本論文之研究目的為研製矽結晶類薄膜並應用於太陽能電池，依據矽結晶類薄膜包覆結晶的基材差異而將薄膜的研製分為矽量子點薄膜與微晶矽薄膜兩大方向探討研究，分別對於製作參數改變之薄膜特性做詳細的材料分析。以矽量子點薄膜而言，本文採用高溫回火富矽氮化矽層之方式，使富矽氮化層中過量之矽於氮化矽薄膜中析出形成矽量子點。經不同的回火溫度及回火時間測試可得到最佳化之回火條件。除此之外，亦藉由調整製作富矽氮化矽層時的沈積氣體比例可控制量子點薄膜析出的數量。實驗發現薄膜中包覆不同密度的矽量子點造成薄膜對於相同入射光源有不同的電流響應產生。應用此薄膜於單晶太陽能電池中作為抗反層，則可使電池轉換效率從原本沒使用抗反射膜的5.42%增加至6.72%。另一方面之研究則為微晶矽薄膜之研製，在研究中使用40.68MHz超高頻電漿增強化學氣相沈積系統製作薄膜，藉由變化不同製程條件，如不同的氫氣通量、矽甲烷通量、製程壓力及電漿功率等製程條件，製作不同性質之本質微晶矽薄膜。由薄膜性質量測與電池製作之結果顯示，增加氫氣通量或降低矽甲烷通量可是薄膜之結晶比例有效上升。結晶比例之提高可使電池轉換效率由4.54%提升至5.39%，但結晶比例之提升有其最佳值，當薄膜之結晶比過高時則反而使效率變差。壓力之提升對於電池轉換效率亦有顯著改善，固定沉積參數(SC=1.67)變化壓力由5Torr增加到7Torr時，電池轉換效率由5.39%增加至6.39%。另外，當微晶矽薄膜具一定結晶比時，則電漿功率之提升對於電池轉換效率則沒有顯著的作用。接著則針對微晶矽薄膜太陽能電池做進一步的改善，分別嘗試以電池結構變化及針對電池p-i接面採取硼氣源處理的方式改善電池轉換效率。結果顯示，以二硼烷氣體在p層表面做短時間的沖刷及抽空，可有效提升電池轉換效率。另外，變化微晶矽薄膜太陽能電池結構，使用p型非晶碳化矽薄膜取代原本的p型微晶矽薄膜雖然會使電池的短路電流微幅下降，但是由於其在開路電壓大幅增加的表現，則仍然使電池轉換效率獲得改善，電池轉換效率可由4.47%提升至5.59%。

The objective of the current study is to develop and fabricate silicon based crystalline materials in order to make into photovoltaic (PV) solar cells. The current study of silicon films for PV applications includes two different parts based on the individual matrix around the crystalline materials. One of the studies is the development and fabrication of applying silicon quantum dots thin films to crystalline silicon solar cells, the other is the study of hydrogenated microcrystalline silicon thin film solar cells. For characterization of silicon quantum dots films under different process conditions, after deposition of silicon rich nitride layer by the PECVD process a high temperature anneal is adopted so that excessive amount of silicon quantum dots can be precipitates in the silicon rich nitride layer. An optimum condition for the anneal to obtain silicon quantum dots film has been verified through series of tests. In addition, the number of silicon quantum dots within the film can be controlled by varying the mixing ratio of silane and ammonia gas. This variation of silicon quantum density within the film causes different photo response. The conversion efficiency of the solar cell with silicon film embedded with silicon quantum dots can be improved from 5.42% to 6.49%. The other part is development and fabrication of microcrystalline silicon thin film solar cells with intrinsic layer deposited at different hydrogen gas flow, silane flow rate, deposition working pressure and power density at 40.68 MHz with very-high-frequency plasma-enhanced chemical vapor deposition system. As the results of film properties, the increase of hydrogen gas flow or the decrease of silane gas flow can increase the crystalline volume ratio in the films. The efficiency of solar cell made by this thin film increases from 4.54% to5.39% as the crystalline volume ratio in the film increases. However, the efficiency of the solar cell decreases as the crystalline volume ratio becomes too high. The increase in fabrication pressure from 5Torr to 7Torr can lead to notable improvement in cell efficiency from 5.39% to6.39%, but the increase in power density does not have any improvement in cell efficiency. Further improvement of the cell efficiency can be achieved by changing the structure of solar cell, and surface treatment on the p-i surface of the solar cell. It is shown that the diborane gas flush treatment on the p layer can improve the cell efficiency. Besides, replacing microcrystalline p layer with the amorphous p type silicon carbide can substantially improve the solar cell efficiency due to the significant increase in Voc but slight decrease in currents density. The conversion efficiency increases from 6.39% to8.35%.

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