TWI396295B - Preparation method of non - vacuum wet copper indium gallium selenium solar cells - Google Patents

Preparation method of non - vacuum wet copper indium gallium selenium solar cells Download PDF

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TWI396295B
TWI396295B TW098143625A TW98143625A TWI396295B TW I396295 B TWI396295 B TW I396295B TW 098143625 A TW098143625 A TW 098143625A TW 98143625 A TW98143625 A TW 98143625A TW I396295 B TWI396295 B TW I396295B
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TW201123506A (en
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Lung Chuang Chuan
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Jenn Feng New Energy Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Description

非真空濕式銅銦鎵硒太陽電池製作方法Non-vacuum wet copper indium gallium selenide solar cell manufacturing method

本發明係有關一種形成銅銦鎵硒太陽電池的方法,尤其是在非真空下以濕式方式完成。The present invention relates to a method of forming a copper indium gallium selenide solar cell, particularly in a wet manner under non-vacuum.

由於銅銦鎵硒(CIGS)太陽電池具有較高的轉換效率,比如單元電池(Cell)可達20%而模組亦可達14%,因此在眾多太陽能電池中特別受到重視,尤其沒有上游原材料的限制。Since copper indium gallium selenide (CIGS) solar cells have high conversion efficiencies, such as up to 20% for cell cells and 14% for modules, they are particularly valued in many solar cells, especially without upstream raw materials. limits.

在習用技術中,製造銅銦鎵硒太陽能電池的方法一般可分為真空製程和非真空製程。在真空製程中,主要是使用濺鍍法或蒸鍍法,但是真空製程需較昂貴的處理設備且材料利用率也較低,因而使得整體製作成本較高。對於非真空製程,通常是使用印刷法或電沈積法,但因大面積太陽電池的量產技術仍不成熟,屬於實驗室開發階段,所以市面上仍無較大面積的商品化產品問世。In the conventional technology, a method for manufacturing a copper indium gallium selenide solar cell can be generally classified into a vacuum process and a non-vacuum process. In the vacuum process, the sputtering method or the evaporation method is mainly used, but the vacuum process requires relatively expensive processing equipment and the material utilization rate is also low, thereby making the overall manufacturing cost high. For the non-vacuum process, the printing method or the electrodeposition method is usually used. However, since the mass production technology of the large-area solar cell is still immature and belongs to the laboratory development stage, there is still no commercial product of a large area on the market.

因此,需要一種具高度整合性的非真空製程方法,尤其是能在背面電極層上依序形成第一透明導電氧化層、銅銦鎵硒層與硫化鎘層、氧化鋅層及第二透明導電氧化層,進而產生高轉換率、高品質、高可靠度且低製造成本的CIGS太陽電池。Therefore, there is a need for a highly integrated non-vacuum process, in particular, a first transparent conductive oxide layer, a copper indium gallium selenide layer and a cadmium sulfide layer, a zinc oxide layer and a second transparent conductive layer can be sequentially formed on the back electrode layer. The oxide layer, in turn, produces a CIGS solar cell with high conversion rate, high quality, high reliability, and low manufacturing cost.

本發明之主要目的在提供一種非真空濕式銅銦鎵硒太陽電池製作方法,用以製造銅銦鎵硒太陽電池,係在非真空下以濕式方式,於背面電極層上依序形成第一透明導電氧化(TCO)層、銅銦鎵硒層與硫化鎘層、氧化鋅層及第二透明導電氧化(TCO)層,進而形成高轉換率的銅銦鎵硒(CIGS)太陽電池,其中背面電極層係位於基板上,且該非真空濕式銅銦鎵硒製程包括依序的第一TCO層形成處理、銅銦鎵硒層與硫化鎘層形成處理、氧化鋅層形成處理及第二TCO層形成處理,而第一TCO層形成處理、氧化鋅層形成處理及第二TCO層形成處理分別包括切割處理,依序對工作件進行雷射及刮刀切割處理,形成分段的次工作件,藉以提高製程的整合性及銅銦鎵硒(CIGS)太陽電池的整體光電品質。The main object of the present invention is to provide a non-vacuum wet copper indium gallium selenide solar cell manufacturing method for manufacturing a copper indium gallium selenide solar cell, which is formed in a wet manner on a back electrode layer in a non-vacuum manner. a transparent conductive oxidation (TCO) layer, a copper indium gallium selenide layer and a cadmium sulfide layer, a zinc oxide layer and a second transparent conductive oxide (TCO) layer, thereby forming a high conversion rate copper indium gallium selenide (CIGS) solar cell, wherein The back electrode layer is disposed on the substrate, and the non-vacuum wet copper indium gallium selenide process comprises a first TCO layer forming process, a copper indium gallium selenide layer and a cadmium sulfide layer forming process, a zinc oxide layer forming process, and a second TCO. a layer forming process, wherein the first TCO layer forming process, the zinc oxide layer forming process, and the second TCO layer forming process respectively comprise a cutting process, and sequentially performing laser and blade cutting processing on the workpiece to form a segmented secondary working piece, In order to improve the integration of the process and the overall optoelectronic quality of copper indium gallium selenide (CIGS) solar cells.

第一TCO層形成處理包括混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,藉以在背面電極層上形成厚度均勻且晶體結構較佳的第一TCO層。The first TCO layer forming process includes a mixing process, a coating layer forming process, a baking process, a densification process, a heat treatment, and a dicing process, thereby forming a first TCO layer having a uniform thickness and a preferable crystal structure on the back electrode layer.

銅銦鎵硒層與硫化鎘層形成處理包括在第一TCO層形成處理所產生的第一漿料塗佈層上依序形成銅銦鎵硒層與硫化鎘層,其中當作吸收層的銅銦鎵硒層係利用混合處理、塗佈層形成處理、烘乾處理、實密化處理、初級硫硒反應處理、熱處理、雜相清除處理及後級硫硒反應處理而形成,當作緩衝層的硫化鎘層係利用化學槽水浴法(Chemical Bath Deposition,CBD)而形成。The formation process of the copper indium gallium selenide layer and the cadmium sulfide layer comprises sequentially forming a copper indium gallium selenide layer and a cadmium sulfide layer on the first slurry coating layer generated by the first TCO layer forming process, wherein the copper layer serving as the absorption layer The indium gallium selenide layer is formed by a mixing treatment, a coating layer forming treatment, a drying treatment, a solidification treatment, a primary sulfur selenium reaction treatment, a heat treatment, a heterogeneous phase removal treatment, and a post-stage sulfur selenium reaction treatment, and is used as a buffer layer. The cadmium sulfide layer is formed by a chemical bath deposition (CBD).

