臺灣博碩士論文加值系統

以氧化鋅材料製備之透明導電薄膜已廣泛被研究於光電產業中的應用。本論文將選用四種不同Al2O3含量(0, 1, 2, 4 wt.%)之鋁氟共摻雜氧化鋅靶材，分別命名為FZO、A1FZO、A2FZO、A4FZO，及使用五種不同氫氣流量比 ( H2 / (Ar + H2) = 0 , 3 , 5 , 7 , 10 % )於濺鍍環境中，於室溫下以射頻磁控濺鍍(RF magnetron sputtering)在玻璃基板上製備氫化鋁氟共摻雜氧化鋅(HAFZO)薄膜，並針對其結構、電性、光學特性做量測分析。
各系列薄膜之載子濃度隨著氫氣流量比的提高而增加，這是由於氫氣在薄膜中扮演著淺層施體的角色提供自由載子，在相同氫氣流量比之下，靶材Al2O3含量由0 wt.%提高至2 wt.%時，將使得載子濃度上升，當Al2O3含量上升至4 wt.%時，將導致載子濃度大幅下降；霍爾遷移率隨著氫氣流量比的上升，呈現先上升後下降的趨勢，這是由於一直上升的氫氣流量比將會使離子化雜質散射的現象變的較為明顯，靶材Al2O3含量由0 wt.%提高至4 wt.%時，整體而言將使得霍爾遷移率下降。不論那種Al2O3含量靶材所製備之薄膜，隨著氫氣流量比超過5 %後，其晶粒尺寸開始逐漸變小。在可見光範圍(400-700 nm)下之薄膜穿透率皆超過91 %以上。在本論文中，使用A1FZO靶材在氫氣流量比為3 %下所製備的薄膜能獲得最低之電阻率為 4.405 × 10-4 Ω-cm，其載子濃度為6.794 × 1020 cm-3 ，霍爾遷移率為20.86 cm2/Vs。
接著，將氫氣流量比為0 %及5 %之各系列樣品薄膜在真空環境下進行200與500 °C之退火後處理，退火時間一小時。各系列非氫化薄膜在真空退火處理後，其結晶性獲得提升，晶粒尺寸隨著退火溫度的增加而逐漸變大；各系列氫化薄膜，當退火溫度到達200 °C時，晶粒尺寸會有下降趨勢，而退火溫度增加至500 °C時，晶粒尺寸會開始上升。各系列薄膜經過真空退火後在光學穿透率皆超過91 %以上。各系列氫化薄膜經過500 °C真空退火後，電阻率有大幅上升之現象。
最後，使用A1FZO靶材，氫氣流量比為0 %及3 %的條件下製成之薄膜，以0.2 %稀鹽酸進行蝕刻，使薄膜霧度上升並當成矽太陽電池之上電極，再以電漿輔助化學氣相沉積(PECVD)依序沉積氫化非晶矽p-i-n層於薄膜上，最後使用熱蒸鍍機(TE)鍍上背電極鋁點，製成矽薄膜太陽能電池，分析電池光電特性。結果顯示，以氫氣流量比3 %的薄膜所製備之矽薄膜太陽電池轉換效率較氫氣流量比0 %的薄膜為佳。

