• Energy Research

In this article, the effect of the various processing steps during the fabrication of c-Si/SiOx/SiCx fired passivating contacts on the silicon bulk lifetime is studied, and the kinetics of defect deactivation by hydrogenation is investigated. It is found that the firing step at 800 degrees C induces shallow bulk defects in float-zone silicon wafers, which can subsequently be passivated with hydrogen provided by an a-SiNx:H/D reservoir layer upon annealing at 450 degrees C. Experimental results and numerical data treatment indicate a rapid passivation of the surface within less than 1 min, followed by a slower passivation of the shallow bulk defects. In situ lifetime measurements are consistent with a slow bulk lifetime improvement by showing similar lifetime evolutions for both p-type and n-type SiCx layers. The kinetics of the hydrogenation process seems to be limited by the available hydrogen supply at the c-Si/SiOx interface, rather than by its diffusion within the bulk of the wafer. Moreover, it is affected by the bulk doping as well as the SiCx layer thickness. Finally, it is shown that hydrogenation is also possible with an a-SiNx:H/D reservoir layer deposited on one side of the wafer only, although resulting in a lower passivation level (s similar to 700 mu s compared to similar to 1300 mu s for symmetrical samples), and slower kinetics (similar to 5 min compared to similar to 0.8 min).

In this work, the hydrogenation mechanism of fired passivating contacts (FPC) based on c-Si/SiO$_{x}$/nc-SiC$_{x}$(p) stacks was investigated, by correlating the passivation and local re-distribution of hydrogen. Secondary ion mass spectroscopy (SIMS) depth profiling was used to assess the hydrogen (/deuterium) content. The SIMS profiles show that hydrogen almost completely effuses out of the SiC$_{x}$(p) during firing, but can be re-introduced by hydrogenation via forming gas anneal (FGA) or by release from a hydrogen containing layer such as SiN$_{x}$:H. A pile-up of H at the c-Si/SiO$_{x}$ interface was observed and identified as a key element in the FPC's passivation mechanism. Moreover, the samples hydrogenated with SiN$_{x}$:H exhibited higher H content compared to those treated by FGA, resulting in higher iV$_{OC}$ values. Further investigations revealed that the doping of the SiC$_{x}$ layer does not affect the amount of interfacial defects passivated by the hydrogenation process presented in this work. Eventually, an effect of the oxide's nature on passivation quality is evidenced. iV$_{OC}$ values of up to 706 mV and 720 mV were reached with FPC test structures using chemical and UV-O$_{3}$ tunneling oxides, respectively, and up to 739 mV using a reference passivation sample featuring a ~25 nm thick thermal oxide. 13 pages, 5 figures

Thin-film chalcogenide kesterites Cu2ZnSnS4 and Cu2 ZnSnSe4 (CZTSSe) are promising candidates for the next-generation thin-film solar cells. They exhibit a high natural abundance of Cu, Zn, Sn and S2, a high absorption coefficient, and a tunable direct bandgap between 1.0 and 1.5 eV. A prerequisite for the use of CZTSSe as absorber layers in photovoltaic applications on large scales is a detailed knowledge of the formation reaction. Recently, we have shown that a decomposition/formation equilibrium governs the formation reaction. The presence of Sn(S,Se) during the high-temperature preparation steps is essential to prevent decomposition. This improves the solar cell efficiency from 0.02% to 6.1%. In this paper, we show that the decomposition is universal. Absorbers produced by high-temperature coevaporation and samples produced by low-temperature precursor fabrication followed by annealing in a tube furnace in S or Se atmosphere are compared in order to elucidate that in all cases, the loss of Sn(S,Se) forms a degraded surface region. We demonstrate that the degraded surface of CZTSe absorbers contains grains of ZnSe. These new insights can be used to explain why some of the synthesis routines described in the literature yield much better efficiencies than others.

AbstractAlkali metal doping and grain boundaries (GB) have been at the center of attention within the Cu(In,Ga)(S,Se)2 photovoltaics community for years. This study provides the first experimental evidence that the GB of sodium‐doped CuInSe2 thin films may undertake reversible oxidation even at room temperature, whereas undoped films may not. The findings are corroborated by cathodoluminescence imaging, secondary ion mass spectrometry, and Kelvin probe force microscopy on air‐exposed films subsequently subject to vacuum. A thermochemical assessment identifies the likely solid–gas equilibria involved. These reactions open new research questions with respect to the beneficial role played by alkali metal dopants in chalcopyrite solar cells and may steer the community toward new breakthroughs.

AbstractCurrently, Sb2Se3 thin films receive considerable research interest as a solar cell absorber material. When completed into a device stack, the major bottleneck for further device improvement is the open‐circuit voltage, which is the focus of the work presented here. Polycrystalline thin‐film Sb2Se3 absorbers and solar cells are prepared in substrate configuration and the dominant recombination path is studied using photoluminescence spectroscopy and temperature‐dependent current–voltage characteristics. It is found that a post‐deposition annealing after the CdS buffer layer deposition can effectively remove interface recombination since the activation energy of the dominant recombination path becomes equal to the bandgap of the Sb2Se3 absorber. The increased activation energy is accompanied by an increased photoluminescence yield, that is, reduced non‐radiative recombination. Finished Sb2Se3 solar cell devices reach open‐circuit voltages as high as 485 mV. Contrarily, the short‐circuit current density of these devices is limiting the efficiency after the post‐deposition annealing. It is shown that atomic layer‐deposited intermediate buffer layers such as TiO2 or Sb2S3 can pave the way for overcoming this limitation.

ABSTRACTCu2ZnSnSe4 (CZTSe) thin film solar cells have been produced via co‐evaporation followed by a high‐temperature annealing. In order to reduce the decomposition of the CZTSe, a SnSe2 capping layer has been evaporated onto the absorber prior to the high‐temperature treatment. This eliminates the Sn losses due to SnSe evaporation. A solar cell efficiency of 5.1% could be achieved with this method. Moreover, the device does not suffer from high series resistance, and the dominant recombination pathway is situated in the absorber bulk. Finally, different illumination conditions (white light, red light, and yellow light) reveal a strong loss in fill factor if no carriers are generated in the CdS buffer layer. This effect, known as red‐kink effect, has also been observed in the closely related Cu(In,Ga)Se2 thin film solar cells. Copyright © 2013 John Wiley & Sons, Ltd.

AbstractAlkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.