Improved Quantum Efficiency of Highly Efficient Perovskite BaSnO₃‑Based Dye-Sensitized Solar Cells

Ternary oxides are potential candidates as an electron-transporting material that can replace TiO₂ in dye-sensitized solar cells (DSSCs), as their electronic/optical properties can be easily controlled by manipulating the composition and/or by doping. Here, we report a new highly efficient DSSC using perovskite BaSnO₃ (BSO) nanoparticles. In addition, the effects of a TiCl₄ treatment on the physical, chemical, and photovoltaic properties of the BSO-based DSSCs are investigated. The TiCl₄ treatment was found to form an ultrathin TiO₂ layer on the BSO surface, the thickness of which increases with the treatment time. The formation of the TiO₂ shell layer improved the charge-collection efficiency by enhancing the charge transport and suppressing the charge recombination. It was also found that the TiCl₄ treatment significantly reduces the amount of surface OH species, resulting in reduced dye adsorption and reduced light-harvesting efficiency. The trade-off effect between the charge-collection and light-harvesting efficiencies resulted in the highest quantum efficiency (<i>i</i>.<i>e</i>., short-circuit photocurrent density), leading to the highest conversion efficiency of 5.5% after a TiCl₄ treatment of 3 min (<i>cf</i>. 4.5% for bare BSO). The conversion efficiency could be increased further to 6.2% by increasing the thickness of the BSO film, which is one of the highest efficiencies from non-TiO₂-based DSSCs

Solvent-Engineering Method to Deposit Compact Bismuth-Based Thin Films: Mechanism and Application to Photovoltaics

Bismuth-based materials have been studied as alternatives to lead-based perovskite materials for photovoltaic applications. However, poor film quality has limited device performance. In this work, we developed a solvent-engineering method and show that it is applicable to several bismuth-based compounds. Through this method, we obtained compact films of methylammonium bismuth iodide (MBI), cesium bismuth iodide (CBI), and formamidinium bismuth iodide (FBI). On the basis of film growth theory and experimental analyses, we propose a possible mechanism of film formation. Additionally, we demonstrate that the resultant compact MBI film is more suitable to fabricate efficient and stable photovoltaic devices compared to baseline MBI films with pinholes. We further employed a new hole-transporting material to reduce the valence-band offset with the MBI. The best-performing photovoltaic device exhibits an open-circuit voltage of 0.85 V, fill factor of 73%, and a power conversion efficiency of 0.71%, the highest reported values for MBI-based photovoltaic devices

Zn₂SnO₄‑Based Photoelectrodes for Organolead Halide Perovskite Solar Cells

We report a new ternary Zn₂SnO₄ (ZSO) electron-transporting electrode of a CH₃NH₃PbI₃ perovskite solar cell as an alternative to the conventional TiO₂ electrode. The ZSO-based perovskite solar cells have been prepared following a conventional procedure known as a sequential (or two-step) process with ZSO compact/mesoscopic layers instead of the conventional TiO₂ counterparts, and their solar cell properties have been investigated as a function of the thickness of either the ZSO compact layer or the ZSO mesoscopic layer. The presence of the ZSO compact layer has a negligible influence on the transmittance of the incident light regardless of its thickness, whereas the thickest compact layer blocks the back-electron transfer most efficiently. The open-circuit voltage and fill factor increase with the increasing thickness of the mesoscopic ZSO layer, whereas the short-circuit current density decreases with the increasing thickness except for the thinnest one (∼100 nm). As a result, the device with a 300 nm-thick mesoscopic ZSO layer shows the highest conversion efficiency of 7%. In addition, time-resolved and frequency-resolved measurements reveal that the ZSO-based perovskite solar cell exhibits faster electron transport (∼10 times) and superior charge-collection capability compared to the TiO₂-based counterpart with similar thickness and conversion efficiency

<i>A</i>‑Site Cation in Inorganic <i>A</i>₃Sb₂I₉ Perovskite Influences Structural Dimensionality, Exciton Binding Energy, and Solar Cell Performance

Inspired by the rapid rise in efficiencies of lead halide perovskite (LHP) solar cells, lead-free alternatives are attracting increasing attention. In this work, we study the photovoltaic potential of solution-processed antimony (Sb)-based compounds with the formula <i>A</i>₃Sb₂I₉ (<i>A</i> = Cs, Rb, and K). We experimentally determine bandgap magnitude and type, structure, carrier lifetime, exciton binding energy, film morphology, and photovoltaic device performance. We use density functional theory to compute the equilibrium structures, band structures, carrier effective masses, and phase stability diagrams. We find the <i>A</i>-site cation governs the structural and optoelectronic properties of these compounds. Cs₃Sb₂I₉ has a 0D structure, the largest exciton binding energy (175 ± 9 meV), an indirect bandgap, and, in a solar cell, low photocurrent (0.13 mA cm^–2). Rb₃Sb₂I₉ has a 2D structure, a direct bandgap, and, among the materials investigated, the lowest exciton binding energy (101 ± 6 meV) and highest photocurrent (1.67 mA cm^–2). K₃Sb₂I₉ has a 2D structure, intermediate exciton binding energies (129 ± 9 meV), and intermediate photocurrents (0.41 mA cm^–2). Despite remarkably long lifetimes in all compounds (54, 9, and 30 ns for Cs-, Rb-, and K-based materials, respectively), low photocurrents limit performance of all devices. We conclude that carrier collection is limited by large exciton binding energies (experimentally observed) and large carrier effective masses (calculated from density functional theory). The highest photocurrent and efficiency (0.76%) were observed in the Rb-based compound with a direct bandgap, relatively lower exciton binding energy, and lower calculated electron effective mass. To reliably screen for candidate lead-free photovoltaic absorbers, we advise that faster and more accurate computational tools are needed to calculate exciton binding energies and effective masses

Improving the Carrier Lifetime of Tin Sulfide via Prediction and Mitigation of Harmful Point Defects

Tin monosulfide (SnS) is an emerging thin-film absorber material for photovoltaics. An outstanding challenge is to improve carrier lifetimes to >1 ns, which should enable >10% device efficiencies. However, reported results to date have only demonstrated lifetimes at or below 100 ps. In this study, we employ defect modeling to identify the sulfur vacancy and defects from Fe, Co, and Mo as most recombination-active. We attempt to minimize these defects in crystalline samples through high-purity, sulfur-rich growth and experimentally improve lifetimes to >3 ns, thus achieving our 1 ns goal. This framework may prove effective for unlocking the lifetime potential in other emerging thin-film materials by rapidly identifying and mitigating lifetime-limiting point defects