在本論文中，我們利用更低成本的電鍍技術來研究製備二硒化銅銦鋁薄膜太陽能電池。本論文研究內容主要可分成四大部分，首先利用循環伏安法來了解各元素與混合物的還原電位並定義出適當的共電鍍電壓，再搭配X光繞射分析推論出製備二硒化銅銦鋁薄膜可能的化學反應過程。研究中發現添加十二烷基硫酸鈉(Sodium dodecyl sulfate，SDS)可使各元素的還原電位更為接近以提供更好的共電鍍環境，同時改變薄膜的成核機制從原先的瞬間成核轉為步階成核，使得前驅薄膜的表面形貌變的平坦。另外經由調整電鍍電壓則可使得薄膜的化學劑量比從含銅量多變成含銅量少，而表面形貌從圓球狀結構變成花椰菜結構。其次則針對二硒化銅銦鋁薄膜的化學劑量以及能帶做調整，此研究中經由調整電鍍液中的鋁與銦濃度，我們已經能控制薄膜的鋁比鋁加銦含量從0.21到0.42，而相對應的能帶變化可從1.17eV到1.48eV，藉此可以使得二硒化銅銦鋁薄膜的能隙更符合理想太陽光譜理論能帶。此外X光繞射分析結果證明了所有二硒化銅銦鋁薄膜的主要成長方向乃是沿著(112)、 (204/220)以及(116/312)結晶面。其三則針對二硒化銅銦鋁薄膜的表面形貌以及薄膜回火前後關係做探討，研究發現經由提升鍍液中的銅濃度能夠改變薄膜的成核機制從瞬間成核轉為步階成核，而瞬間成核機制成長下的前驅薄膜則表現出銅量少、表面粗糙的花椰菜或是三角形形貌。而步階成核機制下成長出的前驅薄膜則表現出銅量多、表面平整的圓球狀形貌。銅量多的前驅薄膜在經由回火處理後能夠得到一個較佳品質、平整緊密且大結晶顆粒的二硒化銅銦鋁薄膜，能更有利於當作太陽能電池的吸收層薄膜。而我們更是首創發表有效率的電鍍二硒化銅銦鋁薄膜太陽能電池，目前效率為1.96% ，開路電壓為0.189mV、短路電流29.21mA/cm2、填充因子35.4%。其四則利用雙層前驅膜結構來改善二硒化銅銦鋁薄膜的表面形貌以及進行二硒化銅銦鋁薄膜與硫化鎘(CdS)界面之探討，研究發現在雙層結構中上層的銅硒化合物在回火過程中能夠形成融熔態，藉此提高元素的移動能力進而促使薄膜表面變平整、粗糙度降低到100nm以下並且形成大顆粒的結晶。後續的硫化鎘沉積也證明了在雙層結構上成長的硫化鎘薄膜有較好的表面覆蓋性與平整度能有效降低漏電流的分佈情況，從暗電流的量測結果可以明顯發現漏電流從原先的4.02 x 10-4 A/cm2 (單層結構)降到4.26 x 10-5 A/cm2 (雙層結構)，下降了一個級數。而太陽能電池效率方面則可藉由開路電壓與短路電流的改善從原先的0.52% (單層結構)提升到1.44% (雙層結構)。

In this dissertation, we exploit the low cost electrodepositon technique to investigate the fabrication of Cu(In,Al)Se2 thin film solar cell. The research content is divided into four segments. In the first segment, the cyclic voltammetric studies are used to realize the element’s and compounds reduction potentials and identify a suitable potential as co-electrodeposition. In combination with the XRD analysis, chemical reaction mechanism for presuming the formation routes of quaternary Cu(In,Al)Se2 films are defined. Furthermore, It is found that the SDS additive promotes the deposited potential of each element closing to each other for a better co-elecorodeposition environment, and simultaneously change the nucleation mechanism of Cu(In,Al)Se2 films from instantaneous nucleation to progressive nucleation. This feature is helpful to obtain a smooth precursor Cu(In,Al)Se2film and round-like structure. In addition, we find the stoichiometry of Cu(In,Al)Se2 film changes from Cu-rich to Cu-poor type and the morphology of Cu(In,Al)Se2 film transfers from round-like structure to cauliflower-like structure by increasing deposited potential.
In the second segment, we focus on the adjustment of stoichiometry and optical energy band gap of Cu(In,Al)Se2 films. By adjusting the Al and In concentration is solutions, the ratio of Al to (Al+In) in Cu(In,Al)Se2 films can be successfully controlled from 0.21 to 0.42, and the corresponding optical energy band gap of Cu(In,Al)Se2 films can be varied from1.17 eV to 1.48 eV to match with optimum band gap value for the solar spectrum. Furthermore, X-ray diffraction (XRD) patterns reveal three preferred growth orientations along the (112), (204/220), and (116/312) planes for all species.
In the third segment, we focus on the surface morphology of Cu(In,Al)Se2 films and the relationship between precursor Cu(In,Al)Se2 films and post-annealed Cu(In,Al)Se2 films. The nucleation mechanism of electrodeposited Cu(In,Al)Se2 films change from instantaneous nucleation to progressive nucleation is observed by increasing the copper concentration. The research results exhibit that precursor Cu(In,Al)Se2 films had roughly cauliflower-like and triangular structures with Cu-poor composition at instantaneous nucleation mechanism, whereas smooth and round structures with Cu-rich composition at progressive nucleation mechanism. After post-annealing treatment, the surface morphology of Cu-rich Cu(In,Al)Se2 films shows high quality with compact structures and large grains, that is more beneficial to be the absorber layer of solar cell. A 1.96% efficient Cu(In,Al)Se2 thin film solar cell fabricated by electrodeposition technique is first time achieved and publish in international journal. The corresponding values of open-circuit voltage (Voc), short-circuit current (Jsc), fill factor (FF), Rsh and Rs are 0.189 V, 29.21 mA/cm2, 35.4%, 125Ω and 2.82Ω, respectively.
In the fourth segment, the binary structure precursor Cu(In,Al)Se2 films are utilized to improve the surface morphology and of Cu(In,Al)Se2 films and investigate the characteristics of CdS and Cu(In,Al)Se2 interface. It is found that the upper Cu–Se compounds in binary structure can form a liquid phases during the post-annealing process, which enhances elemental migration and promotion of large grains and smooth surface formation and reduction of RMS roughness less than 100 nm. The subsequently deposition of CdS film on binary structure Cu(In,Al)Se2 films exhibit good spreadability and smoothness, leading to efficiently diminish the distribution of leakage current paths. The dark current–voltage characteristics of the CdS/CIAS heterojuncions shows that the reverse dark current density is decreased by approximately one order of magnitude from 4.02 x 10-4 A/cm2 (single structure) to 4.26 x 10-5 A/cm2 (binary structure). Furthermore, the conversion efficiency of CIAS solar cells is enhanced from 0.52 % (single structure) to 1.44 % (binary structure) with increase in Voc and Jsc.

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