How small amounts of Ge modify the formation pathways and crystallization of kesterites

被引:138
作者
Giraldo, S. [1 ]
Saucedo, E. [1 ]
Neuschitzer, M. [1 ]
Oliva, F. [1 ]
Placidi, M. [1 ]
Alcobe, X. [2 ]
Izquierdo-Roca, V. [1 ]
Kim, S. [3 ]
Tampo, H. [3 ]
Shibata, H. [3 ]
Perez-Rodriguez, A. [1 ,4 ]
Pistor, P. [1 ,5 ]
机构
[1] Catalonia Inst Energy Res IREC, Jardins Dones Negre 1, Barcelona 08930, Spain
[2] CCiTUB, Lluis Sole & Sabaris 1-3, Barcelona 08028, Spain
[3] Natl Inst Adv Ind Sci & Technol, Res Ctr Photovolta, 1-1-1 Umezono, Tsukuba, Ibaraki 3058568, Japan
[4] Univ Barcelona, Dept Elect, IN2UB, Marti i Franques 111, E-08028 Barcelona, Spain
[5] Martin Luther Univ Halle Wittenberg, Inst Phys, Halle, Germany
基金
欧盟地平线“2020”;
关键词
CU2ZNSNSE4; SOLAR-CELLS; RAMAN-SCATTERING; IMPACT; EFFICIENCY; FILM;
D O I
10.1039/c7ee02318a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The inclusion of Ge into the synthesis of Cu2ZnSn(S,Se)(4) absorbers for kesterite solar cells has been proven to be a very efficient way to boost the device efficiency in a couple of recent publications. This highlights the importance to elucidate the mechanisms by which Ge improves the kesterite solar cells properties to such a large extent. In this contribution, we first show how controlling the position and thickness of a very thin (10-15 nm) layer of Ge greatly influences the crystallization of kesterite thin films prepared in a sequential process. Typically, Cu2ZnSnSe4 (CZTSe) films form in a bi-layer structure with large grains in the upper region and small grains at the back. By introducing Ge nanolayers below our precursors, we observe that large CZTSe grains extending over the whole absorber thickness are formed. Additionally, we observe that Ge induces fundamental changes in the formation mechanism of the kesterite absorber. In a detailed analysis of the phase evolution with and without Ge, we combine the results of X-ray fluorescence, X-ray diffraction and Raman spectroscopy to demonstrate how the Ge influences the preferred reaction scheme during the selenization. We reveal that the presence of Ge causes a large change in the in-depth elemental distribution, induces a stabilizing Cu-Sn intermixing, and thus prevents drastic compositional fluctuations during the annealing process. This finally leads to a change from a tri-molecular towards, mainly, a bi-molecular CZTSe formation mechanism. Kesterite thin films with surprisingly large crystals of several microns in diameter can be fabricated using this approach. The results are related to the increase in device performance, where power conversion efficiencies of up to 11.8% were obtained. Finally, the consequences of the disclosed crystallization pathways and the extension to other chalcogenide technologies are discussed.
引用
收藏
页码:582 / 593
页数:12
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