RESUMEN
The dynamic motion of ions in electrolyte solutions and its effect on recombination was investigated by the heterodyne transient grating method in addition to transient absorption and transient photocurrent methods in dye sensitized solar cells. Realignment of ionic species at the electrode/electrolyte interface was observed after the electron injection in TiO2 on the order of µs. The process was affected by the total quantity of ionic species as well as cation species in the electrolyte. The recombination processes of the electrons were also affected by the constituents; the probability of the electron-electrolyte recombination decreased with decrease in I2 concentration; the dominant recombination process changed from the electron-electrolyte to the electron-dye recombination by decreasing I(-) concentration. It is concluded that sufficient I(-) is necessary for the suppression of the electron-dye recombination and that sufficient I2 is necessary for an efficient redox cycle, while low concentration of I3(-) ions at the electrolyte/TiO2 interface is preferable to suppress the electron-electrolyte recombination. The effect of the cation size in an electrolyte solution on the charge dynamics was also investigated, and it was revealed that the steric hindrance of cations changed the penetration of ionic species into the nanoporous dye/TiO2 electrode, causing a change in the electrostatic properties at the interface. The cation dependence indicated that the presence of large-sized cations suppressed the electron-electrolyte recombination by disturbing the approach of I3(-) paired with the cations.
RESUMEN
In recent years, organometal halide perovskite-based solid-state hybrid solar cells have attracted unexpected increasing interest because of their high efficiency (the record power conversion efficiency has been reported to be over 15%) and low fabrication cost. It has been accepted that the high efficiency was mainly attributed to the strong optical absorption (absorption coefficient: 15,000 cm(-1) at 550 nm) over a broader range (up to 800 nm) and the long lifetimes of photoexcited charge carriers (in the order of 10 ns - a few 100 ns) of the perovskite absorbers. However, much of the fundamental photophysical properties of perovskite relating to the high photovoltaic performance are remained to be investigated. The charge separation and recombination processes at the material interfaces are particularly important for solar cell performances. To better understand the high efficiency of perovskite solar cells, we systematically investigated the charge separation (electron and hole injection) and charge recombination dynamics of CH3NH3PbClI2 hybrid solar cells employing TiO2 nanostructures as the electron transfer material (ETM) and spiro-OMeTAD as the hole transfer material (HTM). The measurements were carried out using transient absorption (TA) techniques on a time scale from sub-picoseconds to milliseconds. We clarified the timescales of electron injection, hole injection, and recombination processes in TiO2/CH3NH3PbClI2/spiro-OMeTAD solar cells. Charge separation and collection efficiency of the perovskite-based solar cells were discussed. In addition, the effect of TiO2 size on the charge separation and recombination dynamics was also investigated. It was found that all TiO2-based perovskite solar cells possessed similar charge separation processes, but quite different recombination dynamics. Our results indicate that charge recombination was crucial to the performance of the perovskite solar cells, which could be effectively suppressed through optimising nanostructured TiO2 films and surface passivation, thus pushing these cells to even higher efficiency.
RESUMEN
Carrier dynamics in quantum-dot sensitized solar cells (QDSSCs) was clarified by combining the information obtained by the heterodyne transient grating (HD-TG), transient absorption (TA) and transient photocurrent (TP) measurements under the short circuit conditions in the time range from microseconds to seconds. The HD-TG signal is sensitive to the ionic species at the electrode/electrolyte interface, and the electrons in the titanium oxide layer injected from quantum dots (QDs) were monitored by the TA signal, and the photocurrent as a final output was monitored by the TP signal. By using the compensating information, the whole picture of the charge dynamics was obtained in the time region after the initial electron injection from QDs into the titanium oxide layer. In the former part of this paper, the assignment of the responses for each measurement was clarified based on the previous paper on dye sensitized solar cells (S. Kuwahara, et al. Phys. Chem. Chem. Phys., 2013, 15(16), 5975-5981). In the latter part, the effect of the device parameters for actual QDSSCs, such as electrolyte concentrations, and coating times of surface passivation of QDs were investigated.