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.
A center from the family of "fourfold coordinated ͑FFC͒ defects", previously predicted theoretically, has been experimentally identified in crystalline silicon. It is shown that the trivacancy ͑V 3 ͒ in Si is a bistable center in the neutral charge state, with a FFC configuration lower in energy than the ͑110͒ planar one. V 3 in the planar configuration gives rise to two acceptor levels at 0.36 and 0.46 eV below the conduction band edge ͑E c ͒ in the gap, while in the FFC configuration it has trigonal symmetry and an acceptor level at E c − 0.075 eV. From annealing experiments in oxygen-rich samples, we also conclude that O atoms are efficient traps for mobile V 3 centers. Their interaction results in the formation of V 3 O complexes with the first and second acceptor levels at E c − 0.46 eV and E c − 0.34 eV. The overall picture, including structural details, relative stability, and electrical levels, is accompanied and supported by ab initio modeling studies.
The trivacancy (V 3) in silicon has been recently shown to be a bistable center in the neutral charge state, with a fourfold-coordinated configuration, V 3[FFC], lower in energy than the (110) planar one. Transformations of the V 3 defect between different configurations, its diffusion, and disappearance upon isochronal and isothermal annealing of electron-irradiated Si:O crystals are reported from joint deep level transient spectroscopy measurements and first-principles density-functional calculations. Activation energies and respective mechanisms for V 3 transformation from the (110) planar configuration to the fourfold-coordinated structure have been determined. The annealing studies demonstrate that V 3 is mobile in Si at T>200C and in oxygen-rich material can be trapped by interstitial oxygen atoms so resulting in the appearance of V 3O complexes. The calculations suggest that V 3 motion takes place via consecutive FFC/planar transformation steps. The activation energy for the long-range diffusion of the V 3 center has been derived and agrees with atomic motion barrier from the calculations. © 2012 American Physical Society
We have recently found that the silicon trivacancy (V3) is a bistable defect that can occur in fourfold coordinated and (110) planar configurations for both the neutral and singly negative charge states [V. P. Markevich et al., Phys. Rev. B 80, 235207 (2009)]. Acceptor levels of V3 in both these configurations have been determined. It has also been shown that at T > 200 °C, the interaction of mobile trivacancies with interstitial oxygen atoms results in the formation of V3O complex with the first and second acceptor levels at Ec −0.46 and −0.34 eV. In the present work we identify donor levels arising from V3 and V3O complexes by means of deep level transient spectroscopy (DLTS) and high‐resolution Laplace DLTS on n+p silicon structures irradiated with 6 MeV electrons, combined with density functional modeling studies. It is found that both defects possess two donor levels in the (110) planar configurations. First donor levels at Ev +0.19 and +0.235 eV, and the second donor levels at Ev +0.105 and +0.12 eV are found for the V3 and V3O complexes, respectively.
Defect reactions associated with the elimination of divacancies (V 2 ) have been studied in n-type Czochralski (Cz) grown and float-zone (FZ) grown Si crystals by means of conventional deep-level transient spectroscopy and highresolution Laplace deep-level transient spectroscopy (LDLTS). Divacancies were introduced into the crystals by irradiation with 4 MeV electrons. Temperature ranges of the divacancy disappearance were found to be 225-275 • C in Cz Si crystals and 300-350 • C in FZ Si crystals upon 30 min isochronal annealing. Simultaneously with the V 2 disappearance in Cz Si crystals a correlated appearance of two electron traps with activation energies for electron emission 0.23 eV {E(0.23)} and 0.47 eV {E(0.47)} was observed.It is argued that the main mechanism of the V 2 disappearance in Cz Si crystals is related to the interaction of mobile divacancies with interstitial oxygen atoms. This interaction results in the formation of V 2 O centres, which are responsible for the E(0.23) and E(0.47) traps. Electronic properties of the V 2 O complex were found to be very similar to those of V 2 but energy levels of the two defects could easily be separated using LDLTS.In FZ Si crystals, a few electron traps appeared simultaneously with the V 2 annihilation. The small concentration of these traps compared with the V 2 concentration before annealing prevented their reliable identification.
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.
The elimination of divacancies (V 2 ) upon isochronal and isothermal annealing has been studied in oxygen-rich p-type silicon by means of deep level transient spectroscopy (DLTS) and high resolution Laplace DLTS. Divacancies were introduced into the crystals by irradiation with 4 or 6 MeV electrons. The temperature range of the divacancy disappearance was found to be 225-300 C upon 30 min isochronal annealing in the samples studied. A clear anti-correlation between the disappearance of V 2 and the appearance of two hole traps with activation energies for hole emission of 0.23 eV and 0.08 eV was observed. It is argued that these traps are related to the first and second donor levels of the divacancy-oxygen (V 2 O) complex, respectively. Significant electric field enhancement of the hole emission from the second donor level of the V 2 O center occurred in the diodes studied. It is shown that in the range of electric field from 4 Â 10 3 to 1.2 Â 10 4 V/cm the emission enhancement is associated with phonon-assisted tunnelling. V C 2014 AIP Publishing LLC. [http://dx.
Electrically active defects introduced into Ge crystals co-doped with tin and phosphorus atoms by irradiation with 6 MeV electrons have been studied by means of transient capacitance techniques and ab-initio density functional modeling. It is shown that Sn atoms are effective traps for vacancies (V) in the irradiated Ge:Sn+P crystals. The electronic structure of Sn-V is unraveled on the basis of hybrid states from a Sn atom and a divacancy. Unlike the case for Si, Sn-V in Ge is not a donor. A hole trap with 0.19 eV activation energy for hole emission to the valence band is assigned to an acceptor level of the Sn-V complex. The Sn-V complex anneals out upon heat-treatments in the temperature range 50-100 °C. Its disappearance is accompanied by the formation of phosphorus-vacancy centers. © 2011 American Institute of Physics
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