In this work, the impact of cation disorder on the electrical properties of biaxially textured Co2ZnO4 and Co2NiO4 thin films grown by pulsed laser deposition are investigated using a combination of ...experiment and theory. Resonant elastic X‐ray diffraction along with conductivity measurements both before and after post‐deposition annealing show that Co2ZnO4 and Co2NiO4 exhibit opposite changes of the conductivity with cation disorder, which can be traced back to their different ground‐state atomic structures, being normal and inverse spinel, respectively. Electronic structure calculations identify a self‐doping mechanism as the origin of conductivity. A novel thermodynamic model describes the non‐equilibrium cation disorder in terms of an effective temperature. This work offers a way of controlling the conductivity in spinels in a quantitative manner by controlling the cation disorder and a new design principle whereby non‐equilibrium growth can be used to create beneficial disorder.
A combination of experiment and theory quantifies the dependence of the conductivity in Co2ZnO4 and Co2NiO4 on the cation disorder. A self‐doping mechanism is identified as the origin of conductivity and a thermodynamic model is used to describe the non‐equilibrium cation disorder in terms of an effective temperature. The conductivity in spinels can be controlled by manipulating the cation disorder.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Copper antimony chalcogenides CuSbCh2 (Ch=S, Se) are an emerging family of
absorbers studied for thin-film solar cells. These non-toxic and Earth-abundant materials
show a layered low-dimensional ...chalcostibite crystal structure, leading to interesting
optoelectronic properties for applications in photovoltaic (PV) devices. This research
update describes the CuSbCh2 crystallographic structures, synthesis methods,
competing phases, band structures, optoelectronic properties, point defects, carrier
dynamics, and interface band offsets, based on experimental and theoretical data.
Correlations between these absorber properties and PV device performance are discussed,
and opportunities for further increase in the efficiency of the chalcostibite PV devices
are highlighted.
High-throughput computational and experimental techniques have been used in the past to accelerate the discovery of new promising solar cell materials. An important part of the development of novel ...thin film solar cell technologies, that is still considered a bottleneck for both theory and experiment, is the search for alternative interfacial contact (buffer) layers. The research and development of contact materials is difficult due to the inherent complexity that arises from its interactions at the interface with the absorber. A promising alternative to the commonly used CdS buffer layer in thin film solar cells that contain absorbers with lower electron affinity can be found in β-In2S3. However, the synthesis conditions for the sputter deposition of this material are not well-established. Here, In2S3 is investigated as a solar cell contact material utilizing a high-throughput combinatorial screening of the temperature-flux parameter space, followed by a number of spatially resolved characterization techniques. It is demonstrated that, by tuning the sulfur partial pressure, phase pure β-In2S3 could be deposited using a broad range of substrate temperatures between 500 °C and ambient temperature. Combinatorial photovoltaic device libraries with Al/ZnO/In2S3/Cu2ZnSnS4/Mo/SiO2 structure were built at optimal processing conditions to investigate the feasibility of the sputtered In2S3 buffer layers and of an accelerated optimization of the device structure. The performance of the resulting In2S3/Cu2ZnSnS4 photovoltaic devices is on par with CdS/Cu2ZnSnS4 reference solar cells with similar values for short circuit currents and open circuit voltages, despite the overall quite low efficiency of the devices (∼2%). Overall, these results demonstrate how a high-throughput experimental approach can be used to accelerate the development of contact materials and facilitate the optimization of thin film solar cell devices.
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CuSbS2 is a promising nontoxic and earth-abundant photovoltaic absorber that is chemically simpler than the widely studied Cu2ZnSnS4. However, CuSbS2 photovoltaic (PV) devices currently have ...relatively low efficiency and poor reproducibility, often due to suboptimal material quality and insufficient optoelectronic properties. To address these issues, here we develop a thermochemical treatment (TT) for CuSbS2 thin films, which consists of annealing in Sb2S3 vapor followed by a selective KOH surface chemical etch. The annealed CuSbS2 films show improved structural quality and optoelectronic properties, such as stronger band-edge photoluminescence and longer photoexcited carrier lifetime. These improvements also lead to more reproducible CuSbS2 PV devices, with performance currently limited by a large cliff-type interface band offset with CdS contact. Overall, these results point to the potential avenues to further increase the performance of CuSbS2 thin film solar cell, and the findings can be transferred to other thin film photovoltaic technologies.