氧化鋅層形成處理包括利用混合處理、塗佈層形成處理理、烘乾處理、實密化處理、熱處理及切割處理,而在硫化鎘層上形成氧化鋅層。The zinc oxide layer forming treatment includes forming a zinc oxide layer on the cadmium sulfide layer by a mixing treatment, a coating layer forming treatment, a drying treatment, a densification treatment, a heat treatment, and a dicing treatment.

第二TCO層形成處理係類似於上述的第一TCO層形成處理,包括混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,藉以在氧化鋅層上形成第二TCO層。The second TCO layer forming process is similar to the first TCO layer forming process described above, including a mixing process, a coating layer forming process, a drying process, a densification process, a heat treatment, and a dicing process, thereby forming a first layer on the zinc oxide layer. Two TCO layers.

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實施。The embodiments of the present invention will be described in more detail below with reference to the drawings and the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

參閱第一圖,本發明非真空濕式銅銦鎵硒太陽電池製作方法的示意圖。如第一圖所示,本發明的非真空濕式銅銦鎵硒太陽電池製作方法係由步驟S10開始,在非真空下以濕式方式,藉第一TCO層形成裝置,對位於基板上的背面電極層進行第一透明導電氧化(TCO)層形成處理以形成第一TCO層,並帶動該基板往前移動。接著在步驟S20中,利用銅銦鎵硒層與硫化鋅層形成裝置,進行銅銦鎵硒層與硫化鋅層形成處理,而在第一TCO層上形成依序由下而上堆疊的銅銦鎵硒層與硫化鎘層,在步驟S30中,利用氧化鋅層形成裝置,進行氧化鋅層形成處理而在硫化鎘層上形成氧化鋅層,最後進入步驟S40,藉第二TCO層形成裝置,進行第二TCO層形成處理而在氧化鋅層上形成第二TCO層,進而完成具有依序由下而上之基板、背面電極層、第一TCO層、銅銦鎵硒層、硫化鎘層及第二TCO層的銅銦鎵硒太陽電池。Referring to the first figure, a schematic diagram of a method for fabricating a non-vacuum wet copper indium gallium selenide solar cell of the present invention. As shown in the first figure, the non-vacuum wet copper indium gallium selenide solar cell manufacturing method of the present invention starts from step S10, and in a wet manner, by a first TCO layer forming device under non-vacuum, is placed on the substrate. The back electrode layer performs a first transparent conductive oxidation (TCO) layer forming process to form a first TCO layer and drives the substrate to move forward. Next, in step S20, a copper indium gallium selenide layer and a zinc sulfide layer forming device are used to form a copper indium gallium selenide layer and a zinc sulfide layer, and a copper indium stacked in this order from bottom to top is formed on the first TCO layer. a gallium selenide layer and a cadmium sulfide layer, in step S30, a zinc oxide layer forming device is used to form a zinc oxide layer forming treatment to form a zinc oxide layer on the cadmium sulfide layer, and finally, the process proceeds to step S40, and the second TCO layer forming device is used. Performing a second TCO layer forming process to form a second TCO layer on the zinc oxide layer, thereby completing a substrate having a bottom-up sequence, a back electrode layer, a first TCO layer, a copper indium gallium selenide layer, a cadmium sulfide layer, and A copper indium gallium selenide solar cell of a second TCO layer.

參閱第二圖,本發明方法的第一TCO層形成處理之示意圖。如第二圖所示,步驟S10的第一TCO層形成處理係由步驟S11開始,利用混合裝置以進行混合處理,將至少一粉體與至少一溶劑均勻混合成第一TCO層漿料,其中該至少一粉體可包括氧化銦錫(ITO)、氧化錫(SnO2)、氧化銦鈦(ITiO)及氧化鋁鋅(AZO)的至少其中之一,該至少一溶劑可包括醇類、胺類、分散劑、黏著劑及流平劑的至少其中之一。Referring to the second figure, a schematic diagram of the first TCO layer formation process of the method of the present invention. As shown in the second figure, the first TCO layer forming process in step S10 is started in step S11, and the mixing device is used to perform a mixing process to uniformly mix at least one powder with at least one solvent into a first TCO layer slurry, wherein The at least one powder may include at least one of indium tin oxide (ITO), tin oxide (SnO 2 ), indium titanium oxide (ITiO), and aluminum zinc oxide (AZO), and the at least one solvent may include an alcohol or an amine. At least one of a dispersant, an adhesive, and a leveling agent.

接著進入步驟S12,利用塗佈層形成裝置以進行塗佈層形成處理,將步驟S11的第一TCO層漿料在背面電極層上形成第一TCO層漿料塗佈層。然後在步驟S13中利用烘乾裝置進行烘乾處理,以預乾並去除第一TCO層漿料塗佈層中的溶劑。Next, proceeding to step S12, the coating layer forming apparatus is used to perform the coating layer forming treatment, and the first TCO layer slurry of the step S11 is formed on the back electrode layer to form the first TCO layer slurry coating layer. Then, a drying process is performed using a drying device in step S13 to pre-dry and remove the solvent in the first TCO layer slurry coating layer.

接著在步驟S14中,利用實密化裝置對烘乾後的第一TCO層漿料塗佈層進行實密化處理,藉實密化裝置施加壓力至第一TCO層漿料塗佈層上,使第一TCO層漿料塗佈層實密化。在步驟S15中利用熱處理裝置對第一TCO層漿料塗佈層進行熱處理,比如快速熱退火處理(RTP),以改善第一TCO層漿料塗佈層的晶體結構,並形成第一TCO層。最後,在步驟S16中利用切割裝置進行切割處理以形成包括基板、背面電極層及第一TCO層的分段工作件。Next, in step S14, the dried first TCO layer slurry coating layer is subjected to a densification treatment by a densification device, and a pressure is applied to the first TCO layer slurry coating layer by a solid densification device. The first TCO layer slurry coating layer is densified. The first TCO layer slurry coating layer is subjected to heat treatment, such as rapid thermal annealing treatment (RTP), in step S15 by using a heat treatment device to improve the crystal structure of the first TCO layer slurry coating layer and form a first TCO layer. . Finally, a dicing process is performed using a dicing apparatus in step S16 to form a segmented workpiece including a substrate, a back electrode layer, and a first TCO layer.

