Organic-inorganic hybrid perovskite solar cells have emerged as cost effective efficient light-to-electricity conversion devices. Unravelling the time scale and the mechanisms that govern the charge carrier dynamics is of paramount importance for a clear understanding and further optimization of the perovskite based devices. For the classical FTO/bulk titania blocking layer/mesoporous titania/perovskite/Spiro-OMeTAD (FTO/TPS) cell, further detailed and systematic studies of the ultrafast events related to exciton generation, electron and hole transfer, ultrafast relaxation are still needed. We characterize the initial ultrafast processes attributed to the exciton-perovskite lattice interactions influenced by charge transfer to the electron and hole transporters that precede the exciton diffusion into free charge carriers occurring in the sensitizer. Time-resolved transient absorption studies of the FTO/perovskite and FTO/TPS samples under excitation at different wavelengths and at low fluence 2 (μJ cm(-2)) indicate the sub-picosecond electron and hole injection into titania and Spiro-OMeTAD, respectively. Furthermore, the power-dependent femtosecond transient absorption measurements support the ultrafast charge transfer and show strong Auger-type multiparticle interactions at early times. We reveal that the decays of the internal trap states are the same for both films, while those at surfaces differ. The contribution of the former in the recombination is small, thus increasing the survival probability of the charges in the excited perovskite.

Despite the unprecedented interest in organic-inorganic metal halide perovskite solar cells, quantitative information on the charge transfer dynamics into selective electrodes is still lacking. In this paper, we report the time scales and mechanisms of electron and hole injection and recombination dynamics at organic PCBM and Spiro-OMeTAD electrode interfaces. On the one hand, hole transfer is complete on the subpicosecond time scale in MAPbI3/Spiro-OMeTAD, and its recombination rate is similar to that in neat MAPbI3. This was found to be due to a high concentration of dark charges, i.e., holes brought about by unintentional p-type doping of MAPbI3. Hence, the total concentration of holes in the perovskite is hardly affected by optical excitation, which manifested as similar decay kinetics. On the other hand, the decay of the photoinduced conductivity in MAPbI3/PCBM is on the time scale of hundreds of picoseconds to several nanoseconds, due to electron injection into PCBM and electron-hole recombination at the interface occurring at similar rates. These results highlight the importance of understanding the role of dark carriers in deconvoluting the complex photophysical processes in these materials. Moreover, optimizing the preparation processes wherein undesired doping is minimized could prompt the use of organic molecules as a more viable electrode substitute for perovskite solar cell devices.

We report on studies of the formamidinium lead triiodide (FAPbI3) perovskite film using time-resolved terahertz (THz) spectroscopy (TRTS) and flash photolysis to explore charge carriers generation, migration, and recombination. The TRTS results show that upon femtosecond excitation above the absorption edge, the initial high photoconductivity (∼75 cm(2) V(-1) s(-1)) remains constant at least up to 8 ns, which corresponds to a diffusion length of 25 μm. Pumping below the absorption edge results in a mobility of 40 cm(2) V(-1) s(-1) suggesting lower mobility of charge carriers located at the bottom of the conduction band or shallow sub-bandgap states. Furthermore, analysis of the THz kinetics reveals rising components of <1 and 20 ps, reflecting dissociation of excitons having different binding energies. Flash photolysis experiments indicate that trapped charge carriers persist for milliseconds.

We report on ultrafast studies of Nile Red (NR) interacting with MCM41 mesoporous materials doped by Al, Ga, Zr, and Ti in dichloromethane suspensions. The steady-state results showed a significant red shift and broadening of the diffuse transmittance and the emission spectra upon interaction with the MCM41-based materials. These findings are explained in terms of H-bonds with the host, different Brønsted/Lewis interactions with the matrix and formation of H-and J-aggregates, in addition to weakly and strongly adsorbed monomers. The pico-to nanosecond timeresolved data support this explanation, showing a significant shortening in the emission lifetimes where NR is interacting with metal-doped MCM41. The femtosecond dynamics of NR loaded into X-MCM41 (X = Si, Al, Ga) indicate that the charge-separated state (CS) is formed at the S 1 state in ∼350 fs. For Zr-and Ti-MCM41 hosts the intramolecular charge transfer (ICT) occurs in less than 200 fs, and a subsequent electron injection to Ti or Zr trap states happens in ∼250 fs. Our studies reveal a strong interaction between the NR species and the framework of MCM41 materials at both the S 0 and S 1 states.

