Perovskite photovoltaics advance rapidly, but questions remain regarding point defects: while experiments have detected the presence of electrically active defects no experimentally confirmed microscopic identifications have been reported. Here we identify lead monovacancy (V_Pb) defects in MAPbI₃ (MA = CH₃NH₃⁺) using positron annihilation lifetime spectroscopy with the aid of density functional theory. Experiments on thin film and single crystal samples all exhibited dominant positron trapping to lead vacancy defects, and a minimum defect density of ~3 × 10¹⁵ cm⁻³ was determined. There was also evidence of trapping at the vacancy complex $$({{{{{\rm{V}}}}}}_{{{{{\rm{Pb}}}}}}{{{{{\rm{V}}}}}}_{{{{{\rm{I}}}}}})^{-}$$( V Pb V I ) − in a minority of samples, but no trapping to MA-ion vacancies was observed. Our experimental results support the predictions of other first-principles studies that deep level, hole trapping, $${{{{{{\rm{V}}}}}}}_{{{{{{\rm{Pb}}}}}}}^{2-}$$V Pb 2 − , point defects are one of the most stable defects in MAPbI₃. This direct detection and identification of a deep level native defect in a halide perovskite, at technologically relevant concentrations, will enable further investigation of defect driven mechanisms.

Alternatives to lead- and tin-based perovskites for photovoltaics and optoelectronics are sought that do not suffer from the disadvantages of toxicity and low device efficiency of present-day materials. Here we report a study of the double perovskite Cs₂TeI₆, which we have synthesized in thin film form for the first time. Exhaustive trials concluded that spin coating CsI and TeI₄ using an anti-solvent method produced uniform films, confirmed as Cs₂TeI₆ by XRD with Rietveld analysis. They were stable up to 250°C, had an optical band gap of ~1.5 eV, absorption coefficients of ~6 x 10⁴ cm^-1, carrier lifetimes of ~2.6 ns (unpassivated 200 nm film), a work function of 4.95 eV and had p-type surface conductivity. Vibrational modes probed by Raman and FTIR spectroscopy showed resonances qualitatively consistent with DFT Phonopy-calculated spectra, offering another route for phase confirmation. It was concluded that the material is a candidate for further study as a potential optoelectronic or photovoltaic material.

The ternary Cu-Sb- and Cu-Bi-chalcogenides present a rich range of compounds of potential use for large-scale photovoltaics from Earth abundant elements. This paper reviews the state of fundamental knowledge about them, and their technological status with regard to solar cells. Research targets and missing data are highlighted, which may provide opportunities to help realize the goal of sustainable photovoltaics.The family of ternary Cu-Sb- and Cu-Bi-chalcogenides and their solid solutions present a rich selection of potential candidates for Earth-abundant low toxicity photovoltaic (PV) absorber materials. Moreover, they have some novel features imparted by the ns²lone pair of electrons on the Sb and Bi ions. This review evaluates them as electronic materials, including experimental and theoretical evaluations of their phases, thermodynamic stability, point defects, conductivity, optical data, and PV performances. Formation of the materials in bulk, thin film, and nanoforms and the properties of the materials are critically assessed with relevance to their suitability for PV devices. There is special emphasis on CuSbS₂and CuSbSe₂which form the mainstay of the device literature and provide the most insights into the present-day limitation of the device efficiencies to 3 or 4%. Missing features of the literature are highlighted and clear statements recommending potential research pathways are made, which may help advance the technological performance from its present stuck position.

As an absorber in photovoltaic devices, Sb₂Se₃ has rapidly achieved impressive power conversion efficiencies despite the lack of fundamental knowledge about its electronic defects. Here, we present a deep level transient spectroscopy (DLTS) study of deep level defects in both bulk crystal and thin film device material. DLTS study of Bridgman-grown n-type bulk crystals revealed traps at 358, 447, 505, and 685 meV below the conduction band edge. Of these, the energetically close pair at 447 and 505 meV could only be resolved using the isothermal transient spectroscopy (rate window variation) method. A completed Sb₂Se₃ thin film solar cell displayed similar trap spectra with traps identified at 378, 460, and 690 meV. The comparable nature of defects in thin film and bulk crystal material implies that there is minimal impact of polycrystallinity in Sb₂Se₃ supporting the concept of benign grain boundaries.

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfill ambitions for net-zero carbon dioxide equivalent (CO₂eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TW_p in 2021 to 8.5 TW_p by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the PVs community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.

Chalcogenide perovskites have been recently proposed as novel absorber materials for photovoltaic applications. BaZrS₃, the most investigated compound of this family, shows a high absorption coefficient, a bandgap of around 1.8 eV, and excellent stability. In addition to the 3D perovskite BaZrS₃, the Ba–Zr–S compositional space contains various 2D Ruddlesden–Popper phases Ba_n + 1Zr_nS_3n + 1 (with n = 1, 2, 3) which have recently been reported. Herein, it is shown that at high temperature the Gibbs free energies of 3D and 2D perovskites are very close, suggesting that 2D phases can be easily formed at high temperatures. The product of the BaS and ZrS₂ solid‐state reaction, in different stoichiometric conditions, presents a mixture of BaZrS₃ and Ba₄Zr₃S₁₀. To carefully resolve the composition, X‐ray diffraction, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy analysis are complemented with Raman spectroscopy. For this purpose, the phonon dispersions, and the consequent Raman spectra, are calculated for the 3D and 2D chalcogenide perovskites, as well as for the binary precursors. This thorough characterization demonstrates the thermodynamic limitations and experimental difficulties in forming phase‐pure chalcogenide perovskites through solid‐state synthesis and the importance of using multiple techniques to soundly resolve the composition of these materials.