參閱第三圖,本發明方法的第一TCO層形成裝置之示意圖。如第三圖所示,第一TCO層形成裝置包括混合裝置11、塗佈層形成裝置12、烘乾裝置13、實密化裝置14、熱處理裝置15及切割裝置16,用以分別進行第二圖中的混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,而在基板10上的背面電極層之上形成第一TCO層,且基板10底下係由複數個滾輪18支撐,並向前帶動。Referring to the third figure, a schematic diagram of a first TCO layer forming apparatus of the method of the present invention. As shown in the third figure, the first TCO layer forming device includes a mixing device 11, a coating layer forming device 12, a drying device 13, a solidifying device 14, a heat treatment device 15, and a cutting device 16, for respectively performing the second In the drawing, the mixing treatment, the coating layer forming treatment, the drying treatment, the densification treatment, the heat treatment, and the dicing treatment, the first TCO layer is formed on the back electrode layer on the substrate 10, and the substrate 10 is composed of plural The rollers 18 are supported and driven forward.

混合裝置11包括粉體槽11A、溶劑槽11B及混合槽11C,其中粉體槽11A容置至少一粉體,溶劑槽11B容置至少一溶劑,混合槽11C可為油墨混合槽,用以將粉體槽11A的該至少一粉體以及溶劑槽11B的該至少一溶劑進行均勻混合以形成第一TCO層漿料。The mixing device 11 includes a powder tank 11A, a solvent tank 11B, and a mixing tank 11C. The powder tank 11A houses at least one powder, the solvent tank 11B houses at least one solvent, and the mixing tank 11C can be an ink mixing tank for The at least one powder of the powder tank 11A and the at least one solvent of the solvent tank 11B are uniformly mixed to form a first TCO layer slurry.

塗佈層形成裝置12可包括用以進行噴塗處理的噴塗裝置、用以進行塗佈處理的塗佈裝置及用以進行浸泡處理的浸泡裝置的其中之一。本實施例係以噴塗裝置為示範性實例,藉以說明本發明特徵。在第三圖中,噴塗裝置12可包括超音波噴頭、超音波控制器及氣壓流量控制器(圖中未顯示),可藉超音波將第一TCO層漿料均勻噴塗至背面電極層上,形成第一TCO層漿料塗佈層。烘乾裝置13為加熱裝置,可包括電熱絲、紅外線源及輻射源的至少其中之一,該輻射源可包括微波輻射源。The coating layer forming device 12 may include one of a spraying device for performing a spray coating process, a coating device for performing a coating process, and an infusion device for performing a soaking process. This embodiment is an exemplary embodiment of a spray coating apparatus to illustrate the features of the present invention. In the third figure, the spraying device 12 may include an ultrasonic nozzle, an ultrasonic controller, and a pneumatic flow controller (not shown), and the first TCO layer slurry may be uniformly sprayed onto the back electrode layer by ultrasonic waves. A first TCO layer slurry coating layer is formed. The drying device 13 is a heating device and may include at least one of a heating wire, an infrared source, and a radiation source, and the radiation source may include a microwave radiation source.

實密化裝置14可包括用以進行滾壓處理的滾壓裝置、用以進行高壓噴液壓合處理的高壓噴液壓合裝置及用以進行高壓噴氣壓合處理的高壓噴氣壓合裝置的其中之一。本實施例係以滾壓裝置為示範性實例,藉以說明本發明特徵。滾壓裝置14可包括複數個滾輪,壓在第一TCO層漿料塗佈層上,分別依序在輕壓區段、中壓區段及重壓區段施加輕度壓力、中度壓力及重度壓力,以逐步使第一TCO層漿料塗佈層實密化。The solidification device 14 may include a rolling device for performing a rolling process, a high pressure spray hydraulic device for performing a high pressure spray hydraulic pressure process, and a high pressure jet press device for performing a high pressure jet press treatment. One. This embodiment is an exemplary embodiment of a rolling device for illustrating the features of the present invention. The rolling device 14 may include a plurality of rollers pressed on the first TCO layer slurry coating layer, and sequentially apply mild pressure, moderate pressure, and the like in the light pressure section, the medium pressure section, and the heavy pressure section, respectively. The pressure is severe to gradually solidify the first TCO layer slurry coating layer.

熱處理裝置15包括利用加熱裝置及冷卻裝置,對第一TCO層漿料塗佈層進行依序的快速升溫結晶處理、多段恆溫結晶處理及多段降溫處理,以改善晶體結構,並形成第一TCO層。切割裝置16包括雷射及刮刀,以進行切割處理。The heat treatment device 15 includes a sequential rapid temperature crystallization treatment, a multi-stage constant temperature crystallization treatment, and a multi-stage cooling treatment on the first TCO layer slurry coating layer by using the heating device and the cooling device to improve the crystal structure and form the first TCO layer. . The cutting device 16 includes a laser and a doctor blade for performing a cutting process.

參閱第四圖,本發明方法的銅銦鎵硒層與硫化鎘層形成處理之示意圖。如第四圖所示,步驟S20的銅銦鎵硒層與硫化鎘層形成處理包括依序之步驟S21的混合處理、步驟S22的塗佈層形成處理、步驟S23的烘乾處理、步驟S24的實密化處理、步驟S25的初級硫硒反應處理、步驟S26的熱處理、步驟S27的雜相清除處理、步驟S28的後級硫硒反應處理及步驟S29的硫化鎘層生長處理,係利用銅銦鎵硒層與硫化鎘層形成裝置,而在第一TCO層上形成銅銦鎵硒層與硫化鎘層。Referring to the fourth figure, a schematic diagram of the formation process of the copper indium gallium selenide layer and the cadmium sulfide layer of the method of the present invention. As shown in the fourth figure, the copper indium gallium selenide layer and the cadmium sulfide layer forming process in step S20 includes the sequential mixing process of step S21, the coating layer forming process of step S22, the drying process of step S23, and the step S24 of step S24. The densification treatment, the primary sulfur selenium reaction treatment in step S25, the heat treatment in step S26, the impurity phase removal treatment in step S27, the subsequent sulfur selenium reaction treatment in step S28, and the cadmium sulfide layer growth treatment in step S29 are performed using copper indium. A gallium selenide layer and a cadmium sulfide layer are formed, and a copper indium gallium selenide layer and a cadmium sulfide layer are formed on the first TCO layer.

