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標題: 鋁與四氟化碳共摻雜氧化鋅薄膜之特性研究
Study on characteristics of Al and CF4 co-doped zinc oxide thin films
作者: 石妙琪
Shih, Miao-Chi
Contributors: 汪芳興
光電工程研究所
關鍵字: 氧化鋅;四氟化碳;透明導電薄膜;濺鍍
ZnO;CF4;TCO;sputtering
日期: 2013
Issue Date: 2013-11-18 11:22:27 (UTC+8)
Publisher: 光電工程研究所
摘要: 本研究使用射頻磁控濺鍍法在氬氣與四氟化碳(CF4)氣氛下沉積氧化鋅共摻雜鋁與氟(AFZO)薄膜於康寧Eagle XG玻璃。以改變鋁含量與四氟化碳流量的方式來探討濺鍍參數對AFZO薄膜結構、表面形貌、組成成分與光電特性的影響,並且討論AFZO薄膜經氫氬電漿後處理所造成的特性改善。最後再以稀鹽酸(HCl)蝕刻薄膜表面,觀察其對表面形貌與光電特性之影響。
分別使用四種含不同Al2O3比例(0 wt%、1 wt%、2 wt%與4 wt%)的氧化鋅靶材,四個靶材簡稱為A0ZO、A1ZO、A2ZO與A4ZO,各靶材所沉積之AFZO薄膜分別簡述為A0FZO、A1FZO、A2FZO與A4FZO,CF4流量變化為0% – 0.5%。以射頻功率100 W、基板不加熱、背景壓力5 × 10-6 Torr、工作壓力5 mTorr與薄膜厚度330 ± 30 nm的條件下沉積AFZO薄膜,A0FZO薄膜隨著CF4流量的增加,電阻率也會隨之下降,在CF4摻雜0.1%時,有最佳值2.24 × 10-3 Ω-cm,而A1FZO、A2FZO與A4FZO三系列薄膜在摻雜了CF4之後,電性都會隨著CF4摻雜比例的增加而下降,最佳光電特性表現為未摻雜CF4之A1FZO薄膜,其電阻率為8.74 × 10-4 Ω-cm,可見光平均穿透率約為93%。再以氫氬電漿(H2:Ar = 1:1)後處理改善薄膜光電特性,條件為電漿功率50 W、基板溫度200˚ C、工作壓力1 Torr,AFZO薄膜經氫氬電漿處理電性均獲得改善,電性愈差的改善程度愈大,最佳光電特性表現的薄膜其電阻率由8.74 × 10-4 Ω-cm降至8.60 × 10-4 Ω-cm,可見光平均穿透率從93%提升至94%。
在稀鹽酸蝕刻部份,使用0.2%的稀鹽酸對AFZO薄膜表面進行蝕刻,薄膜經蝕刻後電阻率有略微上升的趨勢,且薄膜表面變得較粗糙且有明顯的隕石坑形狀,A2FZO薄膜經稀鹽酸蝕刻後,其在可見光區的平均霧度(haze ratio)從1.51%增加至36.85%,未摻雜CF4之A1FZO薄膜應用於矽薄膜太陽能電池轉換效最佳。
Aluminum and fluorine co-doped ZnO (AFZO) films were prepared by ratio frequency (rf) magnetron sputtering with ZnO targets containing 0 wt.%, 1 wt.%, 2 wt.% and 4 wt.% Al2O3 on Corning EagleXG glass at room temperature in Ar/CF4 gas mixtures. The surface morphology, structure, compositional, electrical and optical properties of the as-deposited films as well as the hydrogen-argon plasma treatment ones were investigated.
The electrical and optical parameters (resistivity, carrier concentration, Hall mobility) were correlated with the chemical composition and the structural properties (phases, grain size). For A0FZO films, CF4 incorporation of 0.1%~0.5% concentrations increases the carrier concentration and the Hall mobility. Higher carbon and fluorine incorporation into the films do not improve the electrical properties, which is attributed to the formation of carbide and zinc fluorides. For A1FZO, A2FZO, and A4FZO films, the resistivity increase with increasing CF4 content. Among them, the as-deposited A1FZO films achieved the lowest resistivity of about 8.74 × 10-4 Ω•cm.
The effects of hydrogen plasma treatment on AFZO films were investiged. The lowest resistivity was achieved under the conditions of RF power of 50 W, substrate temperature of 200˚ C, and working pressure of 1 Torr. After plasma treatement, the film resistivity decrease from 8.74 × 10-4 Ω•cm to 8.6 × 10-4 Ω•cm and the average optical transmittance increase from 93% to 94%.
For diluted HCl etched films, the resistivity slightly increased and the surface morphology obviously became rougher. The average haze ratio (400-700 nm) of the etched AFZO films increased from 1.51% to 36.85% after 0.2% diluted HCl etching. The fabricated amorphous Si thin film solar cell with undoped A1FZO film as the front electrode has the best efficiency.
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