Surface Modulation via Conjugated Bithiophene Ammonium Salt for Efficient Inverted Perovskite Solar Cells.

The metal halide perovskite absorbers are prone to surface defects, which severely limit the power conversion efficiencies (PCEs) and the operational stability of the perovskite solar cells (PSCs). Herein, trace amounts of bithiophene propylammonium iodide (bi-TPAI) are applied to modulate the surface properties of the gas-quenched perovskite. It is found that the bi-TPAI surface treatment has negligible impact on the perovskite morphology, but it can induce a defect passivation effect and facilitate the charge carrier extraction, contributing to the gain in the open-circuit voltage (Voc) and fill factor. As a result, the PCE of the gas-quenched sputtered NiOx-based inverted PSCs is enhanced from the initial 20.0% to 22.0%. Most importantly, the bi-TPAI treatment can largely alleviate or even eliminate the burn-in process during the maximum power point tracking measurement, improving the operational stability of the devices.

Critical Role of Perovskite Film Stoichiometry in Determining Solar Cell Operational Stability: a Study on the Effects of Volatile A-Cation Additives.

Volatile A-cation halide (AX) additives such as formamidinium chloride and methylammonium chloride have been widely employed for high-efficiency perovskite solar cells (PSCs). However, it remains unstudied how they influence the perovskite film stoichiometry and the solar cell performance and operational stability. Hereby, our work shows that over annealing of formamidinium chloride-containing perovskite films leads to a Pb-rich surface, resulting in a high initial efficiency, which however decays during maximum power point tracking (MPPT). On the contrary, perovskite films obtained by a shorter annealing time at the same temperature provide good stability during MPPT but a lower initial efficiency. Thus, we deduce that an optimal annealing is vital for both high efficiency and operational stability, which is then confirmed in the case where methylammonium chloride additive is used. With optimized perovskite annealing conditions, we demonstrate efficient and stable p-i-n PSCs that show a best power conversion efficiency of 20.7% and remain 90% of the initial performance after a 200 h MPPT at 60 °C under simulated 1 sun illumination with high UV content. Our work presents a comprehensive understanding on how volatile AX impacts perovskite film stoichiometry and its correlation to the device performance and operational stability, providing a new guideline for fabricating high-efficiency and operationally stable PSCs.

Improving the Morphology Stability of Spiro-OMeTAD Films for Enhanced Thermal Stability of Perovskite Solar Cells.

To guarantee a long lifetime of perovskite-based photovoltaics, the selected materials need to survive relatively high-temperature stress during the solar cell operation. Highly efficient n-i-p perovskite solar cells (PSCs) often degrade at high operational temperatures due to morphological instability of the hole transport material 2,2',7,7'-tetrakis (N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (Spiro-OMeTAD). We discovered that the detrimental large-domain spiro-OMeTAD crystallization is caused by the simultaneous presence of tert-butylpyridine (tBP) additive and gold (Au) as a capping layer. Based on this discovery and our understanding, we demonstrated facile strategies that successfully stabilize the amorphous phase of spiro-OMeTAD film. As a result, the thermal stability of n-i-p PSCs is largely improved. After the spiro-OMeTAD films in the PSCs were stressed for 1032 h at 85 °C in the dark in nitrogen environment, reference PSCs retained only 22% of their initial average power conversion efficiency (PCE), while the best target PSCs retained 85% relative average PCE. Our work suggests facile ways to realize efficient and thermally stable spiro-OMeTAD containing n-i-p PSCs.

Illumination Intensity Dependence of the Recombination Mechanism in Mixed Perovskite Solar Cells.

Recombination mechanisms in solar cells are frequently assessed through the determination of ideality factors. In this work we report an abrupt change of the value of the "apparent" ideality factor (nAP ) in high-efficiency FA0.71 MA0.29 PbI2.9 Br0.1 based mesoscopic perovskite solar cells as a function of light intensity. This change is manifested as a transition from a regime characterized by nAP ∼1.8-2.5 at low light intensities (<10 mWcm-2 ) to one characterized by nAP ∼1. This transition is equally observed in the recombination resistance extracted from open-circuit impedance measurements. We use drift-diffusion simulations with explicit consideration of ion migration to determine the origin of this transition. We find that a change ofrecombination mechanism concurrent with a modification of the concentration of ionic vacancies is the most likely explanation of the observed behaviour. In the drift-diffusion simulations we show that the apparent ideality factor is in fact affected by the ion vacancy concentration so it is not the optimal parameter to assess the dominant recombination mechanism. We argue that a procedure based on a recently derived "electronic" ideality factor obtained from the high frequency feature of the impedance spectrum is better suited to determine the recombination route that dictates the photovoltage.

Electron Microscopy Characterization of P3 Lines and Laser Scribing-Induced Perovskite Decomposition in Perovskite Solar Modules.

Hybrid metal halide perovskites have emerged as a potential photovoltaic material for low-cost thin film solar cells due to their excellent optoelectronic properties. However, high efficiencies obtained with lab-scale cells are difficult to replicate in large modules. The upscaling process requires careful optimization of multiple steps, such as laser scribing, which divides a module into serially connected cells using a pulsed laser beam. In this work, we characterize the effect of laser scribing on the perovskite layer adjacent to a P3 scribe line using analytical scanning and cross-sectional transmission electron microscopy techniques. We demonstrate that lateral flow of residual thermal energy from picosecond laser pulses decomposes the perovskite layer over extended length scales. We propose that the exact nature of the change in perovskite composition is determined by the presence of preexisting PbI2 grains and hence by the original perovskite formation reaction. Furthermore, we show that along the P3 lines, the indium tin oxide contact is also damaged by high-fluence pulses. Our results provide a deeper understanding on the interaction between laser pulses and perovskite solar modules, highlighting the need to minimize material damage by careful tuning of both laser parameters and the device fabrication procedure.

