Reduced graphene oxides (rGO) are synthesized via reduction of GO with reducing agents as a hole‐extraction layer for high‐performance inverted planar heterojunction perovskite solar cells. The best efficiencies of power conversion (PCE) of these rGO cells exceed 16%, much greater than those made of GO and poly(3,4‐ethenedioxythiophene):poly(styrenesulfonate) films. A flexible rGO device shows PCE 13.8% and maintains 70% of its initial performance over 150 bending cycles. It is found that the hole‐extraction period is much smaller for the GO/methylammonium lead‐iodide perovskite (PSK) film than for the other rGO/PSK films, which contradicts their device performances. Photoluminescence and transient photoelectric decays are measured and control experiments are performed to prove that the reduction of the oxygen‐containing groups in GO significantly decreases the ability of hole extraction from PSK to rGO and also retards the charge recombination at the rGO/PSK interface. When the hole injection from PSK to GO occurs rapidly, hole propagation from GO to the indium‐doped tin oxide (ITO) substrate becomes a bottleneck to overcome, which leads to a rapid charge recombination that decreases the performance of the GO device relative to the rGO device.

Electric-field-induced changes in absorption and photoluminescence (PL) spectra and in PL decay profile have been measured for two-dimensional hybrid organic−inorganic halide perovskite semiconductor, ((C 4 H 9 NH 3 ) 2 Pbl 4 ) (N1). Electroabsorption (E-A) spectra observed at room temperature and at a low temperature of 45 K were analyzed by assuming the Stark shift, and the magnitudes of the change in electric dipole moment and polarizability following photoexcitation were determined. The strong signal observed in the E-A spectra at 45 K was interpreted in terms of the weak absorption band which shows extremely large Stark shift resulting from the large change in polarizability following photoexcitation. Electrophotoluminescence spectra of this compound, that is, field-induced change in PL spectra, show that PL of N1 is quenched by the application of electric field. Field effects on PL decay profiles show that the quenching results both from the field-induced decrease of the population of the emitting state following photoexcitation and from the field-induced lifetime shortening caused by the enhancement of the nonradiative decay rate at the emitting state. At a low temperature of 45 K, two exciton emissions, each of which originates from different phase, appear, and both emissions are quenched by the applied electric field with different efficiencies from each other. It is also found that trap emissions observed at low temperature in the wavelength region longer than the sharp exciton bands show more efficient field-induced quenching than that of the exciton emissions, suggesting that energy transfer from the photoexcited state to trapped states is decelerated by the applied electric field.

The dependence of photoluminescence (PL) on excitation power and the effect of an external electric field have been studied for a two-dimensional (2D) perovskite (C4H9NH3)2PbI4 thin-film sample. The efficiency of dissociation of hot excitons to produce free carriers was enhanced with a small excitation power because the relaxation of hot excitons to cold emissive excitons was slow, indicating that the thermal energies of hot carriers can be utilized in solar cells under weak photoirradiation. The dissociation was notably enhanced with an applied electric field, resulting in efficient field-induced quenching of the PL. The present results shed light on an application of 2D perovskite materials to photovoltaic (PV) devices with dim radiation, e.g., for indoor PV applications; the concept of electric field-assisted solar cells might be applicable to next-generation solar cells.