Deep defects in Cu2ZnSnS4 monograin solar cells

AbstractIn this report Cu2ZnSnS4 (CZTS) monograin layer (MGL) solar cells were studied using admittance spectroscopy (AS) (frequency range 20Hz-10MHz) and temperature dependence of quantum efficiency (QE) curves (T=10K-300K). These studies revealed two deep defect states at EA1= 120 meV and at EA2= 167 meV. The first state was present in different CZTS cells while the second state had somewhat different properties in different cells. The temperature dependence of QE curves showed a shift of the long wavelength edge with increasing temperature by about 110 meV towards higher energy. The possible origin of the observed deep defect states is discussed

A photoluminescence study of CuInSe2 single crystals ion implanted with 5 keV hydrogen

CuInSe2 single crystals ion implanted with 5 keV hydrogen at doses from 3 × 1014 to 1016 cm-2 are studied by photoluminescence (PL). The PL spectra before and after implantation reveal two bands, a main dominant band centred at 0.96 eV and a lower intensity band centred at 0.93 eV. Detailed analysis of the shape of these bands, their temperature and excitation intensity dependencies allow the recombination mechanisms to be identified as band-to-tail (BT) and band-to-impurity (BI), respectively. The implantation causes gradual red shifts of the bands increasing linearly with the dose. The average depth of potential fluctuations is also estimated to increase with the dose and saturates for doses above 1015 cm-2. A model is proposed which associates the potential fluctuations with the antisite defects copper on indium site and indium on copper site. The saturation is explained by full randomization of copper and indium atoms on the cation sub-lattice

Optical properties of high quality Cu2ZnSnSe4 thin films

Cu2ZnSnSe4 thin films, fabricated on bare or molybdenum coated glass substrates by magnetron sputtering and selenisation, were studied by a range of techniques. Photoluminescence spectra reveal an excitonic peak and two phonon replicas of a donor-acceptor pair (DAP) recombination. Its acceptor and donor ionisation energies are 27 and 7 meV, respectively. This demonstrates that high-quality Cu2ZnSnSe4 thin films can be fabricated. An experimental value for the longitudinal optical phonon energy of 28 meV was estimated. The band gap energy of 1.01 eV at room temperature was determined using optical absorption spectr

Development of Bi2S3 thin film solar cells by close-spaced sublimation and analysis of absorber bulk defects via in-depth photoluminescence analysis

This study was funded by the Estonian Research Council projects PSG689 “Bismuth Chalcogenide Thin-Film Disruptive Green Solar Technology for Next Generation Photovoltaics”, PRG627 “Antimony chalcogenide thin films for next-generation semi-transparent solar cells applicable in electricity producing windows”, and PRG1023; the Estonian Centre of Excellence project TK141 (TAR16016EK, TAR16016) “Advanced materials and high-technology devices for energy recuperation systems”, and the European Union's H2020 programme under the ERA Chair project 5GSOLAR grant agreement No 952509.The emergence of new PV applications in society requires the design of new materials and devices based on green and earth-abundant elements, with a different set of properties and wider applicability. In this perspective, Bi2S3 semiconductor material have gained attention as a defect-tolerant, non-toxic, and highly stable material for earth-abundant thin film PV technologies. Related to Bi2S3 non-toxic nature, so far it has been very popular to synthesize the material by chemical solution routes, while little research efforts have been dedicated to absorber deposition by physical deposition techniques. In particular, there are no studies on absorber development via rapid, high-volume, and in-line close-spaced sublimation technique. Moreover, in-depth analysis of material defects employing low temperature-dependent photoluminescence (PL) remains largely unexplored. In this work, we systematically study the impact of close-spaced sublimation (CSS) conditions on Bi2S3 absorber growth on various substrates, employing a wide range of source (400–600 °C) and substrate (200–400 °C) temperatures. CSS source temperature of 550 °C and substrate temperature of 400–450 °C were identified as optimal temperatures (grown either on glass, TiO2, or CdS substrates), allowing the fabrication of uniform and dense Bi2S3 films with enhanced [221]-oriented grains. For the first time, a proof of concept solar cell with CSS Bi2S3 is demonstrated and an in-depth analysis on the interrelation between grain structure, interface recombination, and device performance is provided. Employing low-temperature dependence PL, new and complementary insights on possible defects and recombination mechanisms are presented.--//-- M. Koltsov, S.V. Gopi, T. Raadik, J. Krustok, R. Josepson, R. Gržibovskis, A. Vembris, N. Spalatu, Development of Bi2S3 thin film solar cells by close-spaced sublimation and analysis of absorber bulk defects via in-depth photoluminescence analysis, Solar Energy Materials and Solar Cells, Volume 254, 2023, 112292, ISSN 0927-0248, https://doi.org/10.1016/j.solmat.2023.112292.(https://www.sciencedirect.com/science/article/pii/S0927024823001137) Published under the CC BY-NC-ND licence.Estonian Research Council projects PSG689, PRG627 and PRG1023; Estonian Centre of Excellence project TK141 (TAR16016EK, TAR16016); the European Union's H2020 programme under the ERA Chair project 5GSOLAR grant agreement No 952509; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2

