Influence of compositionally induced defects on the vibrational properties of device grade Cu2ZnSnSe4 absorbers for kesterite based solar cells

This work presents a detailed analysis of the impact of compositionally induced defects on the vibrational properties of Cu2ZnSnSe4 absorbers for kesterite based solar cells. Systematic changes in the intensity of the E and B modes located around the 170, 220, and 250 cm-1 frequency regions, which involve mostly cation vibrations, were observed and analyzed in relation to the occurrence of different kinds of defect clusters involving VCu, ZnCu, ZnSn, CuZn, and SnZn point defects. Additional changes are also interpreted in terms of the appearance of SnSe, ZnSe, and CuSe-like contributions at the 185 and 250 cm-1 spectral regions, respectively. The sensitivity of the Raman measurements to the presence of these kinds of defects corroborates the potential of Raman scattering for point defect assessment in these systems. © 2015 AIP Publishing LLCPeer ReviewedPostprint (published version

Influence of compositionally induced defects on the vibrational properties of device grade Cu2ZnSnSe4 absorbers for kesterite based solar cells

This work presents a detailed analysis of the impact of compositionally induced defects on the vibrational properties of Cu2ZnSnSe4 absorbers for kesterite based solar cells. Systematic changes in the intensity of the E and B modes located around the 170, 220, and 250 cm 1 frequency regions, which involve mostly cation vibrations, were observed and analyzed in relation to the occurrence of different kinds of defect clusters involving VCu, ZnCu, ZnSn, CuZn, and SnZn point defects. Additional changes are also interpreted in terms of the appearance of SnSe, ZnSe, and CuSe-like contributions at the 185 and 250 cm 1 spectral regions, respectively. The sensitivity of the Raman measurements to the presence of these kinds of defects corroborates the potential of Raman scattering for point defect assessment in these systems

Scalable heating-up synthesis of monodisperse Cu2ZnSnS4 nanocrystals

Monodisperse Cu2ZnSnS4 (CZTS) nanocrystals (NCs), with quasi spherical shape, were prepared by a facile, high-yield, scalable, and high-concentration heat-up procedure. The key parameters to minimize the NC size distribution were efficient mixing and heat transfer in the reaction mixture through intensive argon bubbling and improved control of the heating ramp stability. Optimized synthetic conditions allowed the production of several grams of highly monodisperse CZTS NCs per batch, with up to 5 wt % concentration in a crude solution and a yield above 90%

Vibrational properties of sulfoselenide solid solutions

In this work, Raman spectroscopy and X-ray diffraction were applied together to evaluate the crystal structure and the phonon modes of photovoltaic grade Cu 2ZnSn(SxSe1−x)4 thin films, leading to a complete characterization of their structural and vibrational properties. Vibrational characterization has been based on Raman scattering measurements performed with different excitation wavelengths and polarization configurations. Analysis of the experimental spectra has permitted identification of 19 peaks, which positions are in good accord with theoretical predictions. Besides, the observation of Cu 2ZnSnS4-like A symmetry peaks related to S vibrations and Cu 2ZnSnSe4-like A symmetry peaks related to Se vibrations, additional Raman peaks, characteristic of the solid solution and previously not reported, are observed, and are attributed to vibrations involving both S and Se anions

Raman tensor of zinc-phosphide (Zn3P2): from polarization measurements to simulation of Raman spectra

Zinc phosphide (Zn3P2) is a II–V compound semiconductor with promising photovoltaic and thermoelectric applications. Its complex structure is susceptible to facile defect formation, which plays a key role in further optimization of the material. Raman spectroscopy can be effectively used for defect characterization. However, the Raman tensor of Zn3P2, which determines the intensity of Raman peaks and anisotropy of inelastic light scattering, is still unknown. In this paper, we use angle-resolved polarization Raman measurements on stoichiometric monocrystalline Zn3P2 thin films to obtain the Raman tensor of Zn3P2. This has allowed determination of the Raman tensor elements characteristic for the A1g, B1g and B2g vibrational modes. These results have been compared with the theoretically obtained Raman tensor elements and simulated Raman spectra from the lattice-dynamics calculations using first-principles force constants. Excellent agreement is found between the experimental and simulated Raman spectra of Zn3P2 for various polarization configurations, providing a platform for future characterization of the defects in this material

Vibrational spectra and lattice thermal conductivity of kesterite-structured Cu2ZnSnS4 and Cu2ZnSnSe4

