中’進行預先混合操作，將包含銅、銦、鎵與 石西的化合物混合成金屬化合物混合物，將稀釋劑加入分散 劑中形成稀釋分散劑，將黏著劑、流平劑以及穩定劑混合 成穩定黏著劑，將防凍劑與延遲凝結劑混合成防凍凝結 劑，將還原劑、金屬絡合劑以及提煉金屬溶劑混合成金屬 還原劑，接著進入步驟S120。在步驟S120中，進行進階混 合操作，將銅銦鎵砸金屬化合物混合物、稀釋分散劑、穩 定黏著劑、防凍凝結劑以及金屬還原劑混合成進階混合 物，進入步驟S130。在步驟Si30中，將進階混合物的溫度 上升至第一預設溫度，進行加熱攪拌，持續第一預設時間， 其中第-預*溫度為1GGX：至135X：，第-預設時間為3〇 分至2小時。㈣進人麵S14Q，將進階混合物的溫度下 降到第二預奶显度，進行加紐拌，持續第二職時間， 其中第二預設溫度為耽至⑽。c，而第二預設時間為加 分至2小時’最後進入步驟S15G，經冷卻後得到所需的溶 膠凝膠溶液。 步驟S11G中的金屬化合物混合物係包括魏亞銅 (CU2Se)、砸化銦（Ιη&3)、砸化鎵(Ga2Se〇、硫化亞銅 9 201021906 (C112S)、硫化銦（ImSs)、硫化鎵(Ga2Ss)、二碼化銅銦鎵 (CuInGaSe2)、二硫化銅銦鎵（CuInGaS2)、二硫化銅銦 (CuInS〗）、二砸化銅銦（CuInSe2)、二硫化銅鎵（cuGaS2)、 -一砸化銅錄（CuGaSeO、二硫化銅銘（CuAlS2)、二砸化銅 銦銘（CuInAlSe2)、硫化鈉（toS)、醋酸銅、醋酸姻、醋酸 鎵、硫酸銅、硫酸錮、硫酸鎵、氣化銅、氯化銦、氯化鎵 以及亞硒酸的至少其中一。 此外’在稀釋分散劑中，稀釋劑包括去離子水以及二 曱氧基乙醇的至少其中之一，而分散劑包括聚丙烯酸以及 聚乙烯酸的至少其中之一。在穩定黏著劑中，黏著劑包括 聚丙稀酸胺以及聚乙烯酰胺的至少其中之一，流平劑包括 聚丙烤酸酯以及乙酸的至少其中之一，而穩定劑包括二乙 醇胺、乙醇胺、乙二醇以及丙二醇的至少其中之一。在防 凍凝結劑中’防凍劑包括乙醇以及異丙醇的至少其中之 一，而延遲凝結劑包括冰醋酸以及草酸的至少其中之一。 在金屬還原劑中’還原劑包括氨水、氫氧化鈉、氫氧化鉀 以及檸檬酸鈉的至少其中之一，金屬絡合劑包括乙酰丙 酮’而提煉金屬溶劑包括乙二酸。 本發明的製造方法所製造的溶膠凝膠溶液，可供墨印 法、喷塗法、浸泡法或旋轉塗佈法使用，藉以形成CIGS太 1%月b電池的CIGS吸光層，因此，本發明的製造方法能提升 201021906 整體CIGS太·電池的製造辟，鱗健造成本。 以上所述者僅為用贿釋本翻之健實施例，並非 企圖據輯本發任倾之關，是以，凡有在相 同之發明精神下所作有關本發明之任何修飾或變更，皆仍 應包括在本發明意圖保護之範疇。 【圖式簡單說明】 % 第一圖為顯示習用技術的CIGS太陽能電池之示意圖。 第二圖為顯示習用技術的c〖GS太陽能電池之製造流程圖。 第二圖為顯示本發明CIGS太陽能電池之溶膠凝膠溶液的製 造方法流程圖。 【主要元件符號說明】 1 CIGS太陽能電池 10玻璃基板 20背面電極層 30 CIGS吸光層 40緩衝層 50透明電極層 L光線 S10在玻璃基板上沉積出背面電極層 S20在背面電極層上沉積出CIGS吸光層 S30在CIGS吸光層上形成緩衝層 11 201021906 S40在緩衝層上形成透明電極層 S110預先混合 S120進階混合 S130加熱攪拌 S140降溫攪拌 S150冷卻The higher band width material of CuGaSe2 forms cu(InGa)Se2, also known as CIGS mixed crystal material, to improve this disadvantage. The photoelectric efficiency of CiGS solar cells is up to 19% and the photoelectric efficiency of the modules can reach 13%. With the different gallium content, the light absorption range can range from 1〇2# to 1.68^, as up to 1〇5cm1. The light absorption efficiency 'so that the thickness is less than one, more than 99% of the photons are absorbed. Referring to the first figure, a schematic diagram of a conventional CIGS solar cell. As shown in the first figure, the CIGS solar cell 1 generally includes a glass substrate 1 〇, a back electrode layer 20, a CIGS light absorbing layer 30, a buffer layer 40, and a transparent electrode layer 50', wherein the back electrode layer 2 is used for conducting electricity, generally Using molybdenum metal, the CIGS light absorbing layer 30 is a p-type semiconductor layer, the most important function is to absorb light, the buffer layer 40 is usually using sulfur tilting (CdS) to form an n-type semiconductor, and the transparent electrode layer 50 is mainly oxidized (Aluminum Zinc) Oxide ' AZO), indium zinc oxide (Indium Zinc (IV), for example, IZ〇) or indium tin oxide (Indium Tin 〇xide, (10), has high light transmittance and conductivity. The sunlight L is shot from top to bottom as indicated by the direction of the arrow. The nGS solar cell 1 'passes through the transparent electrode layer 50 and the buffer layer 4 〇 to reach the CIGS light absorbing 曰 30: after the absorption of the CIGS light absorbing layer 3 产生, a hole electron pair with potential energy is generated and is respectively composed of the transparent electrode layer 50 and The back electrode layer 20 is conducted to the outside to provide electrical energy. 201021906 Referring to the second figure, the manufacturing flow chart of the CIGS solar cell of the conventional technology. As shown in the second figure, first, in step S10, the metal molybdenum target is used. Depositing a back electrode layer having a thickness of about 20,000 on the glass substrate by magnetron sputtering. Then, in step S20, a CIGS light absorbing layer having a thickness of about 2 awake is deposited on the back electrode layer by an appropriate method, and the steps are advanced. S30, using a Chemical Bath Deposition (CBD), forming a buffer layer on the CIGS light absorbing layer, usually CdS, and finally