Abstract

Effective defect passivation of semiconductor surfaces and interfaces is indispensable for the development of high efficiency solar cells. In this study we systematically investigated the surface and grain boundary properties of ${\mathrm{CuInSe}}_{2}$ (CISe) with scanning tunneling microscopy (STM) and spectroscopy (STS) after different surface treatments such as potassium cyanide (KCN) etching, pre-electrolyte treatment with cadmium ions, and annealing in ultrahigh vacuum (UHV). We show that air exposed samples with a subsequent KCN etching step exhibits a highly defective surface. However, a Cd pre-electrolyte treatment passivates most of these defects, which manifests itself by a reduction of the high conductance in the STS measurements at positive sample biases. The origin of the improvement can be traced back to an increase in surface band bending, which leads to a type inversion, induced by a change in the concentration of Cu vacancies. We observe a defect passivation at the CISe surface and at the grain boundaries. Our results give a direct explanation of why the CdS buffer layer in CISe thin film solar cells is of utmost importance for high efficiency devices.

Highlights

  • Polycrystalline copper indium diselenide CuInSe2 (CISe) semiconductors exhibit ideal properties for high performance thin film solar cells [1]

  • In the present study we combined scanning tunneling microscopy and spectroscopy (STS) and x-ray and ultraviolet photoemission spectroscopy (XPS/UPS) in order to link the local density of states at the surface of Cu-rich CISe absorbers to compositional changes induced by various treatments such as KCN etching, cadmium pre-electrolyte treatment, and heat, and we compared our results to the already available data present in literature [24,25,26,35,36]

  • We did see that after ultrahigh vacuum (UHV) annealing a similar band bending effect occurred and the value of the valence band was very close to the one after the Cd pre-electrolyte treatment (CPE) treatment (1.08 eV compared to 1.05 eV)

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Summary

INTRODUCTION

Polycrystalline copper indium diselenide CuInSe2 (CISe) semiconductors exhibit ideal properties for high performance thin film solar cells [1]. Scanning tunneling microscopy of polycrystalline CISe gave important insights into the absorber properties prior to the buffer layer deposition [25,26,27], such as the existence of a reduced defect density at the grain boundaries and heat induced passivation surface passivation. In the present study we combined scanning tunneling microscopy and spectroscopy (STS) and x-ray and ultraviolet photoemission spectroscopy (XPS/UPS) in order to link the local density of states at the surface of Cu-rich CISe absorbers to compositional changes induced by various treatments such as KCN etching, cadmium pre-electrolyte treatment, and heat, and we compared our results to the already available data present in literature [24,25,26,35,36]

EXPERIMENT
Scanning tunneling microscopy and spectroscopy measurements
Valence band onset for KCN and CPE treated absorbers
Photoluminescence measurements
Findings
DISCUSSION
CONCLUSION
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