步驟S21、步驟S22、步驟S23及步驟S24係類似於第二圖的步驟S11、步驟S12、步驟S13及步驟S14,差異點在於步驟S21係利用混合裝置以形成銅銦鎵硒層漿料,所使用的至少一粉體包括銅銦合金(CuIn)、銅銦鎵化合物(CuInGa)、硒化銅銦(CuInSe)、硒化銅銦鎵(CuInGaSe)、硫化銅銦(CuInS)及硫化銅銦鎵(CuInGaS)粉體的至少其中之一,步驟S22的塗佈層形成處理可在第一TCO層上形成銅銦鎵硒層漿料塗佈層,步驟S23的烘乾處理利用烘乾裝置對銅銦鎵硒層漿料塗佈層中的溶劑進行預乾與去除,而步驟S24的實密化處理利用滾壓裝置對烘乾的銅銦鎵硒層漿料塗佈層進行實密化。Step S21, step S22, step S23 and step S24 are similar to step S11, step S12, step S13 and step S14 of the second figure, the difference is that step S21 uses a mixing device to form a copper indium gallium selenide layer slurry. At least one powder used includes CuIn, CuInGa, CuInSe, CuInGaSe, CuInS and CuSS. At least one of (CuInGaS) powder, the coating layer forming process of step S22 may form a copper indium gallium selenide layer slurry coating layer on the first TCO layer, and the drying process of step S23 utilizes a drying device to copper The solvent in the indium gallium selenide layer slurry coating layer is pre-dried and removed, and the solidification treatment in step S24 is performed by using a rolling device to solidify the dried copper indium gallium selenide layer slurry coating layer.

在步驟S25中,初級硫硒反應處理包括初級硫化反應及初級硒化反應係利用初級硫硒反應裝置,使銅銦鎵硒硫漿料塗佈層產生硫化物及硒化物,藉以形成初級的銅銦鎵硒層。步驟S26的快速熱退火處理係類似於第二圖的步驟S15,利用快速熱退火裝置以改善初級的銅銦鎵硒層之晶體結構。在步驟S27中,雜相清除處理利用雜相清除裝置以去除初級的銅銦鎵硒層中雜相的化合物,並進行清洗及烘乾。在步驟S28中,後級硫硒反應處理係類似於初級硫硒反應處理,利用後級硫硒反應裝置對初級的銅銦鎵硒層進行進一步的後級硫化反應及後級硒化反應,以形成後級的銅銦鎵硒層,亦即所需的銅銦鎵硒層。In step S25, the primary sulfur selenium reaction treatment includes a primary sulfurization reaction and a primary selenization reaction system using a primary sulfur selenium reaction device to cause a copper indium gallium selenide sulfur slurry coating layer to generate sulfides and selenides, thereby forming primary copper. Indium gallium selenide layer. The rapid thermal annealing process of step S26 is similar to step S15 of the second figure, using a rapid thermal annealing device to improve the crystal structure of the primary copper indium gallium selenide layer. In step S27, the impurity phase removal process utilizes a heterophase removal device to remove the compound of the impurity phase in the primary copper indium gallium selenide layer, and to perform cleaning and drying. In step S28, the subsequent sulfur-selenium reaction treatment is similar to the primary sulfur-selenium reaction treatment, and the subsequent copper-indium gallium selenide layer is subjected to further post-sulfurization reaction and post-stage selenization reaction by using a post-stage sulfur selenium reaction device. A copper indium gallium selenide layer of the latter stage, that is, a desired copper indium gallium selenide layer, is formed.

在步驟S29中,硫化鎘層生長處理係利用硫化鎘層生長裝置,以化學槽水浴法(Chemical Bath Deposition,CBD)在步驟S28的銅銦鎵硒層上形成硫化鎘層,亦即硫化鎘緩衝層,而且步驟S29進一步包括基板刮除處理及清洗烘乾處理,以分別刮除基板的多餘材料,以及清洗並烘乾該硫化鎘緩衝層。In step S29, the cadmium sulfide layer growth treatment uses a cadmium sulfide layer growth device to form a cadmium sulfide layer on the copper indium gallium selenide layer of the step S28 by a chemical bath deposition (CBD), that is, a cadmium sulfide buffer. And the step S29 further includes a substrate scraping process and a cleaning and drying process to scrape the excess material of the substrate separately, and to clean and dry the cadmium sulfide buffer layer.

參閱第五圖,本發明方法的銅銦鎵硒層與硫化鋅層形成裝置之示意圖。如第五圖所示,銅銦鎵硒層與硫化鋅層形成裝置包括混合裝置21、塗佈層形成裝置22、烘乾裝置23、實密化裝置24、初級硫硒反應裝置25、熱處理裝置26、雜相清除裝置27、後級硫硒反應裝置28及硫化鎘層生長裝置29,其中混合裝置21、塗佈層形成裝置22、烘乾裝置23、實密化裝置24及熱處理裝置26分別類似於第三圖的混合裝置11、塗佈層形成裝置12、烘乾裝置13、實密化裝置14及熱處理裝置15,而混合裝置21包括粉體槽21A、溶劑槽21B及混合槽21C,塗佈層形成裝置22包括超音波噴頭、超音波控制器及氣壓流量控制器(圖中未顯示)。Referring to the fifth figure, a schematic diagram of a copper indium gallium selenide layer and a zinc sulfide layer forming apparatus of the method of the present invention. As shown in the fifth figure, the device for forming a copper indium gallium selenide layer and a zinc sulfide layer comprises a mixing device 21, a coating layer forming device 22, a drying device 23, a solidification device 24, a primary sulfur selenium reaction device 25, and a heat treatment device. 26, a heterogeneous phase removing device 27, a post-stage sulfur selenium reaction device 28 and a cadmium sulfide layer growing device 29, wherein the mixing device 21, the coating layer forming device 22, the drying device 23, the solidifying device 24, and the heat treating device 26 respectively Similar to the mixing device 11, the coating layer forming device 12, the drying device 13, the solidifying device 14, and the heat treatment device 15, which are similar to the third embodiment, the mixing device 21 includes a powder tank 21A, a solvent tank 21B, and a mixing tank 21C. The coating layer forming device 22 includes an ultrasonic jet head, an ultrasonic controller, and a pneumatic flow controller (not shown).