proceeding to step S4G to form a transparent electrode on the buffer layer by money or chemical vapor deposition. The structure of the CIGS solar cell is formed by the first figure. The manufacturing method of the CIGS light absorbing layer includes an evaporation method, a sputtering method, an electrochemical deposition method, and an ink plating method (Ink Coating), wherein the evaporation method and the sputtering method are used. And electrochemical deposition requires a series of vacuum processes, resulting in high hardware investment and manufacturing costs, and the ink-printing method is developed by ISET (Internati〇nal Solar Electric Technology, Inc.) using non-vacuum technology. Nano technology prepares nano-sized metal powder or oxide powder, which is mixed into a slurry by suitable solvent, and then matched with an ink process (Ink Process). The formation of a CIGS light absorbing layer on the molybdenum metal layer can greatly reduce the manufacturing cost. However, the disadvantage of the conventional technique is that the nano-sized metal powder or oxide powder required for the ink printing method is not easy to manufacture and is made into a slurry. The solvent required is not easy to formulate, so that the ink printing method lacks a source of stable and reliable source. 201021906 Therefore, there is a need for a method for producing a mixed slurry of a metal powder and a solvent 'using a suitable mixing process to make different metals The powder and the solvent are thoroughly and uniformly mixed to solve the disadvantages of the conventional technique. SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for producing a sol-gel solution, which uses a pre-mixing process to mix a compound φ containing copper, a mixture, and a ruthenium into a metal compound mixture, and a diluent is added to the dispersant. Forming a diluted dispersant, mixing the adhesive, leveling agent and stabilizer into a stable adhesive. Mixing the antifreeze with the delayed coagulant into an antifreeze coagulant, mixing the reducing agent, the metal complexing agent and the refining metal solvent into a metal reducing agent Then, the metal compound mixture, the diluted dispersant, the stabilizing adhesive, the anti-bead coagulant, and the metal reducing agent are mixed, heated and mixed, and then cooled and mixed, and finally cooled to form a Sol-Gel solution. The ink supply method is formed on the metal thin film layer on the glass substrate to form a CIGS light absorbing layer of the CIGS solar cell. Thus, by the method provided by the present invention, a sol-gel solution having a suitable metal ratio can be provided for ink supply to form a desired cigs absorptive layer, thereby solving all of the above-mentioned drawbacks of the prior art. [Embodiment] Hereinafter, the embodiments of the present invention will be described in more detail with reference to the drawings and the reference numerals, so that those skilled in the art can implement the invention according to 201021906 after studying the present specification. Referring to the third figure, a flow chart of a method for producing a sol-gel solution of a CIGS solar cell of the present invention. As shown in the third figure, starting from step S110, in step S110, 'premixing operation is performed, a compound containing copper, indium, gallium and lithus is mixed into a metal compound mixture, and a diluent is added to the dispersing agent to form a dilution. a dispersing agent, which mixes an adhesive, a leveling agent and a stabilizer into a stable adhesive, mixes the antifreeze with a delayed coagulant into an antifreeze coagulant, and mixes the reducing agent, the metal complexing agent and the metallizing solvent into a metal reducing agent, and then Go to step S120. In step S120, an advanced mixing operation is performed to mix the copper indium gallium antimony metal compound