ABSTRACT
The quest for clean energy conversion has become one of the most important efforts for tackling the greenhouse effect for a sustainable environment. This involves energy-scavenging processes like photovoltaics and catalysis, which have been manifested using the solar spectrum. For high-efficiency and durable conversion processes, the search for the low-cost, stable, and environment-friendly functional materials is elusive. In the field of solar cells and catalysis, double perovskite oxides (DPOs) have emerged as potential candidates in recent years. Through compositional tuning and band gap engineering, a plethora of materials are being developed for pertinent applications in this field of energy. Oxide perovskites possess the advantage of a high carrier lifetime compared to that with halide perovskites, which can be beneficial for energy applications. In this perspective, we have presented theoretical investigations focusing on the different types of double perovskite oxides based on the composition space in a systematic manner. Corresponding electronic and optical properties are discussed along with a future outlook on the novel routes to find efficient members in this family.
ABSTRACT
Bismuth-based zero-dimensional perovskites garner high research interest because of their advantages, such as excellent moisture stability and lower toxicity in comparison to lead-based congeners. However, the wide optical bandgap (>2 eV) and poor photoconductivity of these materials are the bottlenecks for their optoelectronic applications. Herein, we report a combined experimental and theoretical study of the structural features and optoelectronic properties of two novel and stable zero-dimensional bismuth perovskites: (biphenyl bis(methylammonium))1.5BiI6·2H2O (BPBI) and (naphthalene diimide bis(ethylammonium))1.5BiI6·2H2O (NDBI). NDBI features a remarkably narrower bandgap (1.82 eV) than BPBI (2.06 eV) because of the significant orbital contribution of self-assembled naphthalene diimide cations at the band edges of NDBI. Further, the FP-TRMC analysis revealed that the photoconductivity of NDBI is about 3.7-fold greater than that of BPBI. DFT calculations showed that the enhanced photoconductivity in NDBI arises from its type-IIa band alignment, whereas type-Ib alignment was seen in BPBI.
ABSTRACT
Bismuth-based perovskites are attracting intense scientific interest due to low toxicity and excellent moisture stability compared to lead-based analogues. However, high exciton binding energy, poor charge carrier separation, and transport efficiencies lower their optoelectronic performances. To address these issues, we have integrated an electronically active organic cation, naphthalimide ethylammonium, between the [BiI52-]n chains via crystal engineering to form a novel perovskite-like material (naphthalimide ethylammonium)2BiI5 (NBI). Single crystal analysis revealed a one-dimensional quantum-well structure for NBI in which inter-inorganic well electronic coupling is screened by organic layers. It exhibited anisotropic photoconductivity and long-lived charge carriers with milliseconds lifetime, which is higher than that of CH3NH3PbI3. Density functional theory calculations confirmed type-IIa band alignment between organic cations and inorganic chains, allowing the former to electronically contribute to the overall charge transport properties of the material.