初級硫硒反應裝置25係依序分別通入硫化氫及硒化氫,並在升溫下進行初級硫化反應及初級硒化反應。雜相清除裝置27包括雜相清除劑,以清除雜相化合物,包括硒化亞銅(Cu2 Se)及硫化銅(CuS)的至少其中之一,該雜相清除劑包含氰化鈉(NaCN)、氰化鉀(KCN)及溴化物的至少其中之一。後級硫硒反應裝置28類似於初級硫硒反應裝置25,依序分別通入硫化氫及硒化氫,並在升溫下進行後級硫化反應及後級硒化反應。The primary sulfur-selenium reaction device 25 sequentially introduces hydrogen sulfide and hydrogen selenide, respectively, and performs primary sulfurization reaction and primary selenization reaction at elevated temperature. The heterogeneous removal device 27 includes a heterogeneous scavenger to scavenge the heterophasic compound, including at least one of cuprous selenide (Cu 2 Se) and copper sulfide (CuS), the heterogeneous scavenger comprising sodium cyanide (NaCN) At least one of potassium cyanide (KCN) and bromide. The latter sulfur-selenium reaction device 28 is similar to the primary sulfur-selenium reaction device 25, and sequentially passes hydrogen sulfide and hydrogen selenide, and performs post-sulfurization reaction and post-stage selenization reaction at elevated temperature.

硫化鎘層生長裝置29包括含有硫及鎘的水溶液,使銅銦鎵硒層浸泡於該水溶液中,而在銅銦鎵硒層上形成硫化鎘層,且該水溶液包括氯化鹽、氨水及硫尿,該氯化鹽可包括氯化鎘、硫酸鎘、碘化鎘及二乙酸鎘的至少其中之一。The cadmium sulfide layer growth device 29 includes an aqueous solution containing sulfur and cadmium, so that a copper indium gallium selenide layer is immersed in the aqueous solution, and a cadmium sulfide layer is formed on the copper indium gallium selenide layer, and the aqueous solution includes a chloride salt, an ammonia water, and a sulfur In the urine, the chloride salt may include at least one of cadmium chloride, cadmium sulfate, cadmium iodide, and cadmium diacetate.

參閱第六圖,本發明方法的氧化鋅層形成處理之示意圖。如第六圖所示,本發明方法的氧化鋅層形成處理係類似於第二圖的步驟S10,係利用氧化鋅層形成裝置以進行依序之步驟S31的混合處理、步驟S32的塗佈層形成處理、步驟S33的烘乾處理、步驟S34的實密化處理、步驟S35的熱處理及步驟S36的切割處理,其差異點在於該至少一粉體包括氧化鋅粉體,而步驟S31係將氧化鋅粉體與包括醇類、胺類、分散劑、黏著劑及流平劑的至少其中之一的溶劑混合,以形成氧化鋅漿料,再藉步驟S32將氧化鋅漿料在硫化鎘層上形成氧化鋅塗佈層,接著經步驟S33的烘乾處理及步驟S34的實密化處理。步驟S35再藉熱處理以改善氧化鋅塗佈層的晶體結構,而形成氧化鋅層,最後在步驟S36中切割分段。Referring to the sixth drawing, a schematic diagram of the zinc oxide layer forming treatment of the method of the present invention. As shown in the sixth figure, the zinc oxide layer forming treatment of the method of the present invention is similar to the step S10 of the second drawing, using the zinc oxide layer forming apparatus to carry out the sequential mixing treatment of the step S31, and the coating layer of the step S32. The forming process, the drying process of step S33, the densification process of step S34, the heat treatment of step S35, and the dicing process of step S36 are different in that the at least one powder includes zinc oxide powder, and step S31 is oxidized. The zinc powder is mixed with a solvent including at least one of an alcohol, an amine, a dispersant, an adhesive, and a leveling agent to form a zinc oxide slurry, and the zinc oxide slurry is deposited on the cadmium sulfide layer by the step S32. The zinc oxide coating layer is formed, followed by the drying treatment in step S33 and the densification treatment in step S34. Step S35 is further heat treated to improve the crystal structure of the zinc oxide coating layer to form a zinc oxide layer, and finally the segment is cut in step S36.

參閱第七圖,本發明方法的氧化鋅層形成裝置之示意圖。如第七圖所示,氧化鋅層形成裝置類似於第三圖的第一TCO層形成裝置,係包括混合裝置31、塗佈層形成裝置32、烘乾裝置33、實密化裝置34、熱處理裝置35及切割裝置36,用以分別進行第六圖中的混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,而在硫化鎘層上形成氧化鋅層,且混合裝置31包括粉體槽31A、溶劑槽31B及混合槽31C,其差異點在於,粉體槽31A係容置氧化鋅粉體。Referring to the seventh figure, a schematic diagram of a zinc oxide layer forming apparatus of the method of the present invention. As shown in the seventh figure, the zinc oxide layer forming device is similar to the first TCO layer forming device of the third figure, and includes a mixing device 31, a coating layer forming device 32, a drying device 33, a solidifying device 34, and a heat treatment. The device 35 and the cutting device 36 are respectively configured to perform the mixing process, the coating layer forming process, the drying process, the densification process, the heat treatment and the cutting process in the sixth figure, and form a zinc oxide layer on the cadmium sulfide layer. Further, the mixing device 31 includes a powder tank 31A, a solvent tank 31B, and a mixing tank 31C, the difference being that the powder tank 31A accommodates zinc oxide powder.

此外,步驟S40的第二TCO層形成處理係與步驟S10的第一TCO層形成處理相同,係利用第二TCO鋅層形成裝置以進行依序之混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,進而在氧化鋅層上形成第二TCO層,而第二TCO鋅層形成裝置的結構係相同於第三圖的第一TCO鋅層形成裝置,在此不作贅述。Further, the second TCO layer forming process of step S40 is the same as the first TCO layer forming process of step S10, and the second TCO zinc layer forming device is used to perform the sequential mixing process, the coating layer forming process, and the drying process. a solidification treatment, a heat treatment, and a dicing treatment to form a second TCO layer on the zinc oxide layer, and the second TCO zinc layer formation device has the same structure as the first TCO zinc layer formation device in the third embodiment. Do not repeat them.

因此,上述本發明的方法可完成在基板的背面電極層上具有依序由下而上堆疊的第一TCO層、銅銦鎵硒層與硫化鎘層、氧化鋅層及第二TCO層的太陽電池。Therefore, the above method of the present invention can complete the first TCO layer, the copper indium gallium selenide layer and the cadmium sulfide layer, the zinc oxide layer and the second TCO layer which are sequentially stacked on the back electrode layer of the substrate. battery.