mixture, the diluted dispersant, the stabilizing adhesive, the antifreeze coagulant, and the metal reducing agent into the advanced mixture, and the process proceeds to step S130. In step Si30, the temperature of the advanced mixture is raised to a first preset temperature, and heating and stirring are performed for a first preset time, wherein the first pre-* temperature is 1GGX: to 135X:, and the first-preset time is 3. The score is 2 hours. (4) Entering the human face S14Q, the temperature of the advanced mixture is lowered to the second pre-milk degree, and the doubling is continued for the second job time, wherein the second preset temperature is 耽 to (10). c, and the second predetermined time is the addition to 2 hours'. Finally, the process proceeds to step S15G, and after cooling, the desired sol gel solution is obtained. The metal compound mixture in the step S11G includes copper (CU2Se), indium antimonide (Ιη & 3), gallium antimonide (Ga2Se, copper sulfide 9 201021906 (C112S), indium sulfide (ImSs), gallium sulfide ( Ga2Ss), CuInGaSe2, CuInGaS2, CuInS, CuInS, CuInSe2, CuGaS2, -1砸化铜录(CuGaSeO, copper disulfide (CuAlS2), copper indium bismuth (CuInAlSe2), sodium sulfide (toS), copper acetate, acetic acid, gallium acetate, copper sulfate, barium sulfate, gallium sulfate, gas At least one of copper, indium chloride, gallium chloride, and selenite. Further, in the diluted dispersant, the diluent includes at least one of deionized water and dimethoxyethanol, and the dispersant includes poly At least one of acrylic acid and polyvinyl acid. In the stable adhesive, the adhesive includes at least one of polyacrylamide and polyvinyl amide, and the leveling agent includes at least one of polyacrylic acid ester and acetic acid. Stabilizers include diethanolamine, ethanolamine, and B. At least one of an alcohol and propylene glycol. In the antifreeze coagulant, the antifreeze agent includes at least one of ethanol and isopropyl alcohol, and the delayed coagulant includes at least one of glacial acetic acid and oxalic acid. The reducing agent includes at least one of ammonia water, sodium hydroxide, potassium hydroxide, and sodium citrate, the metal complexing agent includes acetylacetone', and the metal solvent is extracted including oxalic acid. The sol-gel solution produced by the manufacturing method of the present invention. It can be used by ink printing method, spray coating method, immersion method or spin coating method to form a CIGS light absorbing layer of CIGS too 1% month b battery. Therefore, the manufacturing method of the present invention can improve the overall CIGS solar battery of 201021906. The invention is based on the practice of using bribes to release the book. It is not an attempt to make a copy of the law. It is the case that the invention is made under the same invention spirit. Any modification or modification shall be included in the scope of the intention of the present invention. [Simplified illustration] % The first figure shows the CIGS solar cell showing the conventional technology. The second figure is a manufacturing flow chart showing the c GS solar cell of the conventional technology. The second figure is a flow chart showing the manufacturing method of the sol gel solution of the CIGS solar cell of the present invention. [Main component symbol description] 1 CIGS solar energy Battery 10 Glass substrate 20 Back electrode layer 30 CIGS light absorbing layer 40 Buffer layer 50 Transparent electrode layer L Light S10 deposits a back electrode layer S20 on a glass substrate. A CIGS light absorbing layer S30 is deposited on the back electrode layer to form a buffer on the CIGS light absorbing layer. Layer 11 201021906 S40 forms a transparent electrode layer on the buffer layer S110 premixes S120 advanced mixing S130 heating stirring S140 cooling stirring S150 cooling
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