201117412 ' 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種太陽能電池CuxZnSnSy薄膜(CZTS)之製造 方法’尤指一種(Ci^ZnSnS4)薄膜之硫化製程。 【先前技術】 太陽能電池在目前能源有限之環境下，為許多產業逐漸重視 ，而大多數的太陽能電池目前為矽晶圓太陽能電池，主要係矽晶 圓太陽能電池具有轉換效率較佳、設備較為低廉、生產效率較為 快速以及良率容易達到等優勢M旦是由於原料因素，即多晶石夕材 料相對缺乏以及所帶動之成本上揚，尤其是在製造大面積發電模 組時，其相對之成本因素更為明顯。 、 因此，市場上在不斷研發下，逐漸有所謂「薄膜太陽能電池 」產生，可以在不同且多樣之基板上製造，例如_之塑膠基板 (或者玻璃、或其他板材）’因此可以具有相當之撓性來因應多種環 境。而且_太陽能電池，其在娜、破璃或是其他板材上形成 • 光電效應所需要之厚度需求相當低，而可以在同一受光面積下， 材料相對節省。 而各種薄膜太陽能電池之種類與技術中，其中有利用溶朦凝. 膠法沉積銅鋅錫硫化物(CZTS)薄膜者，該溶膠-凝膠⑽·㈣是以無 機聚合反應絲礎，以金麟氧錄或無機金屬化合物為前_ (P職·)來源’用水作為水為溶縣製備域化合 物。在溶液中前驅物進行水解、聚縮反應，形成微小粒子，而變 成溶膠，並將溶膠沉積於基板上，形成凝膠膜，當凝膠乾燥後， 201117412 ' 得到一層無機網狀聚合物的薄膜，可再加溫進行晶粒合成處理， 最後成為所需的CZTS薄膜。 又，例如金屬醇氧化物此種溶膠-凝膠(sol-gel)主要有三個步驟 1·水解反應(Hydrolysis) : M(0R)4和水混合後，因酸或鹼的催化下 進行水解，形成M(0H)4。其中之-OR基與水反應，水分子中之-0H 基取代-OR基而形成含有-0H基之金屬醇氧化物，釋出醇類。2. 縮合反應（Condensation):二個M(OH)4會進行縮合，形成 (0H)3M-0-M(0H)3，並脫出一個h20。3.聚合反應： _ (〇η)3Μ-ο-μ(οη)3會和其它的m(oh)4進行聚合反應，形成M02 網狀結構的聚合物。去水(dehydration)及去醇(dealcoholation)兩機 構’在進行水解步驟之同時，聚縮合反應亦同時發生，备有_0H 基之金屬醇氧化物與其他醇氧化物之-OH基或-OR基反應形成架 橋鍵氧(bridging oxygen)。水解步驟可以酸催化(acid catalyzed)或鹼 催化(base catalyzed)進行’不同之催化條件所得之溶膠顆粒截然不 同’酸催化起始於H+之親電子性攻擊’鹼催化起始於〇H-之親核 φ 性攻擊(nucle〇Philic attack)，由反應式得知，酸催化可加速水解反 應，聚縮合速率不高，所以聚合體較小，易呈現直鏈狀結構，薄 膜孔徑較小；相反的，鹼催化水解反應速度較慢，聚合速率高， 交鏈程度較高，易呈現網狀結構’薄膜孔徑較酸催化所製作之薄 膜大。 由於硫相當容易揮發，一般製程所得到的CZTS薄膜，其中 所含硫的成份往往少於其化學組成比，而影響此材料特性甚巨， 為了改善此問題，大都會在事後進行硫化處理以補償其硫成份， 201117412201117412 ' VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a solar cell CuxZnSnSy film (CZTS), particularly a vulcanization process of a (Ci^ZnSnS4) film. [Prior Art] Solar cells are increasingly valued by many industries in the current limited energy environment, and most of the solar cells are currently silicon wafer solar cells, mainly based on silicon wafers with better conversion efficiency and lower equipment. Advantages such as rapid production efficiency and easy yielding are due to raw material factors, namely the relative lack of polycrystalline stone materials and the rising cost, especially when manufacturing large-area power generation modules. More obvious. Therefore, under the continuous research and development in the market, there are gradually so-called "thin film solar cells", which can be fabricated on different and diverse substrates, such as plastic substrates (or glass, or other plates), so they can be quite scratched. Sex comes in a variety of environments. Moreover, _ solar cells, which are formed on na, glass or other plates. • The thickness required for the photoelectric effect is quite low, and the material can be relatively saved under the same light receiving area. Among the various types and technologies of thin-film solar cells, among them, those which use a solution of copper, zinc, tin sulfide (CZTS) by a gel method, the sol-gel (10)·(4) is based on an inorganic polymerization reaction, and gold is used. The argon oxygen or inorganic metal compound is the former _ (P job) source of water as the water to prepare the domain compound. In the solution, the precursor is hydrolyzed and polycondensed to form fine particles, which become sol, and the sol is deposited on the substrate to form a gel film. When the gel is dried, 201117412' obtains a film of inorganic network polymer. It can be heated again for grain synthesis treatment and finally becomes the desired CZTS film. Further, for example, a metal alcohol oxide such a sol-gel has three main steps: 1. Hydrolysis: M(0R)4 and water are mixed, and hydrolysis is carried out by acid or alkali catalysis. M(0H)4 is formed. Among them, the -OR group reacts with water, and the -OH group in the water molecule substitutes the -OR group to form a metal alcohol oxide containing an -OH group, and the alcohol is released. 