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Issue 3, 2018
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How small amounts of Ge modify the formation pathways and crystallization of kesterites

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Abstract

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.

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

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Article information


Submitted
14 Aug 2017
Accepted
25 Oct 2017
First published
27 Oct 2017

This article is Open Access

Energy Environ. Sci., 2018,11, 582-593
Article type
Paper

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

S. Giraldo, E. Saucedo, M. Neuschitzer, F. Oliva, M. Placidi, X. Alcobé, V. Izquierdo-Roca, S. Kim, H. Tampo, H. Shibata, A. Pérez-Rodríguez and P. Pistor, Energy Environ. Sci., 2018, 11, 582
DOI: 10.1039/C7EE02318A

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