Intensity Modulated Photocurrent Microspectrosopy for Next Generation Photovoltaics.

In this report, a large-area laser beam induced current microscope that has been adapted to perform intensity modulated photocurrent spectroscopy (IMPS) in an imaging mode is described. Microscopy-based IMPS method provides a spatial resolution of the frequency domain response of the solar cell, allowing correlation of the optoelectronic response with a particular interface, bulk material, specific transport layer, or transport parameter. The system is applied to study degradation effects in back-contact perovskite cells where it is found to readily differentiate areas based on their markedly different frequency response. Using the diffusion-recombination model, the IMPS response is modeled for a sandwich structure and extended for the special case of lateral diffusion in a back-contact cell. In the low-frequency limit, the model is used to calculate spatial maps of the carrier ambipolar diffusion length. The observed frequency response of IMPS images is then discussed.

Interpretation of Mott-Schottky plots of photoanodes for water splitting.

A large body of literature reports that both bismuth vanadate and haematite photoanodes are semiconductors with an extremely high doping density between 1018 and 1021 cm-3. Such values are obtained from Mott-Schottky plots by assuming that the measured capacitance is dominated by the capacitance of the depletion layer formed by the doping density within the photoanode. In this work, we show that such an assumption is erroneous in many cases because the injection of electrons from the collecting contact creates a ubiquitous capacitance step that is very difficult to distinguish from that of the depletion layer. Based on this reasoning, we derive an analytical resolution limit that is independent of the assumed active area and surface roughness of the photoanode, below which doping densities cannot be measured in a capacitance measurement. We find that the reported doping densities in the literature lie very close to this value and therefore conclude that there is no credible evidence from capacitance measurements that confirms that bismuth vanadate and haematite photoanodes contain high doping densities.

Combining Modulated Techniques for the Analysis of Photosensitive Devices.

Small-perturbation techniques such as impedance spectroscopy (IS), intensity-modulated photocurrent spectroscopy (IMPS), and intensity-modulated photovoltage spectroscopy (IMVS) are useful tools to characterize and model photovoltaic and photoelectrochemical devices. While the analysis of the impedance spectra is generally carried out using an equivalent circuit, the intensity-modulated spectroscopies are often analyzed through the measured characteristic response times. This makes the correlation between the two methods of analysis generally unclear. In this work, by taking into consideration the absorptance and separation efficiency, a unified theoretical framework and a procedure to combine the spectral analysis of the three techniques are proposed. Such a joint analysis of IS, IMPS, and IMVS spectra greatly reduces the sample space of possible equivalent circuits to model the device and allows obtaining parameters with high reliability. This theoretical approach is applied in the characterization of a silicon photodiode to demonstrate the validity of this methodology, which shows great potential to improve the quality of analysis of spectra obtained from frequency domain small-perturbation methods.

Comment on "Resolving spatial and energetic distributions of trap states in metal halide perovskite solar cells".

Ni et al (Research Articles, 20 March 2020, p. 1352) report bulk trap densities of 1011 cm-3 and an increase in interfacial trap densities by one to four orders of magnitude from drive-level capacitance profiling of lead halide perovskites. From electrostatic arguments, we show that the results are not trap densities but are a consequence of the geometrical capacitance and charge injection into the perovskite layer.

Effects of Frequency Dependence of the External Quantum Efficiency of Perovskite Solar Cells.

Perovskite solar cells are known to show very long response time scales, on the order of milliseconds to seconds. This generates considerable doubt over the validity of the measured external quantum efficiency (EQE) and consequently the estimation of the short-circuit current density. We observe a variation as high as 10% in the values of the EQE of perovskite solar cells for different optical chopper frequencies between 10 and 500 Hz, indicating a need to establish well-defined protocols of EQE measurement. We also corroborate these values and obtain new insights regarding the working mechanisms of perovskite solar cells from intensity-modulated photocurrent spectroscopy measurements, identifying the evolution of the EQE over a range of frequencies, displaying a singular reduction at very low frequencies. This reduction in EQE is ascribed to additional resistive contributions hindering charge extraction in the perovskite solar cell at short-circuit conditions, which are delayed because of the concomitant large low-frequency capacitance.

Stability of dye-sensitized solar cells under extended thermal stress.

In the last few decades, dye-sensitized solar cell (DSC) technology has been demonstrated to be a promising candidate for low cost energy production due to cost-effective materials and fabrication processes. Arguably, DSC stability is the biggest challenge for making this technology appealing for industrial exploitation. This work provides further insight into the stability of DSCs by considering specific dye-electrolyte systems characterized by Raman and impedance spectroscopy analysis. In particular, two ruthenium-based dyes, Z907 and Ru505, and two commercially available electrolytes, namely, the high stability electrolyte (HSE) and solvent-free Livion 12 (L-12), were tested. After 4700 h of thermal stress at 85 °C, the least stable device composed of Z907/HSE showed an efficiency degradation rate of ∼14%/1000 h, while the Ru505/L-12 system retained 96% of its initial efficiency by losing ∼1% each 1000 h. The present results show a viable route to stabilize the DSC technology under prolonged annealing conditions complying with the IEC standard requirements.

Surface Polarization Model for the Dynamic Hysteresis of Perovskite Solar Cells.

The dynamic hysteresis of perovskite solar cells consists of the occurrence of significant deviations of the current density-voltage curve shapes depending on the specific conditions of measurement such as starting voltage, waiting time, scan rate, and other factors. Dynamic hysteresis is a serious impediment to stabilized and reliable measurement and operation of the perovskite solar cells. In this Letter, we formulate a model for the dynamic hysteresis based on the idea that the cell accumulates a huge quantity of surface electronic charge at forward bias that is released on voltage sweeping, causing extra current over the normal response. The charge shows a retarded dynamics due to the slow relaxation of the accompanying ionic charge, that produces variable shapes depending on scan rate or poling value and time. We show that the quantitative model provides a consistent description of experimental results and allows us to determine significant parameters of the perovskite solar cell for both the transient and steady-state performance.