ZnO-based transparent conducting thin films have been widely studied in opto-electronic field. In this research, Al, F co-doped zinc oxide targets with four different Al2O3 contents (0, 1, 2, 4 wt.%), named FZO, A1FZO, A2FZO and A4FZO, and five different hydrogen flow ratios (H2 / Ar + H2 = 0, 3, 5, 7, 10% ) in the sputtering atmosphere were used to prepared hydrogenated Al, F co-doped zinc oxide thin films by RF magnetron sputtering on glass substrates at room temperature. The structural, electrical and optical properties of the prepared thin films were investigated.
The carrier concentrations of all thin films increased with the increasing hydrogen flow ratio because hydrogen might act as a shallow donor and provides free carrier in films. The Hall mobility presented an increase with increasing hydrogen flow ratio and then decreased due to ionized impurity scattering. The crystallite sizes of thin films began to decrease gradually as the hydrogen flow ratio was over 5% in spite of Al2O3 contents in targets. The average transmittances in the visible wavelength region (400-700 nm) of the all samples were more than 91%. The minimum resistivity of 6.0×10−4 Ω-cm, together with the carrier concentration of 6.794 × 1020 cm-3 and the Hall mobility of 20.86 cm2/Vs was obtained with the A1FZO target and the hydrogen flow ratio of 3%.
Secondly, the samples prepared with the hydrogen flow ratios of 0% and 5% were furnace annealed in vacuum at the temperatures of 200 °C and 500 °C for 1 h. After post-annealing treatment, the crystallinity of all serial non-hydrogenated thin films was improved and the crystallite size was gradually increased. However, the crystallite size of the hydrogenated thin films worsened at the annealing temperature of 200 °C and improved at 500 °C. The optical transmittance of all serial post-annealed thin films exceeded 91%. The resistivity of all serial hydrogenated thin films was increased dramatically after a 500 °C vacuum-annealing treatment.
Finally, 1000 nm-thick thin films prepared by the A1FZO target and hydrogen flow ratios of 0% and 3% were etched by a 0.2% HCl solution to increase their haze ratios as front electrodes of silicon thin film solar cells. Then, the amorphous silicon (p-i-n) thin films were deposited by PECVD, and aluminum electrodes were thermally evaporated with a patterned shadow mask as back electrodes. The result of I-V measurement shows that the solar cell with the hydrogenated AFZO thin film as the front electrode has better conversion efficiency than that with the non-hydrogenated film.

誌謝 i
摘要 ii
Abstract iv
目錄 vi
圖目錄 viii
表目錄 xii
第一章 緒論 1
1.1前言 1
1.2研究動機與目的 1
第二章 基礎理論與文獻回顧 3
2.1氧化鋅晶體結構及特性 3
2.2氫化共摻雜鋁與氟之氧化鋅(HAFZO)薄膜 4
2.2.1電學性質 4
2.2.2光學性質 6
2.3電漿基礎原理 7
2.4射頻磁控濺鍍 8
2.4.1濺鍍原理 8
2.4.2直流與射頻濺鍍 9
2.4.3磁控濺鍍 9
第三章 實驗步驟與方法 10
3.1實驗製程與分析流程 10
3.2靶材製作流程 11
3.2.1粉末配製 11
3.2.2靶材製程 12
3.3基板切割與清洗流程 13
3.4薄膜沉積 14
3.4.1薄膜沉積設備 14
3.4.2氫化共摻雜鋁氟氧化鋅(HxAyFZO)薄膜製程參數 14
3.4.3後退火處理 16
3.4.4稀鹽酸蝕刻流程與實驗參數 16
3.4.5矽薄膜太陽能電池製作與實驗參數 17
3.5薄膜量測分析 17
3.5.1薄膜結構分析 17
3.5.2薄膜電性量測 19
3.5.3薄膜光學測量 20
3.5.4元素成分分析 21
第四章 實驗結果與討論 22
4.1 氫氣流量比對於薄膜特性之影響 22
4.1.1薄膜沉積速率 22
4.1.2薄膜XRD分析 23
4.1.3薄膜SEM分析 27
4.1.4薄膜AFM分析 33
4.1.5薄膜電性分析 35
4.1.6薄膜光學分析 37
4.1.7薄膜可靠度分析 44
4.1.8薄膜XPS分析 46
4.2退火後處理對氫化薄膜特性之影響 51
4.2.1退火後處理之薄膜XRD分析 51
4.2.2退火後處理之薄膜SEM分析 56
4.2.3退火後處理之薄膜電性分析 61
4.2.4退火後處理之薄膜光學分析 65
4.3薄膜太陽電池應用 70
4.3.1蝕刻速率 71
4.3.2蝕刻前後薄膜表面型態 71
4.3.3蝕刻前後薄膜電性分析 72
4.3.4蝕刻前後薄膜光學分析 72
4.3.5薄膜太陽能電池量測特性 74
第五章 結論 77
參考文獻 79

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