Silicon solar cells containing boron and oxygen are one of the most rapidly growing forms of electricity generation. However, they suffer from significant degradation during the initial stages of use. This problem has been studied for 40 years resulting in over 250 research publications. Despite this, there is no consensus regarding the microscopic nature of the defect reactions responsible. In this paper, we present compelling evidence of the mechanism of degradation. We observe, using deep level transient spectroscopy and photoluminescence, under the action of light or injected carriers, the conversion of a deep boron-di-oxygen-related donor state into a shallow acceptor which correlates with the change in the lifetime of minority carriers in the silicon. Using ab initio modeling, we propose structures of the BsO2 defect which match the experimental findings. We put forward the hypothesis that the dominant recombination process associated with the degradation is trap-assisted Auger recombination. This assignment is supported by the observation of above bandgap luminescence due to hot carriers resulting from the Auger process.
Results available in the literature on minority carrier trapping and light‐induced degradation (LID) effects in silicon materials containing boron and oxygen atoms are briefly reviewed. Special attention is paid to the phenomena associated with “deep” electron traps (J. A. Hornbeck and J. R. Haynes, Phys. Rev. 1955, 97, 311) and the recently reported results that have linked LID with the transformation of a defect consisting of a substitutional boron atom and an oxygen dimer (BsO2) from a configuration with a deep donor state into a recombination active configuration associated with a shallow acceptor state (M. Vaqueiro‐Contreras et al., J. Appl. Phys. 2019, 125, 185704). It is shown that the BsO2 complex is a defect with negative‐U properties, and it is responsible for minority carrier trapping and persistent photoconductivity in nondegraded Si:B+O samples and solar cells. It is argued that the “deep” electron traps observed by Hornbeck and Haynes are the precursors of the “slow” forming shallow acceptor defects, which are responsible for the dominant LID in boron‐doped Czochralski silicon (Cz‐Si) crystals. Both the deep and shallow defects are BsO2 complexes, transformations between charge states and atomic configurations of which account for the observed electron trapping and LID phenomena.
Float zone silicon (FZ-Si) is typically assumed to be an extremely high quality material, with high minority carrier lifetimes and low concentrations of recombination active defects. However, minority carrier lifetime in FZ-Si has previously been shown to be unstable following thermal treatments between 450 and 700 °C, with a range of unidentified deep level states being linked to reduced carrier lifetime. There are suspicions that nitrogen doping, which occurs from the growth atmosphere, and intrinsic point defects play a role in the degradation. This study aims to address this by using deep level transient spectroscopy (DLTS), minority carrier transient spectroscopy, Laplace DLTS, and photoluminescence lifetime measurements to study recombination active defects in nitrogen-doped and nitrogen-lean n-type FZ-Si samples. We find that nitrogen-doped samples experience increased degradation due to higher concentrations of deep level defects during thermal treatments compared to nitrogen-lean samples. In an attempt to explain this difference, in-diffusion of nickel has been used as a marker to demonstrate the existence of higher vacancy concentrations in the nitrogen-doped samples. The origin of the recombination active defects responsible for the thermally induced lifetime degradation in FZ-Si crystals is discussed.
It has been acknowledged for over 50 years that treatments with hydrogen can improve silicon semiconductor devices. In recent years, these have been used to an advantage in silicon solar cells reducing the loss of photo‐generated carriers at the silicon surface or at the silicon interface with dielectrics. However, we have found that in some types of silicon the in‐diffusion of hydrogen can result in the formation of powerful recombination centers composed of carbon, oxygen, and hydrogen which reduce the carrier lifetime and ultimately the efficiency of solar cells made from such material.
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