本發明的特點在於整合第一TCO層形成處理、銅銦鎵硒層與硫化鎘層形成處理、氧化鋅層形成處理及第二TCO層形成處理,而在非真空下以濕式方式進行,於背面電極層上依序形成第一TCO層、銅銦鎵硒層與硫化鎘層、氧化鋅層及第二TCO層,進而形成高轉換率的銅銦鎵硒(CIGS)太陽電池,適合大批量生產製作,同時降低製作成本,並簡化製作流程,提高產品良率。The invention is characterized in that the first TCO layer forming process, the copper indium gallium selenide layer and the cadmium sulfide layer forming process, the zinc oxide layer forming process and the second TCO layer forming process are integrated, and the method is performed in a wet manner under non-vacuum. A first TCO layer, a copper indium gallium selenide layer and a cadmium sulfide layer, a zinc oxide layer and a second TCO layer are sequentially formed on the back electrode layer to form a high conversion rate copper indium gallium selenide (CIGS) solar cell, which is suitable for large quantities. Production and production, while reducing production costs, and simplify the production process to improve product yield.

以上所述者僅為用以解釋本發明之較佳實施例,並非企圖據以對本發明做任何形式上之限制,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。The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, and any modifications or alterations to the present invention made in the spirit of the same invention. All should still be included in the scope of the intention of the present invention.

10...基板10. . . Substrate

11...混合裝置11. . . Mixing device

11A...粉體槽11A. . . Powder slot

11B...溶劑槽11B. . . Solvent tank

11C...混合槽11C. . . Mixing tank

12...塗佈層形成裝置12. . . Coating layer forming device

13...烘乾裝置13. . . Drying device

14...實密化裝置14. . . Solidification device

15...熱處理裝置15. . . Heat treatment device

16...切割裝置16. . . Cutting device

18...滾輪18. . . Wheel

21...混合裝置twenty one. . . Mixing device

21A...粉體槽21A. . . Powder slot

21B...溶劑槽21B. . . Solvent tank

21C...混合槽21C. . . Mixing tank

22...塗佈層形成裝置twenty two. . . Coating layer forming device

23...烘乾裝置twenty three. . . Drying device

24...實密化裝置twenty four. . . Solidification device

25...初級硫硒反應裝置25. . . Primary sulfur selenium reaction unit

26...熱處理裝置26. . . Heat treatment device

27...雜相清除裝置27. . . Miscellaneous phase cleaning device

28...後級硫硒反應裝置28. . . Subsequent sulfur-selenium reaction device

29...硫化鎘層生長裝置29. . . Cadmium sulfide layer growth device

31...混合裝置31. . . Mixing device

31A...粉體槽31A. . . Powder slot

31B...溶劑槽31B. . . Solvent tank

31C...混合槽31C. . . Mixing tank

32...塗佈層形成裝置32. . . Coating layer forming device

33...烘乾裝置33. . . Drying device

34...實密化裝置34. . . Solidification device

35...熱處理裝置35. . . Heat treatment device

36...切割裝置36. . . Cutting device

S10...第一透明導電氧化層形成處理S10. . . First transparent conductive oxide layer forming process

S11...混合處理S11. . . Mixed processing

S12...塗佈層形成處理S12. . . Coating layer formation treatment

S13...烘乾處理S13. . . Drying treatment

S14...實密化處理S14. . . Solidification

S15...熱處理S15. . . Heat treatment

S16...切割處理S16. . . Cutting treatment

S20...銅銦鎵硒層與硫化鎘層形成處理S20. . . Formation process of copper indium gallium selenide layer and cadmium sulfide layer

S21...混合處理S21. . . Mixed processing

S22...塗佈層形成處理S22. . . Coating layer formation treatment

S23...烘乾處理S23. . . Drying treatment

S24...實密化處理S24. . . Solidification

S25...初級硫硒反應處理S25. . . Primary sulfur selenium reaction treatment

S26...熱處理S26. . . Heat treatment

S27...雜相清除處理S27. . . Miscellaneous phase removal

S28...後級硫硒反應處理S28. . . Subsequent sulfur and selenium reaction treatment

S29...硫化鎘層生長處理S29. . . Cadmium sulfide layer growth treatment

S30...氧化鋅層形成處理S30. . . Zinc oxide layer formation treatment

S31...混合處理S31. . . Mixed processing

S32...塗佈層形成處理S32. . . Coating layer formation treatment

S33...烘乾處理S33. . . Drying treatment

S34...實密化處理S34. . . Solidification

S35...熱處理S35. . . Heat treatment

S36...切割處理S36. . . Cutting process

S40...第二透明導電氧化層形成處理S40. . . Second transparent conductive oxide layer forming process

第一圖為本發明非真空濕式銅銦鎵硒太陽電池製作方法的示意圖。The first figure is a schematic diagram of a method for fabricating a non-vacuum wet copper indium gallium selenide solar cell of the present invention.

第二圖為本發明方法的第一TCO層形成處理之示意圖。The second figure is a schematic diagram of the first TCO layer formation process of the method of the present invention.

第三圖為本發明方法的第一TCO層形成裝置之示意圖。The third figure is a schematic illustration of a first TCO layer forming apparatus of the method of the present invention.

第四圖為本發明方法的銅銦鎵硒層與硫化鋅層形成處理之示意圖。The fourth figure is a schematic diagram of the formation process of the copper indium gallium selenide layer and the zinc sulfide layer of the method of the present invention.

第五圖為本發明方法的銅銦鎵硒層與硫化鋅層形成裝置之示意圖。The fifth figure is a schematic view of a device for forming a copper indium gallium selenide layer and a zinc sulfide layer according to the method of the present invention.

第六圖為本發明方法的氧化鋅層形成處理之示意圖。Figure 6 is a schematic illustration of the zinc oxide layer formation process of the method of the present invention.

第七圖為本發明方法的氧化鋅層形成裝置之示意圖。Figure 7 is a schematic illustration of a zinc oxide layer forming apparatus of the method of the present invention.

S10...第一透明導電氧化層形成處理S10. . . First transparent conductive oxide layer forming process

S20...銅銦鎵硒層與硫化鎘層形成處理S20. . . Formation process of copper indium gallium selenide layer and cadmium sulfide layer

S30...氧化鋅層形成處理S30. . . Zinc oxide layer formation treatment

S40...第二透明導電氧化層形成處理S40. . . Second transparent conductive oxide layer forming process

Claims (16)