Temperature dependent photoreflectance study of Cu2SnS3 thin films produced by pulsed laser deposition

The energy band structure of Cu2SnS3 (CTS) thin films fabricated by pulsed laser deposition was studied by photoreflectance spectroscopy (PR). The temperature-dependent PR spectra were measured in the range of T = 10–150 K. According to the Raman scattering analysis, the monoclinic crystal structure (C1c1) prevails in the studied CTS thin film; however, a weak contribution from cubic CTS (F-43m) was also detected. The PR spectra revealed the valence band splitting of CTS. Optical transitions at EA = 0.92 eV, EB = 1.04 eV, and EC = 1.08 eV were found for monoclinic CTS at low-temperature (T = 10 K). Additional optical transition was detected at EAC = 0.94 eV, and it was attributed to the low-temperature band gap of cubic CTS. All the identified optical transition energies showed a blueshift with increasing temperature, and the temperature coefficient dE/dT was about 0.1 meV/K

Optical spectroscopy studies of Cu2ZnSnSe4 thin films

Cu2ZnSnSe4 thin films were synthesised by selenisation of magnetron sputtered metal precursors. The band gap determined from the absorption spectra increases from 1.01 eV at 300 K to 1.05 eV at 4.2 K. In lower quality films photoluminescence spectra show a broad, low intensity asymmetric band associated with a recombination of free electrons and holes localised on acceptors in the presence of spatial potential fluctuations. In high quality material the luminescence band becomes intense and narrow resolving two phonon replicas. Its shifts at changing excitation power suggest donor–acceptor pair recombination mechanisms. The proposed model involving two pairs of donors and acceptors is supported by the evolution of the band intensity and spectral position with temperature. Energy levels of the donors and acceptors are estimated using Arrhenius quenching analysis

Radiative recombination in Cu2ZnSnSe4 thin films with Cu deficiency and Zn excess

Thin films of Cu2ZnSnSe4 (CZTSe) with copper de�ficiency and zinc excess were fabricated at Northumbria University by the selenisation of metallic precursors deposited on Mo/glass and bare glass substrates. Absorption and photoluminescence (PL) measurements were used to examine the �film on glass whereas fi�lms on Mo/glass were used to produce a solar cell with ef�ficiency of 8.1%. Detailed temperature and excitation intensity analysis of PL spectra allows identifi�cation of the main recombination mechanisms as band-to-tail and band-to-band transitions. The latter transition was observed in the spectra from 6 to 300 K

A luminescence study of Cu2ZnSnSe4/Mo/glass films and solar cells with near stoichiometric copper content

