Chlorine incorporation in triple halide perovskites reduces trap density and enhances the efficiency of indoor light harvesting.

Indoor photovoltaics are receiving tremendous attention due to the continuous development of the Internet of Things (IoT). Here we report a triple anion (TA) perovskite CH3NH3PbI2.6(BrCl)0.2 with a tailored bandgap suitable for maximizing indoor light harvesting compared to methyl ammonium lead iodide CH3NH3PbI3. The best-performing TA perovskite indoor-photovoltaic device achieved a steady-state power conversion efficiency (PCE) of 25.1 output power density of 75 microW/cm2 under 1000 lux indoor illumination (0.3 mW/cm2 irradiance). This PCE is almost 40 equivalent CH3NH3PbI3-based devices (PCE of 17.9 reduced density of trap states and improved crystalline quality were achieved by the triple anion alloying method. The decisive role of chlorine (Cl) in the better performance of TA-based indoor photovoltaic devices was further investigated by successively reducing the Cl content and correlating it with the corresponding photovoltaic device performance. Replacing the commonly used hole transporting layer of Spiro-MeOTAD with undoped P3HT was found to significantly reduce the current-voltage hysteresis under indoor lighting conditions. A graphene-coated textile fiber-based temperature sensor was successfully powered by the triple anion perovskite indoor photovoltaic devices. The results from the present study demonstrate a novel route to maximize the PCE of halide perovskite indoor photovoltaic devices and their potential for application in the IoT industry.

One of the great advantages of organic–inorganic metal halides is that their structures and properties are highly tuneable and this is important when optimizing materials for photovoltaics or other optoelectronic devices. One of the most common and effective ways of tuning the electronic structure is through anion substitution. Here, we report the inclusion of bromine into the layered perovskite [H3N(CH2)6NH3]PbBr4 to form [H3N(CH2)6NH3]PbBr4·Br2, which contains molecular bromine (Br2) intercalated between the layers of corner-sharing PbBr6 octahedra. Bromine intercalation in [H3N(CH2)6NH3]PbBr4·Br2 results in a decrease in the band gap of 0.85 eV and induces a structural transition from a Ruddlesden–Popper-like to Dion–Jacobson-like phase, while also changing the conformation of the amine. Electronic structure calculations show that Br2 intercalation is accompanied by the formation of a new band in the electronic structure and a significant decrease in the effective masses of around two orders of magnitude. This is backed up by our resistivity measurements that show that [H3N(CH2)6NH3]PbBr4·Br2 has a resistivity value of one order of magnitude lower than [H3N(CH2)6NH3]PbBr4, suggesting that bromine inclusion significantly increases the mobility and/or carrier concentration in the material. This work highlights the possibility of using molecular inclusion as an alternative tool to tune the electronic properties of layered organic–inorganic perovskites, while also being the first example of molecular bromine inclusion in a layered lead halide perovskite. By using a combination of crystallography and computation, we show that the key to this manipulation of the electronic structure is the formation of halogen bonds between the Br2 and Br in the [PbBr4]∞ layers, which is likely to have important effects in a range of organic–inorganic metal halides.