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The earth-abundant material CuSbS2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason ...for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuIn x Ga(1–x)Se2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.
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This paper presents the efficiency tables of materials considered as emerging inorganic absorbers for photovoltaic solar cell technologies. The materials collected in these tables are selected based ...on their progress in recent years, and their demonstrated potential as future photovoltaic absorbers. The first part of the paper consists of the criteria for the inclusion of the different technologies in this paper, the verification means used by the authors, and recommendation for measurement best practices. The second part details the highest world-class certified solar cell efficiencies, and the highest non-certified cases (some independently confirmed). The third part highlights the new entries including the record efficiencies, as well as new materials included in this version of the tables. The final part is dedicated to review a specific aspect of materials research that the authors consider of high relevance for the scientific community. In this version of the Efficiency tables, we are including an overview of the latest progress in theoretical methods for modeling of new photovoltaic absorber materials expected to be synthesized and confirmed in the near future. We hope that this emerging inorganic Solar Cell Efficiency Tables (Version 1) paper, as well as its future versions, will advance the field of emerging photovoltaic solar cells by summarizing the progress to date and outlining the future promising research directions.
Chemically and structurally complex solid compounds, including those with significant off-stoichiometry, are rapidly extending new material functionality across a variety of applications. Accelerated ...development of these compounds requires accurate predictions of material defect properties including effective defect formation energies and equilibrium defect concentrations. Traditional first-principles approaches typically examine dilute defect concentrations and relatively ordered atomic structures to identify the lowest energy defect sites. These approaches are rarely suitable for describing the disorder present in these systems and its influence on defect formation, which can lead to unphysically large predictions for defect concentrations. Here, we demonstrate a new method to accurately predict the temperature and pressure dependence of oxygen vacancy concentrations and proton interstitial concentrations in complex oxides. This method extends standard dilute defect calculations to incorporate atomic and magnetic disorder, employs the ensemble descriptions of defect sites resulting in improved predictions of defect formation energies, and accounts for effects beyond the dilute defect limit. To demonstrate our method, we show that the predicted defect concentrations in perovskites used as ceramic fuel cell cathodes, including Ba0.5Sr0.5Fe0.8Zn0.2O3−δ, Ba0.5Sr0.5Co0.8Fe0.2O3−δ, and BaCo1–x–y–z Fe x Zr y Y z O3−δ, are in good agreement with experimental values, thereby opening the door for predictive design of complex oxides by these applications.
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Binary III-N nitride semiconductors with wurtzite crystal structure such as GaN and AlN have been long used in many practical applications ranging from optoelectronics to telecommunication. The ...structurally related ZnGeN2 or ZnSnN2 derived from the parent binary compounds by cation mutation (elemental substitution) have recently attracted attention, but such ternary nitride materials are mostly limited to II-IV-N2 compositions. This paper demonstrates synthesis and characterization of zinc niobium nitride (Zn2NbN3) – a previously unreported II2-V-N3 ternary nitride semiconductor. The Zn2NbN3 thin films are synthesized using a one-step adsorption-controlled growth, and a two-step deposition/annealing method that suppresses the loss of Zn and N. Measurements indicate that this sputtered Zn2NbN3 crystalizes in cation-disordered wurtzite-derived structure, in contrast to chemically related rocksalt-derived Mg2NbN3 compound, also synthesized here for comparison using the two-step method. The estimated wurtzite lattice parameter ratio of Zn2NbN3 is 1.55, and the optical absorption onset is at 2.1 eV. Both of these values are lower compared to published Zn2NbN3 computational values of c/a = 1.62 and Eg = 3.5 - 3.6 eV. Additional theoretical calculations indicate that this difference is due to cation disorder in experimental samples, suggesting a way to tune the structural parameters and the resulting properties of heterovalent ternary nitride materials. Overall, this work expands the wurtzite family of nitride semiconductors to include Zn2NbN3, and suggests that related II2-V-N3 and other ternary nitrides should be possible to synthesize.
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