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

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

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 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

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

Micro Concentrator Concept for Cost Reduction and Efficiency Enhancement of Thin Film Chalcopyrite Photovoltaics Results from EU Joint Research Program CHEETAH

Results for research on chalcopyrite micro concentrator solar cells obtained within the framework of CHEETAH joint program are shown. A top down proof of concept study reveals close to 30 relative efficiency increase under light concentration using inkjet printed CIGSSe. A novel bottom up approach for local chalcopyrite absorbers grown from indium islands demonstrates working CISe micro cells. Millimeter sized lenses are fabricated from PMMA by a casting process to be applied as concentrator optics. For a combined exploitation of direct and diffuse light components an angular splitting concentrator based on chalcopyrite and kesterite absorber material is proposed. The scientific innovation brought will enrich further development of CIGSe solar cells and contribute to their relevance in photovoltaic energy productio

Cathodoluminescence characterization of Ge-doped CdTe crystals

Cathodoluminescence (CL) microscopic techniques have been used to study the spatial distribution of structural defects and the deep levels in CdTe:Ge bulk crystals. The effect of Ge doping with concentrations of 10(17) and 10(19) cm(-3) on the compensation of V-Cd in CdTe has been investigated. Dependence of the intensity distribution of CL emission bands on the dopant concentration has been studied. Ge doping causes a substantial reduction of the generally referred to 1.40 eV luminescence, which is often present in undoped CdTe crystals, and enhances the 0.91 and 0.81 eV emissions

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

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