- 學位論文
以化學浴沉積法成長氧化亞銅摻雜鎳之回火特性研究
Annealing study of Ni-doped Curprous Oxide(Cu2O:Ni) film by chemical bath deposition
摘要
氧化亞銅(Cu2O)為直接能隙半導體，能隙為 2.1 eV，其特性為在可見光範圍吸收係數大、穿透率低、且氧化亞銅來源取得容易，銅金屬在地殼中含量豐富，此材料具有低價位、簡單、無毒等優點，應用在太陽能電池研製上，可期望以低價位開發新型太陽能電池。 本研究利用化學浴沉積法(Chemical Bath Deposition, CBD)在銅基板上成長Cu2O薄膜，並藉由摻雜Ni元素來探討不同摻雜濃度以及回火處理對薄膜的影響。 化學浴沉積法分別於未摻雜與摻雜鎳的情況下製備Cu2O薄膜。未摻雜時使用硫酸銅（CuSO4）水溶液做為成長溶液；摻雜鎳時則使用硫酸鎳（NiSO4）與CuSO4的混和水溶液作為成長溶液，其中NiSO4為摻雜源。實驗中特別改變水溶液中NiSO4相對於CuSO4之莫爾濃度比(CuSO4/NiSO4)以其調變控制Cu2O 薄膜中不同程度的摻雜濃度。 本實驗透過觀察低溫PL量測，主要觀察兩峰值的消長，氧空缺720 nm(1.72 eV)以及銅空缺905 nm(1.37 eV)，分別為造成n型導電型態以及p型導電型態的發光，我們透過不同回火處理，使得銅空缺取得主導發光。 C-V量測部分發現，氧化亞銅摻鎳薄膜的載子濃度會隨著回火溫度提高而降低，顯示希望透過回火，將薄膜導電型態轉換的方法可行。 在Hot-probe system的量測結果中，發現在透過回火溫度500℃以及通入氮氣和氧氣的處理過後，導電型態已成功由n型轉換成p型。
並列摘要
Cuprous oxide is a direct band-gap semiconductor, energy gap size is 2.1eV with a high absorption coefficient in the visible region and the obtained cuprous oxide sources easily, copper abundant metal in the earth, this material with low-cost, simple, non-toxic, etc. In this study, we used chemical bath deposition (Chemical Bath Deposition, CBD) to grow Cu2O in copper substrate, and Ni elements by doping with different concentrations and annealing different temperature. The Cu2O:Ni films were prepared using copper sulfate (CuSO4) solution with the addition of Nickel Sulfate (NiSO4) as Ni2+ source. The molar ratio of NiSO4 to CuSO4 ([NiSO4]/[CuSO4]) was varied from 0 to 0.2. According to low temperature(15K) PL measurement showed that spectrum include two peaks at 720nm (1.72eV) and 647nm (1.91eV) respectively. The 1.72eV peak is bound exciton composed by oxygen vacancies (VO). The other peak 1.91eV is intrinsic property of the crystal perturbed by the presence of impurity centres or stoichiometry defects. Oxygen vacancies was the cause of n-type film.The PL spectrum results show a peak 906nm (1.37eV) when the annealing temperature is above 500˚C with N2 and O2, and the Cu2O:Ni film will change to p-type by Hot-probe measurement results. When annealing temperature reaches 550˚C ,the 1.91eV peak will vanished, intensity of 1.72eV peak will decreased also, the peak at 1.37eV will be the highest one. This phenomenon can be conjectured that Ni atoms in crystal were steamed and becoming copper vacancies (VCu). CV measurement results found that after annealing, so Cu2O: Ni carrier concentration decreases, this result can be judged with increasing temperature, film conductive patterns gradually move to P-type. In Hot-probe system, it found annealing temperature at 500 ℃ and treatment with nitrogen and oxygen, the conductive concentration have been successfully converted from n-type to p-type.
參考文獻
延伸閱讀
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