Ultrafast vibrational control of organohalide perovskite optoelectronic devices using vibrationally promoted electronic resonance

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses

Origins of the open-circuit voltage in ternary organic solar cells and design rules for minimized voltage losses

The power conversion efficiency of ternary organic solar cells (TOSCs), consisting of one host binary blend and one guest component, remains limited by large voltage losses. The fundamental understanding of the open-circuit voltage (V OC) in TOSCs is controversial, limiting rational design of the guest component. In this study, we systematically investigate how the guest component affects the radiative and non-radiative related parts of V OC of a series of TOSCs using the detailed balanced principle. We highlight that the thermal population of charge-transfer and local exciton states provided by the guest binary blend (that is, the guest-component-based binary blend) has a significant influence on the non-radiative voltage losses. Ultimately, we provide two design rules for enhancing the V OC in TOSCs: high emission yield for the guest binary blend and similar charge-transfer-state energies for host/guest binary blends; high miscibility of the guest component with the low gap component in the host binary blend

Untangling free carrier and exciton dynamics in layered hybrid perovskites using ultrafast optical and terahertz spectroscopy

Layered hybrid perovskites (LPKs) are promising as alternatives or additives to 3D metal halide perovskites for optoelectronic applications including photovoltaic cells, LEDs and lasers due to their increased stability. However, high exciton binding energies in these materials mean that excitons are the majority species under the operating conditions of many devices. Although the efficiency of devices that incorporate LPKs has been increasing, much is still unknown about the interplay of excitons and free charge-carriers in these materials, which is vital information for understanding how optoelectronic properties dictate device efficiency. In this work, we employ optical pump/THz probe spectroscopy (OPTP) and visible transient absorption spectroscopy (TAS) to analyse the optoelectronic properties and charge-carrier dynamics of phenylethylammonium lead iodide (PEA)2PbI4. By combining these techniques, we are able to disentangle the contributions from excitons and free charge-carriers. We observe fast cooling of free charge-carriers and exciton formation on a timescale of ∼400 fs followed by slower bimolecular recombination of residual free charge-carriers with a rate constant k 2 ∼ 109 cm3s−1. Excitons recombine via two monomolecular processes with lifetimes t 1 ∼ 11 ps and t2 ∼ 83 ps. Furthermore, we detect signatures of exciton–phonon coupling in the transient absorption kinetic traces. These findings provide new insight into the interplay between free charge-carriers and excitons as well as a possible mechanism to further understand the charge-carrier dynamics in LPKs

Efficient Terahertz Generation via Optical Rectification in Halide Perovskites

THz emission from the all-organic, halide perovskite N-methyl-1,4-diazabicyclo [2.2.2] octan-1-ium (methyl-DABCO) ammonium iodide (MDNI) has been demonstrated for the first time. The generation mechanism was shown to be optical rectification, and a peak field strength of up to 0.8 kV/cm was achieved, demonstrating the promise of this class of materials as efficient THz emitter