Cu2ZnSnSe4 (CZTSe) is one of the leading candidates for the absorber layer in sustainable solar cells. Thin films of CZTSe with a near stoichiometric [Cu]/[Zn  +  Sn] were used to produce solar cells with conversion efficiency η  =  6.4% by a standard solar cell processing including KCN etching and the deposition of CdS and ZnO. Both CZTSe films and solar cells were examined using photoluminescence (PL) to analyse the nature of radiative recombination and photoluminescence excitation (PLE) at 4.2 K to determine the bandgap (E g ). Low temperature PL spectra of the films reveal an intense band P1 at 0.81 eV and a low intensity band P2 at 0.93 eV. Their temperature and excitation intensity dependencies suggest that they both involve recombinations of free electrons with holes localised at acceptors with the energy level influenced by potential fluctuations in the valence band. We associate P1 and P2 with different fractions of CZTSe: with a lower and higher degree of order of Cu and Zn on the cation sub-lattice, respectively. Device processing reduced the intensity of P1 by 2.5 whereas the intensity of P2 increased by a 1.5. We assign this to a low temperature annealing due to CdS and ZnO deposition which increased the fraction of CZTSe with high degree of Cu/Zn order and decreased the fraction with low degree of Cu/Zn order. Device processing increased E g , blue shifted P1, decreased its width, j-shift and the mean depth of potential fluctuations. These can also be related to the annealing and/or KCN etching and the chemical effect of Cd, due to CdS replacing copper at the CdS-CZTSe interface layer. Processing induced a new broad band P3 at 1.3 eV (quenching with E a = 200 meV) which we attributed to defects in the CdS layer

Effects of selenisation temperature on photoluminescence and photoluminescence excitation spectra of ZnO/CdS/Cu2ZnSnSe4/Mo/glass

The effect of solar cell processing (including etching in KCN along with deposition of CdS and ZnO) on photoluminescence (PL) spectra and bandgap Eg (measured at 4.2 K by photoluminescence excitation) of Cu2ZnSnSe4 films, produced by selenising metallic precursors at 450 °C, 500 °C and 550 °C, was studied. Temperature and excitation intensity analysis of the P1 dominant band in the PL spectra of solar cells suggests that after processing this band still can be assigned to the free-to-bound recombination of free electrons with holes bound at deep acceptor levels influenced by valence band-tails. However processing increased the intensity of P1 and blue shifted it. The strongest effect was observed for the film selenised at 500 °C. For the film selenised at 450 °C the blue shift and increase in the intensity were smaller and only a slight intensity rise was found for the film selenised at 550 °C. The intensity increase we assign to a reduction in the concentration of non-radiative recombination centers on the surface because of the etching and changes in doping due to inter-diffusion of Cd, S, Se and Zn after the deposition of CdS. Such an inter-diffusion depends on the elemental composition of the films defining the chemistry of defects and influencing Eg which increased in the film selenised at 500 °C but decreased in the other films. Processing increased the P1 shift rate (j-shift) with excitation power change in all the films demonstrating a higher compensation degree in the solar cells which is consistent with the formation of an interface layer containing new donors CdCu

Impact of the selenisation temperature on the structural and optical properties of CZTSe absorbers

We present structural and optical spectroscopy studies of thin films of Cu2ZnSnSe4 (CZTSe) with strong copper deficiency deposited on Mo/Glass substrates and selenised at 450, 500 or 550 °C. Solar cells fabricated from these films demonstrated efficiencies up to 7.4% for selenisation at 500 °C. Structural analysis based on X-ray diffraction and Raman spectroscopy revealed the presence of SnSe2 in the film selenised at 450 °C but not detected in the films selenised at higher temperatures. A progressive decrease of the Sn and Se content was observed as the selenisation temperature increased. Photoluminescence excitation was used to determine the bandgaps at 4.2 K. Detailed measurements of the temperature and excitation intensity dependencies of the photoluminescence spectra allow the recombination mechanisms of the observed emission bands to be identified as band-to-impurity and band-to-band transitions, and their evolution with selenisation temperature changes to be analysed. The strongest band-to-band transition is recorded in the PL spectra of the film selenised at 500 °C and can be observed from 6 K to room temperature. The compositional and structural changes in the films and their influence on the optoelectronic properties of CZTSe and solar cells are discussed