2. Condensation: Two M(OH)4 will condense to form (0H)3M-0-M(0H)3 and desorb a h20. 3. Polymerization: _(〇η)3Μ -ο-μ(οη)3 will be polymerized with other m(oh)4 to form a polymer of M02 network structure. Dehydration and dealcoholation's two processes simultaneously carry out the hydrolysis step, and the polycondensation reaction also occurs simultaneously, and the -OH group or -OR of the other alcoholic oxides is provided. The radical reaction forms bridging oxygen. The hydrolysis step can be carried out by acid catalyzed or base catalyzed. The sol particles obtained by different catalytic conditions are distinctly different. The acid catalyzed the electrophilic attack starting from H+. The base catalysis starts from 〇H- Nucle φ sexual attack (nucle〇Philic attack), the reaction formula shows that acid catalysis can accelerate the hydrolysis reaction, the polycondensation rate is not high, so the polymer is small, easy to present a linear structure, the membrane pore size is smaller; The alkali-catalyzed hydrolysis reaction rate is slow, the polymerization rate is high, the degree of cross-linking is high, and the network structure is easy to appear. The membrane pore size is larger than that of the membrane produced by acid catalysis. Because sulfur is relatively easy to volatilize, the CZTS film obtained in the general process often contains less sulfur than its chemical composition ratio, which affects the material. In order to improve this problem, the metropolis will be vulcanized afterwards to compensate. Its sulfur content, 201117412
、 而一般硫化處理製程大都採用密閉性非常高的真空系統，將CZTS 沉積物置放其中，然後通入硫化氫(HA)氣體並加高溫來進行CZTS 的硫化處理，以上所述，須使用較昂貴的真空密閉系統來進行， 乃因為硫化虱(I^S)氣體具有毒性，而且系統排放的廢氣仍須妥善 處理，所費不貲。 【發明内容】 有鑑於先前技術之問題，本發明者認為應有一種改善之製 程，本發明解決先前技術問題之技術手段，係設計一種太陽能電 • 池CuxZnSnSy薄膜(CZTS)之製造方法，其中0$x$2,0SyS4。其 步驟至少包括：取可形成CZTS溶膠凝膠之前驅物的化合物加入 溶劑： A. 形成 CZTS 溶膠凝膠(sol-gel)前驅物(precursors): B. 將基板置入此含有該前驅物之溶液中進行薄膜沉積，經沉積後 取出’在基板上便可得到一層CZTS沉積物： C. 然後將此CZTS沉積物以硫蒸氣披覆，完成CZTS薄膜硫化處 Φ 理製程。 該披覆之具體實施例係藉由該硫粉與CZTS沉積物置放於加熱 設備中’進行加溫後，使硫粉形成硫蒸氣披覆CZTS沉積物而達 到硫化之目的。由於硫粉之價格相對較為低廉，且無需採用較昂 貴的真空密閉系統來進行，因此可以達到相對簡易，且降低硫對 於排放以及環境之污染。 【實施方式】 以下藉由圖式之辅助，說明本發明之内容、特色以及實施例 201117412 、’請參閱第-圖所示，相關元件配合第二圖至第四圖所示，本發 明^^關於-種太陽能電池CuxZnSnSy薄膜哎丁8)之製造方法，其 步驟包括： ' A. 取可形成CZTS溶膠凝膠之前驅物的化合物(丨)與溶劑(2): 該化合物基於容易溶解之目的，較佳可以為： 無機金屬化合物：例如氣化亞銅、氯化鋅、氯化錫與硫脲，該 溶劑較佳為去離子水與乙醇之溶液。 金屬醋酸鹽水合物：例如銅醋酸塩水合物、鋅醋酸塩水合物、 修 亞錫氯化物二水合物，該溶劑較佳為單乙醇 氨油酸塩與甲氧乙醇之溶液。 B. 形成 CZTS 溶膠-凝膠(s〇l-gd)前驅物(3)(precurs()rs): 較佳是經過加熱或攪拌，按，而此種溶膠凝膠法的主要是利用 金屬醇化物或金屬鹽類溶於溶劑中進行水解和縮合反應而行成 凝膠，對於形成薄膜有其優異之處。 而其中所謂之溶膠(Sol)係指極小膠體，因凡得瓦爾力及電 φ 雙層作用下，均勻分散在系統中而形成。至於凝膠(Gel)為經過 水解(Hydrolysis)及縮合(Condensation)反應之後，分子單體經由 鍵結逐漸形成大分子之凝膠狀態。 C. 將基板置入此含有該前驅物⑶之溶液中進行薄膜沉積，經沉積 後取出，在基板(4)上便可以得到一層CZTS沉積物(9):該基板 (4)可以為塑膠、金屬、玻璃或更多之材質，使得本發明具有多 •7G之基板得以適用。 D. 然後將此CZTS沉積物(9)以硫蒸氣披覆，完成CZTS薄膜硫化 201117412 ' 處理製程。 請配合第三圖係本發明初步置放硫粉之狀態示意圖，本發明將 該硫粉⑻與該CZTS沉積物(9)置放於如第四圖所示之加熱器附 進行加溫。因此使硫粉⑻形成硫蒸氣，藉由蒸氣之溺漫而披覆於 CZTS沉積物(9) ’藉由此-硫化處理，完成CZTS薄膜硫化處理製 程。 本發明之具體製法說明如下：配合第—圖，相關元件請配合 第二至四圖所示，配置可形成CZTS溶膠凝膠之前驅物的化合物⑴ • 與溶劑(2)形成溶液而放入如第四圖所示之該沉積槽(5)。 然後經由第四圖所示之加熱器(6)進行加溫，並且進行攪拌， 而因為調配而得到如第一圖與第二圖所示之CZTS溶膠凝膠前驅 物(3) ’然後配合第四圖所示，將基板(4)置入於裝著調配好的溶膠 凝膠沉積槽(5)裡，經一段時間之沉積，配合第三圖所示，該溶膠 凝膠則驅物(3)可均勻地披覆在基板(4)上，形成一層CZTS沉積物 ⑼。 φ 其流程較佳可再以如第四圖所示之加熱器(6)加熱處理，或者 自然置放些許時間後，可將殘留溶劑揮發，即得CUxZnSnSy均勻 的膜層(即太陽能薄膜之吸收層）。以上步驟可重複進行以達到所需 薄膜厚度。 如第三圖所示，將所得到的CZTS沉積物(9)置放於一容器(7) (例如實驗用之坩堝)中，本發明較佳之容器⑺内環境，可以通入純 氣或以抽氣的方式排除容器内的氧氣，以防止產生氧的硫化物。 