一種非真空濕式銅銦鎵硒太陽電池製作方法,用以在非真空下以濕式方式製造銅銦鎵硒太陽電池的第一透明導電氧化層、銅銦鎵硒層與硫化鎘層、氧化鋅層及第二透明導電氧化層,該方法係包括以下依序進行之步驟:對具有背面電極層的基板,利用第一透明導電氧化層形成裝置,進行第一透明導電氧化層形成處理,該背面電極層係位於基板上,且該基板底下係由複數個滾輪支撐並向前帶動,該第一透明導電氧化層形成處理包括混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,進而在該背面電極層上形成該第一透明導電氧化層;利用銅銦鎵硒層與硫化鎘層形成裝置,進行銅銦鎵硒層與硫化鎘層形成處理,包括混合處理、塗佈層形成處理、烘乾處理、實密化處理、初級硫硒反應處理、熱處理、雜相清除處理、後級硫硒反應處理及硫化鎘層生長處理,藉以在該第一透明導電氧化層上依序形成銅銦鎵硒層與硫化鎘層;利用氧化鋅層形成裝置以進行氧化鋅層形成處理,包括混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,進而在該硫化鎘層上形成氧化鋅層;以及利用第二透明導電氧化層形成裝置,進行第二透明導電氧化層形成處理,包括混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理,藉以在該氧化鋅層上形成第二透明導電氧化層。Non-vacuum wet copper indium gallium selenide solar cell manufacturing method for manufacturing first transparent conductive oxide layer, copper indium gallium selenide layer and cadmium sulfide layer of copper indium gallium selenide solar cell in a wet manner under non-vacuum a zinc layer and a second transparent conductive oxide layer, the method comprising the steps of: performing a first transparent conductive oxide layer forming process on the substrate having the back electrode layer by using the first transparent conductive oxide layer forming device, The back electrode layer is located on the substrate, and the bottom of the substrate is supported by a plurality of rollers and is driven forward. The first transparent conductive oxide layer forming process includes a mixing process, a coating layer forming process, a drying process, and a solidification process. And heat-treating and cutting, further forming the first transparent conductive oxide layer on the back electrode layer; forming a copper indium gallium selenide layer and a cadmium sulfide layer by using a copper indium gallium selenide layer and a cadmium sulfide layer forming device, including mixing Treatment, coating layer formation treatment, drying treatment, solidification treatment, primary sulfur selenium reaction treatment, heat treatment, impurity phase removal treatment, post-stage sulfur selenium reaction treatment a cadmium sulfide layer growth treatment, in which a copper indium gallium selenide layer and a cadmium sulfide layer are sequentially formed on the first transparent conductive oxide layer; and a zinc oxide layer forming device is used to perform a zinc oxide layer forming treatment, including a mixing treatment and a coating layer Forming treatment, drying treatment, solidification treatment, heat treatment and cutting treatment, further forming a zinc oxide layer on the cadmium sulfide layer; and performing a second transparent conductive oxide layer formation treatment by using the second transparent conductive oxide layer forming device, A mixing treatment, a coating layer forming treatment, a drying treatment, a densification treatment, a heat treatment, and a cutting treatment are included to form a second transparent conductive oxide layer on the zinc oxide layer. 依據申請專利範圍第1項所述之方法,其中該第一透明導電氧化層形成裝置包括混合裝置、塗佈層形成裝置、烘乾裝置、實密化裝置、熱處理裝置及切割裝置,藉以分別進行混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理。The method of claim 1, wherein the first transparent conductive oxide layer forming device comprises a mixing device, a coating layer forming device, a drying device, a solidification device, a heat treatment device, and a cutting device, respectively Mixing treatment, coating layer forming treatment, drying treatment, solidification treatment, heat treatment, and cutting treatment. 依據申請專利範圍第1項所述之方法,其中該銅銦鎵硒層與硫化鎘層形成裝置包括混合裝置、塗佈層形成裝置、烘乾裝置、實密化裝置、初級硫硒反應裝置、熱處理裝置、雜相清除裝置、後級硫硒反應裝置及硫化鎘層生長裝置,藉以分別進行混合處理、塗佈層形成處理、烘乾處理、實密化處理、初級硫硒反應處理、熱處理、雜相清除處理、後級硫硒反應處理及硫化鎘層生長處理。According to the method of claim 1, wherein the copper indium gallium selenide layer and the cadmium sulfide layer forming device comprise a mixing device, a coating layer forming device, a drying device, a solidification device, a primary sulfur selenium reaction device, The heat treatment device, the impurity phase cleaning device, the post-stage sulfur selenium reaction device and the cadmium sulfide layer growth device are respectively subjected to mixing treatment, coating layer formation treatment, drying treatment, solidification treatment, primary sulfur selenium reaction treatment, heat treatment, Hybrid phase removal treatment, post-stage sulfur selenium reaction treatment and cadmium sulfide layer growth treatment. 依據申請專利範圍第1項所述之方法,其中該氧化鋅層形成裝置包括混合裝置、塗佈層形成裝置、烘乾裝置、實密化裝置、熱處理裝置及切割裝置,以分別進行混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理。The method according to claim 1, wherein the zinc oxide layer forming device comprises a mixing device, a coating layer forming device, a drying device, a solidification device, a heat treatment device, and a cutting device, for separately performing mixing treatment, Coating layer forming treatment, drying treatment, solidification treatment, heat treatment, and cutting treatment. 依據申請專利範圍第1項所述之方法,其中該第二透明導電氧化層形成裝置包括混合裝置、塗佈層形成裝置、烘乾裝置、實密化裝置、熱處理裝置及切割裝置,藉以對透明導電氧化物粉體及至少一溶劑進行混合處理、塗佈層形成處理、烘乾處理、實密化處理、熱處理及切割處理。The method of claim 1, wherein the second transparent conductive oxide layer forming device comprises a mixing device, a coating layer forming device, a drying device, a densification device, a heat treatment device, and a cutting device, thereby being transparent The conductive oxide powder and at least one solvent are subjected to a mixing treatment, a coating layer forming treatment, a drying treatment, a densification treatment, a heat treatment, and a cutting treatment. 依據申請專利範圍第2項至第5項中任一項所述之方法,其中該混合裝置包括粉體槽、溶劑槽及混合槽,該粉體槽係用以容置至少一粉體,該溶劑槽係用以容置至少一溶劑,該混合槽將該至少一粉體及該至少一溶劑均勻混合。