Cu2ZnSnS4 (CZTS) is a promising material for photovoltaic and thermoelectric applications. Issues with quaternary semiconductors include chemical disorder (e.g., Cu–Zn antisites) and disproportionation into secondary phases (e.g., ZnS and Cu2SnS3). To provide a reference for the pure kesterite structure, we report the vibrational spectra—including both infra-red and Raman intensities—from lattice-dynamics calculations using first-principles force constants. Three-phonon interactions are used to estimate phonon lifetimes (spectral linewidths) and thermal conductivity. CZTS exhibits a remarkably low lattice thermal conductivity, competitive with high-performance thermoelectric materials. Transition from the sulfide to selenide (Cu2ZnSnSe4) results in softening of the phonon modes and an increase in phonon lifetimes

Point defects, compositional fluctuations, and secondary phases in non-stoichiometric kesterites

The efficiency of kesterite-based solar cells is limited by various non-ideal recombination paths, amongst others by a high density of defect states and by the presence of binary or ternary secondary phases within the absorber layer. Pronounced compositional variations and secondary phase segregation are indeed typical features of non-stoichiometric kesterite materials. Certainly kesterite-based thin film solar cells with an off-stoichiometric absorber layer composition, especially Cu-poor/Zn-rich, achieved the highest efficiencies, but deviations from the stoichiometric composition lead to the formation of intrinsic point defects (vacancies, anti-sites, and interstitials) in the kesterite-type material. In addition, a non-stoichiometric composition is usually associated with the formation of an undesirable side phase (secondary phases). Thus the correlation between off-stoichiometry and intrinsic point defects as well as the identification and quantification of secondary phases and compositional fluctuations in non-stoichiometric kesterite materials is of great importance for the understanding and rational design of solar cell devices. This paper summarizes the latest achievements in the investigation of identification and quantification of intrinsic point defects, compositional fluctuations, and secondary phases in non-stoichiometric kesterite-type materials

Promoting Persistent Superionic Conductivity in Sodium Monocarba-closo-dodecaborate NaCB11H12 via Confinement within Nanoporous Silica

Superionic phases of bulk anhydrous salts based on large cluster-like polyhedral (carba)borate anions are generally stable only well above room temperature, rendering them unsuitable as solid-state electrolytes in energy-storage devices that typically operate at close to room temperature. To unlock their technological potential, strategies are needed to stabilize these superionic properties down to subambient temperatures. One such strategy involves altering the bulk properties by confinement within nanoporous insulators. In the current study, the unique structural and ion dynamical properties of an exemplary salt, NaCB11H12, nanodispersed within porous, high-surface-area silica via salt-solution infiltration were studied by differential scanning calorimetry, X-ray powder diffraction, neutron vibrational spectroscopy, nuclear magnetic resonance, quasielastic neutron scattering, and impedance spectroscopy. Combined results hint at the formation of a nanoconfined phase that is reminiscent of the high-temperature superionic phase of bulk NaCB11H12, with dynamically disordered CB11H12-anions exhibiting liquid-like reorientational mobilities. However, in contrast to this high-temperature bulk phase, the nanoconfined NaCB11H12 phase with rotationally fluid anions persists down to cryogenic temperatures. Moreover, the high anion mobilities promoted fast-cation diffusion, yielding Na+ superionic conductivities of similar to 0.3 mS/cm at room temperature, with higher values likely attainable via future optimization. It is expected that this successful strategy for conductivity enhancement could be applied as well to other related polyhedral (carba)borate-based salts. Thus, these results present a new route to effectively utilize these types of superionic salts as solid-state electrolytes in future battery applications

Understanding the growth mechanism of BaZrS3_3 chalcogenide perovskite thin films from sulfurized oxide precursors

Barium zirconium sulfide (BaZrS$_3$) is an earth-abundant and environmentally friendly chalcogenide perovskite with promising properties for various energy conversion applications. Recently, sulfurization of oxide precursors has been suggested as a viable solution for effective synthesis, especially from the perspective of circumventing the difficulty of handling alkali earth metals. In this work, we explore in detail the synthesis of BaZrS$_3$ from Ba-Zr-O oxide precursor films sulfurized at temperatures ranging from 700 $^\circ$C to 1000 $^\circ$C. We propose a formation mechanism of BaZrS$_3$ based on a two-step reaction involving an intermediate amorphization step of the BaZrO3 crystalline phase. We show how the diffusion of sulfur (S) species in the film is the rate-limiting step of this reaction. The processing temperature plays a key role in determining the total fraction of conversion from oxide to sulfide phase at a constant flow rate of the sulfur-containing H2S gas used as a reactant. Finally, we observe the formation of stoichiometric BaZrS$_3$ (1:1:3), even under Zr-rich precursor conditions, with the formation of ZrO$_2$ as a secondary phase. This marks BaZrS$_3$ quite unique among the other types of chalcogenides, such as chalcopyrites and kesterites, which can instead accommodate quite a large range of non-stoichiometric compositions. This work opens up a pathway for further optimization of the BaZrS$_3$ synthesis process, straightening the route towards future applications of this material.Comment: Equal contributio