CZTS沉積物(9)周圍置放硫粉⑻，將容器⑺密封以得到飽和 201117412 的硫蒸氣持續的M CZTS沉_(9)進行硫域理，碱czts薄 膜。藉由本㈣可以提高硫化效率，並且防止硫錄發。而且本 發明之方法㈣可行且沒有尺寸的限制。 二：由於認為本創作符合可專利之要件，麦依法提出 本創作”作產業上―触實補，舉凡依 。作申4湖鱗之化，·瓣標的之祕 201117412 ♦ 【圖式簡單說明】 第一圖係本發明之流程示意圖 第二圖係本發明之溶膠凝膠調配示意圖 第三圖係本發明初步置放硫粉之狀態示意圖 第四圖係本發明硫化完成之狀態示意圖 【主要元件符號說明】 (1) .化合物 (2) .溶劑 • (3).前驅物 (4) .基板 (5) .沉積槽 ⑹.加熱器 ⑺.容器 (8) .硫粉 (9) .沉積物However, most of the general vulcanization processes use a highly airtight vacuum system in which CZTS deposits are placed, and then hydrogen sulfide (HA) gas is introduced and high temperature is applied to cure the CZTS. As described above, it is expensive to use. The vacuum-tight system is carried out because the bismuth sulfide (I^S) gas is toxic, and the exhaust gas emitted by the system must be properly disposed of. SUMMARY OF THE INVENTION In view of the problems of the prior art, the present inventors believe that there should be an improved process, and the technical means for solving the prior art problem of the present invention is to design a manufacturing method of a solar cell CuxZnSnSy film (CZTS), wherein $x$2,0SyS4. The steps include at least: adding a compound capable of forming a precursor of the CZTS sol gel to the solvent: A. forming a CZTS sol-gel precursor: B. placing the substrate into the precursor containing the precursor Film deposition in the solution, after deposition, removes a layer of CZTS deposit on the substrate: C. The CZTS deposit is then coated with sulfur vapor to complete the CZTS film vulcanization process. The specific embodiment of the coating is carried out by placing the sulfur powder and the CZTS deposit in a heating device. After the heating, the sulfur powder is formed into a sulfur vapor to coat the CZTS deposit to achieve the purpose of vulcanization. Since the price of sulphur powder is relatively low and does not require the use of a more expensive vacuum containment system, it can be relatively simple and reduces sulfur emissions and environmental pollution. [Embodiment] Hereinafter, the contents, features, and embodiments of the present invention will be described with the aid of the drawings. Referring to Fig. 1, the related components are shown in the second to fourth figures. Regarding the manufacturing method of the solar cell CuxZnSnSy film crucible 8), the steps thereof include: 'A. taking a compound (丨) and a solvent (2) which can form a precursor of the CZTS sol gel: the compound is based on the purpose of easy dissolution Preferably, it may be: an inorganic metal compound such as vaporized cuprous, zinc chloride, tin chloride and thiourea, and the solvent is preferably a solution of deionized water and ethanol. The metal acetate hydrate: for example, ruthenium copper acetate hydrate, cesium zinc acetate hydrate, and tin sulphide dihydrate, the solvent is preferably a solution of lanthanum monoethanol oleate and methoxyethanol. B. Forming a CZTS sol-gel (s〇l-gd) precursor (3) (precurs() rs): preferably heated or stirred, and the sol-gel method is mainly based on metal alcoholation The product or the metal salt is dissolved in a solvent to carry out hydrolysis and condensation reaction to form a gel, which is excellent for forming a film. The so-called sol (Sol) refers to a very small colloid, which is formed by uniformly dispersing in the system under the action of the van der Waals force and the electric φ double layer. As for the gel (Gel), after the hydrolysis and condensation reaction, the molecular monomer gradually forms a gel state of the macromolecule