Organometal halide perovskite-based solar cells have recently been reported to be highly efficient, giving an overall power conversion efficiency of up to 15%. However, much of the fundamental photophysical properties underlying this performance has remained unknown. Here, we apply photoluminescence, transient absorption, time-resolved terahertz and microwave conductivity measurements to determine the time scales of generation and recombination of charge carriers as well as their transport properties in solution-processed CH3NH3PbI3 perovskite materials. We found that electron-hole pairs are generated almost instantaneously after photoexcitation and dissociate in 2 ps forming highly mobile charges (25 cm(2) V(-1) s(-1)) in the neat perovskite and in perovskite/alumina blends; almost balanced electron and hole mobilities remain very high up to the microsecond time scale. When the perovskite is introduced into a TiO2 mesoporous structure, electron injection from perovskite to the metal oxide is efficient in less than a picosecond, but the lower intrinsic electron mobility of TiO2 leads to unbalanced charge transport. Microwave conductivity measurements showed that the decay of mobile charges is very slow in CH3NH3PbI3, lasting up to tens of microseconds. These results unravel the remarkable intrinsic properties of CH3NH3PbI3 perovskite material if used as light absorber and charge transport layer. Moreover, finding a metal oxide with higher electron mobility may further increase the performance of this class of solar cells.

Solar cells based on organometal halide perovskites have seen rapidly increasing efficiencies, now exceeding 15%. Despite this progress, there is still limited knowledge on the fundamental photophysics. Here we use microwave photoconductance and photoluminescence measurements to investigate the temperature dependence of the carrier generation, mobility, and recombination in (CH3NH3)PbI3. At temperatures maintaining the tetragonal crystal phase of the perovskite, we find an exciton binding energy of about 32 meV, leading to a temperature-dependent yield of highly mobile (6.2 cm(2)/(V s) at 300 K) charge carriers. At higher laser intensities, second-order recombination with a rate constant of γ = 13 × 10(-10) cm(3) s(-1) becomes apparent. Reducing the temperature results in increasing charge carrier mobilities following a T(-1.6) dependence, which we attribute to a reduction in phonon scattering (Σμ = 16 cm(2)/(V s) at 165 K). Despite the fact that Σμ increases, γ diminishes with a factor six, implying that charge recombination in (CH3NH3)PbI3 is temperature activated. The results underline the importance of the perovskite crystal structure, the exciton binding energy, and the activation energy for recombination as key factors in optimizing new perovskite materials.

A vibronic exciton model is applied to explain the long-lived oscillatory features in the two-dimensional (2D) electronic spectra of the Fenna–Matthews–Olson (FMO) complex. Using experimentally determined parameters and uncorrelated site energy fluctuations, the model predicts oscillations with dephasing times of 1.3 ps at 77 K, which is in a good agreement with the experimental results. These long-lived oscillations originate from the coherent superposition of vibronic exciton states with dominant contributions from vibrational excitations on the same pigment. The oscillations obtain a large amplitude due to excitonic intensity borrowing, which gives transitions with strong vibronic character a significant intensity despite the small Huang–Rhys factor. Purely electronic coherences are found to decay on a 200 fs time scale.

A light-induced photoluminescence (PL) enhancement in surface-deposited methylammonium lead iodide (CH3NH3PbI3) perovskites was investigated in detail using time-resolved luminescence microscopy. We found the PL intensity to increase up to three orders of magnitude upon light illumination with an excitation power density of 0.01-1 W cm(-2). The PL enhancement is accompanied by an increase of the PL lifetime from several nanoseconds to several hundred nanoseconds and also by an increase of the initial amplitude of the PL decay. The latter suggests excited state quenching at the subpicosecond timescale. We propose a model where the trapping sites responsible for non-radiative charge recombination can be de-activated by a photochemical reaction involving oxygen. The reaction zone is spatially limited by the excitation light-penetration depth and diffusion length of the charge carriers. The latter increases in the course of the light-curing process making the reaction zone spreading from the surface towards the interior of the crystal. The PL enhancement can be reversed by switching on/off the excitation light or switching the atmosphere between oxygen and nitrogen. Slow diffusion of the reactants and products and equilibrium between the active and "cured" trapping sites are proposed to be the reasons for peculiar responses of PL to such varied experimental conditions.

Lead halide perovskites (LHPs) nanocrystals (NCs), owing to their outstanding photophysical properties, have recently emerged as a promising material not only for solar cells but also for lighting and display applications. The photophysical properties of these materials can be further improved by chemical engineering such as cation exchange. Hot carrier (HC) cooling, as one of the key photophysical processes in LHPs, can strongly influence performance of LHPs NCs based devices. Here, we study HC relaxation dynamics in LHP NCs with cesium (Cs), methylammonium (MA, CH3NH3 +), and formamidinium (FA, CH­(NH2)2 +) cations by using femtosecond transient absorption spectroscopy. The LHP NCs show excitation intensity and excitation energy-dependent HC cooling. We investigate the details of HC cooling in CsPbBr3, MAPbBr3, and FAPbBr3 at three different excitation energies with low excitation intensity. It takes longer time for the HCs at high energy to relax (cool) to the band edge, compared to the HCs generated by low excitation energy. At the same excitation energy (350 nm, 3.54 eV), all the three LHP NCs show fast HC relaxation (<0.4 ps) with the cooling time and rate in the following order: CsPbBr3 (0.39 ps, 2.9 meV/fs) > MAPbBr3 (0.27 ps, 4.6 meV/fs) > FAPbBr3 (0.21 ps, 5.8 meV/fs). The cation dependence can be explained by stronger interaction between the organic cations with the Pb–Br frameworks compared to the Cs. The revealed cation-dependent HC relaxation process is important for providing cation engineering strategies for developing high performance LHP devices.

Fluorescence super-resolution microscopy showed correlated fluctuations of photoluminescence intensity and spatial localization of individual perovskite (CH3NH3PbI3) nanocrystals of size ∼200 × 30 × 30 nm(3). The photoluminescence blinking amplitude caused by a single quencher was a hundred thousand times larger than that of a typical dye molecule at the same excitation power density. The quencher is proposed to be a chemical or structural defect that traps free charges leading to nonradiative recombination. These trapping sites can be activated and deactivated by light.

No abstract

Conjugated polymers are becoming interesting materials for a range of optoelectronic applications. However, their often complex electronic and structural properties prevent establishment of straightforward property-function relationships. In this paper, we summarize recent results on the photophysics and excited state dynamics of conjugated polymers, in order to paint a picture of exciton formation, quenching, and generation of charge carriers.