Snaith group

Abstract:

Metal halide perovskite photodiodes (PPDs) offer high responsivity and broad spectral sensitivity, making them attractive for low-cost visible and near-infrared sensing. A significant challenge in achieving high detectivity in PPDs is lowering the dark current density (J_D) and noise current (i_n). This is commonly accomplished using charge-blocking layers to reduce charge injection. By analyzing the temperature dependence of J_D for lead-tin based PPDs with different bandgaps and electron-blocking layers (EBL), we demonstrate that while EBLs eliminate electron injection, they facilitate undesired thermal charge generation at the EBL-perovskite interface. The interfacial energy offset between the EBL and the perovskite determines the magnitude and activation energy of J_D. By increasing this offset we realized a PPD with ultralow J_D and i_n of 5 × 10^-8 mA cm^-2 and 2 × 10^-14 A Hz^-1/2, respectively, and wavelength sensitivity up to 1050 nm, establishing a new design principle to maximize detectivity in perovskite photodiodes.

Abstract:

Mixed halide perovskites can provide optimal bandgaps for tandem solar cells which are key to improved cost-efficiencies, but can still suffer from detrimental illumination-induced phase segregation. Here we employ optical-pump terahertz-probe spectroscopy to investigate the impact of halide segregation on the charge-carrier dynamics and transport properties of mixed halide perovskite films. We reveal that, surprisingly, halide segregation results in negligible impact to the THz charge-carrier mobilities, and that charge carriers within the I-rich phase are not strongly localised. We further demonstrate enhanced lattice anharmonicity in the segregated I-rich domains, which is likely to support ionic migration. These phonon anharmonicity effects also serve as evidence of a remarkably fast, picosecond charge funnelling into the narrow-bandgap I-rich domains. Our analysis demonstrates how minimal structural transformations during phase segregation have a dramatic effect on the charge-carrier dynamics as a result of charge funnelling. We suggest that because such enhanced recombination is radiative, performance losses may be mitigated by deployment of careful light management strategies in solar cells.

Abstract:

A newly reported compound, CuAgBiI5, is synthesized as powder, crystals, and thin films. The structure consists of a 3D octahedral Ag+/Bi3+ network as in spinel, but occupancy of the tetrahedral interstitials by Cu+ differs from those in spinel. The 3D octahedral network of CuAgBiI5 allows us to identify a relationship between octahedral site occupancy (composition) and octahedral motif (structure) across the whole CuI–AgI–BiI3 phase field, giving the ability to chemically control structural dimensionality. To investigate composition–structure–property relationships, we compare the basic optoelectronic properties of CuAgBiI5 with those of Cu2AgBiI6 (which has a 2D octahedral network) and reveal a surprisingly low sensitivity to the dimensionality of the octahedral network. The absorption onset of CuAgBiI5 (2.02 eV) barely changes compared with that of Cu2AgBiI6 (2.06 eV) indicating no obvious signs of an increase in charge confinement. Such behavior contrasts with that for lead halide perovskites which show clear confinement effects upon lowering dimensionality of the octahedral network from 3D to 2D. Changes in photoluminescence spectra and lifetimes between the two compounds mostly derive from the difference in extrinsic defect densities rather than intrinsic effects. While both materials show good stability, bulk CuAgBiI5 powder samples are found to be more sensitive to degradation under solar irradiation compared to Cu2AgBiI6.

Abstract:

Hybrid organic-inorganic perovskites (HOIPs) have emerged as a versatile class of semiconductors for numerous optoelectronic applications. Here, we demonstrate light-excitation-dependent two-dimensional (2D) position-sensitive detectors (PSDs) using a mixed-phase perovskite, FA_0.83Cs_0.17Pb(I_0.9Br_0.1)₃, as the active semiconductor, incorporated within a five-terminal device geometry. The light-induced lateral photovoltage, which is initiated by selective charge transfer across the metal-perovskite barrier interface, is utilized to achieve the excitation-position-dependent electric response. The 2D PSD devices exhibit a spatially dependent linear variation of the photosignal with sensitivity >50 μV mm^-1 and a low position detection error (1-2%), making them suitable for applications such as quadrant detectors. Further, it is observed that the device architecture plays a key role in controlling the dynamics and linearity of the HOIP PSDs. The large active area devices (up to ∼2 cm × 2 cm) exhibit a distinct spatial variation of the photosignal. We utilize the functionality of the PSD device for light-tracking applications by implementing a continuous detection scheme.