via the bond. C. The substrate is placed in the solution containing the precursor (3) for film deposition, and after deposition, a layer of CZTS deposit (9) can be obtained on the substrate (4): the substrate (4) can be plastic, The metal, glass or more material makes the substrate of the invention having a multi-7G suitable for use. D. The CZTS deposit (9) is then coated with sulfur vapor to complete the CZTS film vulcanization 201117412 'treatment process. Please refer to the third figure for the state in which the sulfur powder is initially placed in the present invention. The present invention places the sulfur powder (8) and the CZTS deposit (9) on a heater as shown in Fig. 4 for heating. Therefore, the sulfur powder (8) is formed into a sulfur vapor, and the CZTS film vulcanization process is completed by the vulcanization of the CZTS deposit (9) by the vulcanization. The specific preparation method of the present invention is as follows: in conjunction with the first figure, the relevant components, as shown in the second to fourth figures, are arranged to form a compound (1) which can form a precursor of the CZTS sol gel, and form a solution with the solvent (2). The deposition tank (5) shown in the fourth figure. Then, the heater (6) shown in the fourth figure is heated and stirred, and the CZTS sol-gel precursor (3) as shown in the first and second figures is obtained by blending. As shown in the four figures, the substrate (4) is placed in a prepared sol-gel deposition tank (5) and deposited over a period of time, as shown in the third figure, the sol-gel is driven (3). ) can be uniformly coated on the substrate (4) to form a layer of CZTS deposits (9). The process of φ is preferably heat-treated by the heater (6) as shown in the fourth figure, or after a natural time, the residual solvent can be volatilized to obtain a uniform film layer of CUxZnSnSy (ie, absorption of the solar film). Floor). The above steps can be repeated to achieve the desired film thickness. As shown in the third figure, the obtained CZTS deposit (9) is placed in a container (7) (for example, for experimental use), and the environment of the preferred container (7) of the present invention can be purged with pure gas or The method of pumping removes oxygen from the container to prevent the formation of oxygen sulfide. Sulfur powder (8) is placed around the CZTS deposit (9), and the vessel (7) is sealed to obtain a saturated sulfur vapor of the 201117412. The continuous M CZTS sinks _(9) to carry out the sulfur domain, the alkali czts film. With this (4), the vulcanization efficiency can be improved and the sulfur can be prevented from being recorded. Moreover, the method (4) of the present invention is feasible and has no size limitation. Second: Because this creation is in line with the patentable elements, Mai proposed the creation of the book according to the law. “Industry-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- The first diagram is a schematic diagram of the flow of the present invention. The second diagram is a schematic diagram of the sol-gel formulation of the present invention. The third diagram is a schematic diagram of the state of the preliminary placement of the sulfur powder of the present invention. The fourth diagram is a schematic diagram of the state of the vulcanization of the present invention. Description] (1) .Compound (2). Solvent • (3). Precursor (4). Substrate (5). Deposition tank (6). Heater (7). Container (8). Sulfur powder (9). Sediment