Model for the Prediction of the Lifetime and Energy Yield of Methyl Ammonium Lead Iodide Perovskite Solar Cells at Elevated Temperatures.

With the realization of highly efficient perovskite solar cells, the long-term stability of these devices is the key challenge hindering their commercialization. In this work, we study the temperature-dependent stability of perovskite solar cells and develop a model capable of predicting the lifetime and energy yield of perovskite solar cells outdoors. This model results from the measurement of the kinetics governing the degradation of perovskite solar cells at elevated temperatures. The individual analysis of all key current-voltage parameters enables the prediction of device performance under thermal stress with high precision. An extrapolation of the device lifetime at various European locations based on historical weather data illustrates the relation between the laboratory data and real-world applications. Finally, the understanding of the degradation mechanisms affecting perovskite solar cells allows the definition and implementation of strategies to enhance the thermal stability of perovskite solar cells.

Light Management Enhancement for Four-Terminal Perovskite-Silicon Tandem Solar Cells: The Impact of the Optical Properties and Thickness of the Spacer Layer between Sub-Cells.

Mechanical stacking of a thin film perovskite-based solar cell on top of crystalline Si (cSi) solar cell has recently attracted a lot of attention as it is considered a viable route to overcome the limitations of cSi single junction power conversion efficiency. Effective light management is however crucial to minimize reflection or parasitic absorption losses in either the top cell or in the light in-coupling of the transmitted light to the bottom sub-cell. The study here is focused on calculating an optimum performance of a four-terminal mechanically stacked tandem structure by varying the optical property and thickness of the spacer between top and bottom sub-cells. The impact of the nature of the spacer material, with its refractive index and absorption coefficient, as well as the thickness of that layer is used as variables in the optical simulation. The optical simulation is done by using the transfer matrix-method (TMM) on a stack of a semi-transparent perovskite solar cell (top cell) mounted on top of a cSi interdigitated back contact (IBC) solar cell (bottom cell). Two types of perovskite absorber material are considered, with very similar optical properties. The total internal and external short circuit current (Jsc) losses for the semitransparent perovskite top cell as a function of the different optical spacers (material and thickness) are calculated. While selecting the optical spacer materials, Jsc for both silicon (bottom cell) and perovskite (top cell) were considered with the aim to optimize the stack for maximum overall short circuit current. From these simulations, it was found that this optimum in our four-terminal tandem occurred at a thickness of the optical spacer of 160 nm for a material with refractive index n = 1.25. At this optimum, with a combination of selected semi-transparent perovskite top cell, the simulated maximum overall short circuit current (Jsc-combined, max) equals to 34.31 mA/cm². As a result, the four-terminal perovskite/cSi multi-junction solar cell exhibits a power conversion efficiency (PCE) of 25.26%, as the sum of the perovskite top cell PCE = 16.50% and the bottom IBC cSi cell PCE = 8.75%. This accounts for an improvement of more than 2% absolute when compared to the stand-alone IBC cSi solar cell with 23.2% efficiency.

Highly Efficient and Stable Flexible Perovskite Solar Cells with Metal Oxides Nanoparticle Charge Extraction Layers.

In this study, the fabrication of highly efficient and durable flexible inverted perovskite solar cells (PSCs) is reported. Presynthesized, solution-derived NiOx and ZnO nanoparticles films are employed at room temperature as a hole transport layer (HTL) and electron transport layer (ETL), respectively. The triple cation perovskite films are produced in a single step and for the sake of comparison, ultrasmooth and pinhole-free absorbing layers are also fabricated using MAPbI3 perovskite. The triple cation perovskite cells exhibit champion power conversion efficiencies (PCEs) of 18.6% with high stabilized power conversion efficiency of 17.7% on rigid glass/indium tin oxide (ITO) substrates (comparing with 16.6% PCE with 16.1% stabilized output efficiency for the flexible polyethylene naphthalate (PEN)/thin film barrier/ITO substrates). More interestingly, the durability of flexible PSC under simulation of operative condition is proved. Over 85% of the maximum stabilized output efficiency is retained after 1000 h aging employing a thin MAPbI3 perovskite (over 90% after 500 h with a thick triple cation perovskite). This result is comparable to a similar state of the art rigid PSC and represents a breakthrough in the stability of flexible PSC using ETLs and HTLs compatible with roll to roll production speed, thanks to their room temperature processing.

Outdoor Measurement and Modeling of Perovskite Module Temperatures.

Photovoltaic cells and modules are exposed to partially rapid changing environmental parameters that influence the device temperature. The evolution of the device temperature of a perovskite module of 225 cm2 area is presented during a period of 25 days under central European conditions. The temperature of the glass-glass packaged perovskite solar module is directly measured at the back contact by a thermocouple. The device is exposed to ambient temperatures from 3 to 34 °C up to solar irradiation levels exceeding 1300 W m-2. The highest recorded module temperature is 61 °C under constant high irradiation levels. Under strong fluctuations of the global solar irradiance, temperature gradients of more than 3 K min-1 with total changes of more than 20 K are measured. Based on the experimental data, a dynamic iterative model is developed for the module temperature evolution in dependence on ambient temperature and solar irradiation. Furthermore, specific thermal device properties that enable an extrapolation of the module response beyond the measured parameter space can be determined. With this set of parameters, it can be predicted that the temperature of the perovskite layer in thin-film photovoltaic devices is exceeding 70 °C under realistic outdoor conditions. Additionally, perovskite module temperatures can be calculated in final applications.