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

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)

49. 高雅君, 錯合劑對電沉積二硒化銅銦薄膜的影響研究, 國立成功大學, 碩士論文, 2008

12. 張智閔, 利用電沉積方法製備CIS太陽能電池結構, 國立成功大學, 碩士論文, 2007

32. 邱立仁, 電沉積二硒化銅銦太陽能電池之研究, 國立成功大學, 碩士論文, 2007

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

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

主題瀏覽