The method according to any one of the preceding claims, wherein the mixing device comprises a powder tank, a solvent tank and a mixing tank, the powder tank is for accommodating at least one powder, The solvent tank is configured to accommodate at least one solvent, and the mixing tank uniformly mixes the at least one powder and the at least one solvent. 依據申請專利範圍第2項至第5項中任一項所述之方法,其中該塗佈層形成裝置包括用以進行噴塗處理的噴塗裝置、用以進行塗佈處理的塗佈裝置及用以進行浸泡處理的浸泡裝置的其中之一,且該噴塗裝置包括超音波噴頭、超音波控制器及氣壓流量控制器。The method according to any one of claims 2 to 5, wherein the coating layer forming device comprises a spraying device for performing a spraying process, a coating device for performing a coating process, and One of the soaking devices for performing the soaking treatment, and the spraying device includes an ultrasonic nozzle, an ultrasonic controller, and a pneumatic flow controller. 依據申請專利範圍第2項至第5項中任一項所述之方法,其中該烘乾裝置為加熱裝置,包括電熱絲、紅外線源及輻射源的至少其中之一,該輻射源包括微波輻射源。The method according to any one of the preceding claims, wherein the drying device is a heating device comprising at least one of a heating wire, an infrared source and a radiation source, the radiation source comprising microwave radiation source. 依據申請專利範圍第2項至第5項中任一項所述之方法,其中該實密化裝置係包括用以進行滾壓處理的滾壓裝置、用以進行高壓噴液壓合處理的高壓噴液壓合裝置及用以進行高壓噴氣壓合處理的高壓噴氣壓合裝置的其中之一,且該滾壓裝置包括複數個滾輪,用以依序施加輕度壓力、中度壓力及重度壓力,藉以逐步達到密化。The method according to any one of claims 2 to 5, wherein the solidification device comprises a rolling device for performing a rolling process, and a high pressure spray for performing a high pressure spray hydraulic treatment. a hydraulic combination device and one of a high pressure jet compression device for performing high pressure jet compression treatment, and the rolling device includes a plurality of rollers for sequentially applying mild pressure, medium pressure and heavy pressure, thereby Gradually reach densification. 依據申請專利範圍第2項至第5項中任一項所述之方法,其中該熱處理裝置包括利用加熱裝置及冷卻裝置,以進行依序的快速升溫結晶處理、多段恆溫結晶處理及多段降溫處理。The method according to any one of claims 2 to 5, wherein the heat treatment device comprises a heating device and a cooling device for performing sequential rapid temperature crystallization treatment, multi-stage constant temperature crystallization treatment, and multi-stage cooling treatment. . 依據申請專利範圍第2項、第4項及第5項中任一項所述之方法,其中該切割裝置包括雷射及刮刀。The method of any of claims 2, 4, and 5, wherein the cutting device comprises a laser and a doctor blade. 依據申請專利範圍第6項所述之方法,其中該第一透明導電氧化層形成裝置的粉體槽所容置的該至少一粉體包括氧化銦錫、氧化錫、氧化銦鈦及氧化鋁鋅的至少其中之一,該銅銦鎵硒層與硫化鎘層形成裝置的粉體槽所容置的該至少一粉體包括銅銦合金、銅銦鎵化合物、硒化銅銦、硒化銅銦鎵、硫化銅銦及硫化銅銦鎵粉體的至少其中之一,該氧化鋅層形成裝置的粉體槽所容置的該至少一粉體包括氧化鋅粉體,該第二透明導電氧化層形成裝置的粉體槽所容置的該至少一粉體包括氧化銦錫、氧化錫、氧化銦鈦及氧化鋁鋅的至少其中之一,該第一透明導電氧化層形成裝置、該銅銦鎵硒層與硫化鎘層形成裝置、該氧化鋅層形成裝置及該第二透明導電氧化層形成裝置的溶劑槽所容置的該至少一溶劑可包括醇類、胺類、分散劑、黏著劑及流平劑的至少其中之一。According to the method of claim 6, wherein the at least one powder contained in the powder tank of the first transparent conductive oxide layer forming device comprises indium tin oxide, tin oxide, indium titanium oxide and aluminum zinc oxide. At least one of the at least one powder of the copper indium gallium selenide layer and the cadmium sulfide layer forming device includes a copper indium alloy, a copper indium gallium compound, copper indium selenide, and copper indium selenide. At least one of gallium, copper indium sulfide, and copper indium gallium sulfide powder, the at least one powder contained in the powder tank of the zinc oxide layer forming device includes zinc oxide powder, and the second transparent conductive oxide layer The at least one powder contained in the powder tank of the forming device includes at least one of indium tin oxide, tin oxide, indium titanium oxide and aluminum zinc oxide, the first transparent conductive oxide layer forming device, the copper indium gallium The at least one solvent contained in the selenium layer and the cadmium sulfide layer forming device, the zinc oxide layer forming device, and the solvent tank of the second transparent conductive oxide layer forming device may include alcohols, amines, dispersants, adhesives, and At least one of the leveling agents. 依據申請專利範圍第3項所述之方法,其中該初級硫硒反應裝置係依序分別通入硫化氫及硒化氫,並在升溫下進行初級硫化反應及初級硒化反應。According to the method of claim 3, the primary sulfur selenium reaction device sequentially passes hydrogen sulfide and hydrogen selenide, respectively, and performs primary sulfurization reaction and primary selenization reaction at elevated temperature. 依據申請專利範圍第3項所述之方法,其中該雜相清除裝置包括雜相清除劑,以清除雜相化合物,包括硒化亞銅及硫化銅的至少其中之一,該雜相清除劑包含氰化鈉、氰化鉀及溴化物的至少其中之一。The method of claim 3, wherein the impurity phase scavenging device comprises a heterogeneous scavenger to scavenge at least one of the heterogeneous compound, including cuprous selenide and copper sulfide, the heterogeneous scavenger comprising At least one of sodium cyanide, potassium cyanide and bromide. 依據申請專利範圍第3項所述之方法,其中該後級硫硒反應裝置係依序分別通入硫化氫及硒化氫,並在升溫下進行後級硫化反應及初級硒化反應。According to the method of claim 3, wherein the subsequent sulfur-selenium reaction device sequentially passes hydrogen sulfide and hydrogen selenide, respectively, and performs a post-sulfidation reaction and a primary selenization reaction at a temperature rise. 依據申請專利範圍第3項所述之方法,其中該硫化鎘層生長裝置包括含有硫及鎘的水溶液,使該銅銦鎵硒層浸泡於該水溶液中,而在該銅銦鎵硒層上形成硫化鎘層,且該水溶液包括氯化鹽、氨水及硫尿,該氯化鹽可包括氯化鎘、硫酸鎘、碘化鎘及二乙酸鎘的至少其中之一。According to the method of claim 3, wherein the cadmium sulfide layer growth device comprises an aqueous solution containing sulfur and cadmium, the copper indium gallium selenide layer is immersed in the aqueous solution, and formed on the copper indium gallium selenide layer. a cadmium sulfide layer, and the aqueous solution includes a chloride salt, ammonia water, and thiourea, and the chloride salt may include at least one of cadmium chloride, cadmium sulfate, cadmium iodide, and cadmium diacetate.
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