The lead halide perovskite photovoltaic cells, especially the iodide compound CH3NH3PbI3 family, exhibited enormous progress in the energy conversion efficiency in the past few years. Although the first attempt to use the perovskite was as a sensitizer in a dye-sensitized solar cell, it has been recognized at the early stage of the development that the working of the perovskite photovoltaics is akin to that of the inorganic thin film solar cells. In fact, theoretically perovskite is always treated as an ordinary direct band gap semiconductor and hence the perovskite photovoltaics as a p-i-n diode. Despite this recognition, research effort along this line of thought is still in pieces and incomplete. Different measurements have been applied to different types of devices (different not only in the materials but also in the cell structures), making it difficult to have a coherent picture. To make the situation worse, the perovskite photovoltaics have been plagued by the irreproducible optoelectronic properties, most notably the sweep direction dependent current-voltage relationship, the hysteresis problem. Under such circumstances, it is naturally very difficult to analyze the data. Therefore, we set out to make hysteresis-free samples and apply time-tested models and numerical tools developed in the field of inorganic semiconductors. A series of electrical measurements have been performed on one type of CH3NH3PbI3 photovoltaic cells, in which a special attention was paid to ensure that their electronic reproducibility was better than the fitting error in the numerical analysis. The data can be quantitatively explained in terms of the established models of inorganic semiconductors: current/voltage relationship can be very well described by a two-diode model, while impedance spectroscopy revealed the presence of a thick intrinsic layer with the help of a numerical solver, SCAPS, developed for thin film solar cell analysis. These results point to that CH3NH3PbI3 is an ideal intrinsic semiconductor, which happens to be very robust against accidental doping, and that the perovskite photovoltaic cell is in fact a model p-i-n diode. The analytical methods and diagnostic tools available in the inorganic semiconductor PV cells are useful and should be fully exploited in the effort of improving the efficiency. One outstanding question is why the perovskite stays intrinsic. Considering the defects and impurities that must abound in the perovskite layers formed by the spin-coating process, for example, there must be physicochemical mechanism keeping it from being doped. This may be related to the special band structure making up the band gap in this ionic solid. Understanding the mechanism may open a door for the wider utility of this class of solid.

Perovskite solar cells fabricated using chlorine-mediated interdiffusion method showed promising stability over 2 months with encapsulation and no immediate degradation under continuous light exposure.

Ion migration has been suspected as the origin of various irreproducible and unstable properties, most notably the hysteresis, of lead halide perovskite photovoltaic (PV) cells since the early stage of the research. Although many evidence of ionic movement have been presented both numerically and experimentally, a coherent and quantitative picture that accounts for the observed irreproducible phenomena is still lacking. At the same time, however, it has been noticed that in certain types of PV cells, the hysteresis is absent or at least within the measurement reproducibility. We have previously shown that the electronic properties of hysteresis-free cells are well represented in terms of the conventional inorganic semiconductors. The reproducibility of these measurements was confirmed typically within tens of minutes under the biasing field of -1 V to +1.5 V. In order to probe the effect of ionic motion in the hysteresis-free cells, we extended the time scale and the biasing rage in the electronic measurements, from which we conclude the following: (1) From various evidence, it appears that ion migration is inevitable. However, it does not cause detrimental effects to the PV operation. (2) We propose, based on the quantitative characterization, that the degradation is more likely due to the chemical change at the interfaces between the carrier selective layers and perovskite rather than the compositional change of the lead iodide perovskite bulk. Together, they give much hope in the use of the lead iodide perovskite in the use of actual application.

Low-temperature solution-processed perovskite solar cells are attracting immense interest due to their ease of fabrication and potential for mass production on flexible substrates. However, the unfavorable surface properties of planar substrates often lead to large variations in perovskite crystal size and weak charge extractions at interfaces, resulting in inferior performance. Here, we report the improved performance, reproducibility, and high stability of "p-i-n" planar heterojunction perovskite solar cells. The key fabrication process is the addition of the amine-polymer poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN-P1) to a simple spin-coating process. The PFN-P1 works as a surfactant and helps promote uniform crystallization. As a result, perovskite films with PFN-P1 have a uniform distribution of grain sizes and improved open circuit voltage. Devices with PFN-P1 showed the best efficiency (13.2%), with a small standard deviation (0.40), out of 60 cells. Moreover, ∼90% of the initial efficiency was retained over more than 6 months. Additionally, devices fabricated from PFN-P1 mixed perovskite films showed higher stability under continuous operation at maximum power point over 150 h. Our results show that this approach is simple and effective for improving device performance, reproducibility, and stability by modifying perovskite properties with PFN-P1. Because of the simplicity of the fabrication process and reliable performance increase, this approach marks important progress in low-temperature solution-processed perovskite solar cells.

Electronic properties of perovskite lead-halide photovoltaic cells have been studied. The dc current/voltage characteristics were found to be well fitted by a standard diode equation under optical excitation and in the dark, while the impedance spectroscopy revealed a pronounced slow process under light illumination, which is absent in the dark. A simple model is proposed, which can explain all aspects of the observed behavior quantitatively and consistently.