Marina Mousel

Atom probe study of Cu2ZnSnSe4 thin-films prepared by co-evaporation and post-deposition annealing

We use atom probe tomography (APT) for resolving nanometer scale compositional fluctuations in Cu2ZnSnSe4 (CZTSe) thin-films prepared by co-evaporation and post-deposition annealing. We detect a complex, nanometer–sized network of CZTSe and ZnSe domains in these films. Some of the ZnSe domains contain precipitates having a Cu- and Sn-rich composition, where the composition cannot be assigned to any of the known equilibrium phases. Furthermore, Na impurities are found to be segregated at the CZTSe/ZnSe interface. The insights given by APT are essential for understanding the growth of CZTSe absorber layers for thin-film solar cells and for optimizing their optoelectronic properties.

Detecting ZnSe secondary phase in Cu2ZnSnSe4 by room temperature photoluminescence

Secondary phases, such as ZnSe, occur in Cu2ZnSnSe4 and can be detrimental to the resulting solar cell performance. Therefore, it is important to have simple tools to detect them. We introduce subband gap defect excitation room temperature photoluminescence of ZnSe as a practical and non-destructive method to discern the ZnSe secondary phase in the solar cell absorber. The PL is excited by the green emission of an Ar ion laser and is detected in the energy range of 1.2–1.3 eV. A clear spatial correlation with the ZnSe Raman signal confirms this attribution.

Admittance spectroscopy in kesterite solar cells: Defect signal or circuit response

Unlike Cu(In,Ga)Se2 based solar cells, Cu2ZnSn(S,Se)4 solar cells show a strong increase in series resistance with decreasing temperature. In this study we deduce the series resistance from temperature dependent current-voltage measurements on a 5.5% efficient Cu2ZnSnSe4 solar cell. By applying a simple circuit model an increasing series resistance with decreasing temperature alone results in a capacitance step within the C-f profile. We show that this step needs to be distinguished from a step caused by a defect state or a carrier freeze-out. Consequently, the deduced activation energy is strongly distorted by the circuit response.

The three A symmetry Raman modes of kesterite in Cu 2 ZnSnSe 4

We investigate CZTSe films by polarization dependent Raman spectroscopy. The main peaks at 170 cm(-1), and 195 cm(-1) are found to have A symmetry. The Raman signal at 170 cm(-1) is found to be composed of two modes at 168 cm(-1) and 172 cm(-1). We attribute these three Raman peaks to the three A symmetry modes predicted for kesterite ordered Cu(2)ZnSnSe(4). The main Raman peak is asymmetrically broadened towards lower energies. Possible sources of the broadening are tested through temperature and depth dependent measurements. The broadening is attributed to phonon confinement effects related to the presence of lattice defects.

Direct Evaluation of Defect Distributions From Admittance Spectroscopy

Evaluating interfering capacitance steps in admittance spectroscopy for solar cell defect analysis is still a problem which needs to be solved. While the common analysis developed by Walter et al.[1] is capable of extracting defect distributions from the capacitance data, it results in erroneous defect densities in the presence of overlapping capacitance steps. We derive an expression for the capacitance step caused by defects with a density of states distributed in energy. By adding several of these defect distributions, interfering capacitance steps can be described. Thus, it is possible to fit the entire capacitance spectrum simultaneously for all temperatures. We apply the presented method to Cu2ZnSnSe4 -based solar cells with power conversion efficiencies between 5% and 7%. Comparing the obtained defect parameters with the ones obtained by the method from Walter et al. reveals that the Walter method overestimates the defect densities in the case of overlapping capacitance steps.

Multiple phases of Cu2ZnSnSe4 detected by room temperature photoluminescence

Cu2ZnSnSe4 based solar cells are promising but suffer from low open circuit voltage relative to their band gap. Additionally, the bandgap as extrapolated from quantum efficiency (QE) measurements varies without clear correlation to the growth conditions. Using room temperature photoluminescence, we show that different materials with different bandgaps coexist within micrometer sized areas of the absorbers. Simulations of the effect of multiple bandgaps on both the absorption and the Shockley-Queisser radiative recombination limit, explain the variations of the bandgap extrapolated from QE and the deficiencies of the solar cell parameters.

Detection of a MoSe2 secondary phase layer in CZTSe by spectroscopic ellipsometry

We demonstrate the application of Spectroscopic Ellipsometry (SE) for identification of secondary phase MoSe2 in polycrystalline Cu2ZnSnSe4 (CZTSe) samples. A MoSe2 reference sample was analyzed, and its optical constants (e1 and e2) were extracted by SE analysis. This dataset was implemented into an optical model for analyzing SE data from a glass/Mo/CZTSe sample containing MoSe2 at the back side of the absorber. We present results on the n and k values of CZTSe and show the extraction of the thickness of the secondary phase MoSe2 layer. Raman spectroscopy and scanning electron microscopy were applied to confirm the SE results.

Detection of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases in co-evaporated Cu2ZnSnSe4 thin-films

Cu{sub 2}ZnSnSe{sub 4} thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu{sub 2}Zn{sub 5}SnSe{sub 8} and Cu{sub 2}Zn{sub 6}SnSe{sub 9} composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu{sub 2}ZnSnSe{sub 4} and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu{sub 2}Zn{sub 5}SnSe{sub 8} and Cu{sub 2}Zn{sub 6}SnSe{sub 9} phases. Possible effects of these phases on solar cell performance are discussed.Cu2ZnSnSe4 thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu2ZnSnSe4 and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases. Possible effects of these phases on solar cell performance are discussed.

Role of high series resistance in admittance spectroscopy of kesterite solar cells

Cu2ZnSn(S, Se)4 (CZTSSe) solar cells suffer from parasitic resistance effects when decreasing the temperature. This effect can cause distortions in the admittance spectrum. We perform temperature dependent current-voltage (IVT) and admittance measurements on six different CZTSe devices with efficiencies between 4 % and 6 %. From IVT measurements we deduce a thermally activated series resistance. This activation energy agrees with an activation energy obtained from admittance measurements. The activation energy of the series resistance is identified with one of the capacitance steps in the C-f profile. The origin of the series resistance remains unclear, even though hints for a barrier are present.

Detection of Cu{sub 2}Zn{sub 5}SnSe{sub 8} and Cu{sub 2}Zn{sub 6}SnSe{sub 9} phases in co-evaporated Cu{sub 2}ZnSnSe{sub 4} thin-films

Cu{sub 2}ZnSnSe{sub 4} thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu{sub 2}Zn{sub 5}SnSe{sub 8} and Cu{sub 2}Zn{sub 6}SnSe{sub 9} composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu{sub 2}ZnSnSe{sub 4} and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu{sub 2}Zn{sub 5}SnSe{sub 8} and Cu{sub 2}Zn{sub 6}SnSe{sub 9} phases. Possible effects of these phases on solar cell performance are discussed.Cu2ZnSnSe4 thin-films for photovoltaic applications are investigated using combined atom probe tomography and ab initio density functional theory. The atom probe studies reveal nano-sized grains of Cu2Zn5SnSe8 and Cu2Zn6SnSe9 composition, which cannot be assigned to any known phase reported in the literature. Both phases are considered to be metastable, as density functional theory calculations yield positive energy differences with respect to the decomposition into Cu2ZnSnSe4 and ZnSe. Among the conceivable crystal structures for both phases, a distorted zinc-blende structure shows the lowest energy, which is a few tens of meV below the energy of a wurtzite structure. A band gap of 1.1 eV is calculated for both the Cu2Zn5SnSe8 and Cu2Zn6SnSe9 phases. Possible effects of these phases on solar cell performance are discussed.