We report on high-resolution potential imaging of heterogeneous surfaces by means of Kelvin probe force microscopy, working in frequency modulation mode ͑FM-KPFM͒, performed in ultrahigh vacuum. To study the limits of potential and lateral resolutions in FM-KPFM, we have investigated clean surface of compound semiconductor InSb͑001͒ and the same surface with some submonolayer coverages of KBr and Au. It was found that long-and short-range bias-dependent interactions, acting between the tip and the surface, could be detected and that both interactions contribute to the measured contact potential difference ͑CPD͒ signal. On the one hand, when only the long-range electrostatic interactions between the tip and the surface are active, the CPD map provides the distribution of the local surface potential on the imaged sample with the lateral resolution and the correctness of the measured values depending on the measurement conditions. For this case, the experimental findings were compared with the predictions of theoretical calculations based on a realistic model for the cantilever-sample geometry. On the other hand, when the short-range and bias-dependent interactions are detected, FM-KPFM provides even the sub-nanometer contrast in the CPD signal. In this situation, however, the measured CPD signal is not related to the sample surface potential but reflects the properties of the front tip atom-surface atom interactions.

This study explores the excitation wavelength and fluence dependence of processes occurring in formamidinium lead triiodide (FAPbI) film using time-resolved transient absorption and terahertz spectroscopies. The results indicate that second-order processes are responsible for charge carrier recombination at low fluences of the absorbed photons (below 8.4 × 10 ph per cm). An increase in fluence leads to the appearance and successive reduction of the time component assigned to the Auger recombination of free charge carriers (240-120 ps). Simultaneously, the bimolecular recombination time decreases from ∼1400 to ∼700 ps. Further increasing the pump fluence produces an exciton population that recombines in 6 ps. The comparison of two characteristic bleaching bands located at 480 and 775 nm provides evidence for the validity of the two valence bands model. Excitation with higher fluences results in a marked difference in the probed dynamics at these bands, reflecting the action of two excited states at the conduction band. Our results demonstrate that a single model cannot be applied in characterizing the perovskite absorber transitions at all pump fluences. These findings are relevant in understanding their operating mechanism under specific experimental conditions, which should differ for perovskite based solar cells, lasing media or photon detectors.

A nanographene formed by the fusion of 22 benzene rings has been prepared by combining an in-solution Pd-catalyzed cycloaddition reaction and on-surface Au-promoted cyclodehydrogenation. The structure and electronic properties of the resulting three-fold symmetric C66H24 molecule have been characterized by scanning probe microscopy with atomic resolution and corroborated by theoretical modelling.

Understanding electron and hole (e,h) transport at semiconductor interfaces is paramount to developing efficient optoelectronic devices. Halide perovskite/semiconductor quantum dots (QDs) have emerged as smart hybrid systems with a huge potential for light emission and energy conversion. However, the dynamics of generated e-h pairs are not fully understood. Ultrafast UV-VIS transient absorption and THz spectroscopies have enabled us to unravel the processes of the e-h recombination within a hybrid film of methylammonium lead triiodide (MAPbI3) interacting with different amount of PbS/CdS core/shell QDs. To accurately analyse the complex behaviour, we applied a new model for e-h events in this hybrid material. The results obtained with sample having a high concentration of QDs (7.3 mass percentage) indicate: (i) a large population (92%) of the photogenerated charge carriers are affected by QDs presence. The main part of these carriers (85% of the total) in perovskite domain diffuse towards QDs, where they transfer to the interface (electrons) and QD´s valence bands (holes) with rate constants of 1.2×10 10 s-1 and 4.6×10 10 s-1 , respectively. 7% of these affected charged entities 2 are excitons in the perovskite domain in close vicinity of the interface, and show a recombination rate constant of 3.7×10 10 s-1. (ii) The carriers not affected by QDs presence (8%) recombine through known perovskite deactivation channels. Lowering the QDs mass percentage to 0.24 causes a decrease of electron and hole effective transfer rate constants, and disappearance of excitons. These results provide clues to improve the performance of perovskite/QD based devices.