脈衝式電鍍CuInSe2在抗反射結構基板之薄膜型太陽能電池研製

本研究利用脈衝式電壓電化學沉積法，結合非硒化熱處理製程，製造二硒化銅銦(CuInSe2,簡稱CIS)薄膜，並製造上蓋板結構(Superstrate)，與下基板結構(Substrate)之CIS薄膜型太陽能電池，其結構分別為Glass/ITO/ZnO/CIS/Mo與Glass/Mo/CIS/ZnO/ITO。除CIS吸收層薄膜為脈衝式電壓電化學沉積法外，其餘透明導電層700 nm之ITO薄膜、50 nm之緩衝層ZnO與厚度為1 m背電極Mo，皆是利用射頻磁控濺鍍機台沉積。本研究利用KOH濕式蝕刻技術，蝕刻<100>方向之單晶矽，形成倒金字塔陣列的抗反射結構，再使用SIGA製程(Silizium-Mikrostruktur, Galvanoformun, Abformung, SIGA)，電鑄鎳鈷合金膜仁，成功製作出底部大小為45×45 m2，深度約30m之倒金字塔結構陣列，可用來熱壓低轉化溫度(glass transition temperature, Tg)玻璃基板，形成抗反射結構。本研究成功由脈衝式電壓電鍍參數、鹽酸濃度與三乙醇胺(Triethanolamine, TEA)螯合劑濃度中，找出適合本研究非硒化熱處理製程之CIS薄膜，在ITO接觸電極基板上，其最佳化參數：三乙醇胺濃度1.0 M，鹽酸濃度0.845 M，Voff與Von分別為-0.4 V與-0.8 V，工作週期(duty cycle)選用50 %，電鍍時間320秒；在鉬背電極基板上之最佳參數：三乙醇胺濃度0.7 M，鹽酸濃度0.56 M，Voff與Von分別為0 V與-0.8 V，工作週期同樣選用50 %，電鍍時間600秒。本研究為了使用非硒化爐熱處理製程，故將熱處理前之CIS吸收層成分比例，Cu：In：Se調整為1：1：5，並利用鹽酸濃度的調配與熱處理氣體選擇，將鍍層含氧量降至5 %以下，成功克服了一般電鍍製程中，鍍層含氧量偏高之現象。其最佳熱處理參數為使用7 %氫與93 %氬混和氣體，在200 °C 溫度下進行1.5小時之再結晶製程。最後得到薄膜成分Cu：In：Se比例約為1：1：2，此時CIS薄膜呈現類花椰菜之黃銅礦(Chalcopyrite)結構，其結晶顆粒大小約為1.5 m至2 m。

關鍵字

銅銦化二硒；脈衝式電鍍；非硒化；薄膜型太陽能電池

並列摘要

This study fabricated CuInSe2 layer by electrodeposition and non-selenization for CuInSe2, also called CIS, thin film solar cells, and compared the substrate and superstrate whose structure are Glass/Mo/CIS/ZnO/ITO and Glass/ITO/ZnO/CIS/Mo. Exception for CIS layers were produced by pulse voltage electrodeposition, other layers of solar cells, such as 700 nm ITO for contact electrodes, 50 nm ZnO for buffer layers, and 1 m Mo for back electrodes, were fabricated by RF sputtering. We used KOH to etch <100> silicon wafers for arrayed inversed pyramids structure which can be an anti-reflection structure for monocrystalline silicon solar cells. We used this etched wafer whose bottom area of pyramids are 45×45 m2，30m in depth, to fabricate a Ni-Co mold by SIGA process( Silizium-Mikrostruktur, Galvanoformun, Abformung, also called SIGA) for hot embossing the low transition temperature, Tg, glasses of CIS solar cells as anti-reflection substrates. For CIS layer, we successfully tuned the parameters of TEA, HCl, and other settings in pulse voltage electrodeposition. For ITO contact electrodes, the best parameters are 1.0 M TEA, 0.845 M HCl, -0.4 V for Voff, -0.8 V for Voff, 50% for duty cycle, and electrodeposited for 320 seconds. For Mo back electrodes, 0.7 M TEA, 0.56 M HCl, 0 V for Voff, -0.8 V for Voff, 50% for duty cycle, electrodeposited for 600 seconds. To avoid selenization process, we adjusted the composition ratios of Cu:In:Se in CIS layer as 1:1:5, and used concentration of HCl and ambient gas of heat treatment to reduce the oxygen content of CIS layers to 5 %. The best heat treatment was 200 °C for 1.5 hours in 7% H2 and 93% Ar mixed gas. As the result, we could get the composition ratio of Cu:In:Se are 1:1:2, the crystalline are about 1 to 1.5 m.

並列關鍵字

CuInSe2 ； CIS ； pulse voltage electrodeposition ； non-selenization ； thin film solar cell

參考文獻

19. U.P. Singh and S.P. Patra, Progress in polycrystalline thin-film Cu(In,Ga)Se2 solar cells, International Journal of Photoenergy, 2010 (2010)

38. 王湘儀, 高穿透氯及滴接觸阻抗的氧化銦鉬在P型氮化鎵之歐姆接觸研究, 國立台灣大學, 碩士論文, 2006

46. 許能傑, 黃泰錦, 濺鍍Mo薄膜在不同基板上之表面特性分析, Journal of China Institute of Technology, 40 (2009)

1. 古鎮南, 微/奈米抗反射結構應用於矽晶太陽能電池之研製, 國立臺灣師範大學, 碩士論文, 2010

2. R. Bhattacharya, Electrodeposition of CuIn1-xGaxSe2 materials for solar cells, NREL, 2011

國際替代計量

脈衝式電鍍CuInSe2在抗反射結構基板之薄膜型太陽能電池研製

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