Sublimed C60 for efficient and repeatable perovskite-based solar cells.

Thermally evaporated C60 is a near-ubiquitous electron transport layer in state-of-the-art p-i-n perovskite-based solar cells. As perovskite photovoltaic technologies are moving toward industrialization, batch-to-batch reproducibility of device performances becomes crucial. Here, we show that commercial as-received (99.75% pure) C60 source materials may coalesce during repeated thermal evaporation processes, jeopardizing such reproducibility. We find that the coalescence is due to oxygen present in the initial source powder and leads to the formation of deep states within the perovskite bandgap, resulting in a systematic decrease in solar cell performance. However, further purification (through sublimation) of the C60 to 99.95% before evaporation is found to hinder coalescence, with the associated solar cell performances being fully reproducible after repeated processing. We verify the universality of this behavior on perovskite/silicon tandem solar cells by demonstrating their open-circuit voltages and fill factors to remain at 1950 mV and 81% respectively, over eight repeated processes using the same sublimed C60 source material. Notably, one of these cells achieved a certified power conversion efficiency of 30.9%. These findings provide insights crucial for the advancement of perovskite photovoltaic technologies towards scaled production with high process yield.

Spatial Localization of Defects in Halide Perovskites Using Photothermal Deflection Spectroscopy.

Photothermal deflection spectroscopy (PDS) emerges as a highly sensitive noncontact technique for measuring absorption spectra and serves for studying defect states within semiconductor thin films. In our study, we applied PDS to methylammonium lead bromide single crystals. By analyzing the frequency dependence of the PDS spectra and the phase difference of the signal, we can differentiate between surface and bulk deep defect absorption states. This methodology allowed us to investigate the effects of bismuth doping and light-induced degradation. The identified absorption states are attributed to MA+ vibrational states and structural defects, and their influence on the nonradiative recombination probability is discussed. This distinction significantly enhances our capability to characterize and analyze perovskite materials at a deeper level.

Evolution of Structure and Optoelectronic Properties During Halide Perovskite Vapor Deposition.

The efficiency of perovskite-based solar cells has increased dramatically over the past decade to as high as 25%, making them very attractive for commercial use. Vapor deposition is a promising technique that potentially enables fabrication of perovskite solar cells on large areas. However, to implement a large-scale deposition method, understanding and controlling the specific growth mechanisms are essential for the reproducible fabrication of high-quality layers. Here, we study the structural and optoelectronic kinetics of MAPbI3, employing in-situ photoluminescence (PL) spectroscopy and grazing-incidence small/wide-angle X-ray scattering (GI-SAXS/WAXS) simultaneously during perovskite vapor deposition. Such a unique combination of techniques reveals MAPbI3 formation from the early stages and uncovers the morphology, crystallographic structure, and defect density evolution. Furthermore, we show that the nonmonotonous character of PL intensity contrasts with the increasing volume of the perovskite phase during the growth, although bringing valuable information about the presence of defect states.

Life on the Urbach Edge.

The Urbach energy is an expression of the static and dynamic disorder in a semiconductor and is directly accessible via optical characterization techniques. The strength of this metric is that it elegantly captures the optoelectronic performance potential of a semiconductor in a single number. For solar cells, the Urbach energy is found to be predictive of a material's minimal open-circuit-voltage deficit. Performance calculations considering the Urbach energy give more realistic power conversion efficiency limits than from classical Shockley-Queisser considerations. The Urbach energy is often also found to correlate well with the Stokes shift and (inversely) with the carrier mobility of a semiconductor. Here, we discuss key features, underlying physics, measurement techniques, and implications for device fabrication, underlining the utility of this metric.

Combined in Situ Photoluminescence and X-ray Scattering Reveals Defect Formation in Lead-Halide Perovskite Films.

Lead-halide perovskites have established a firm foothold in photovoltaics and optoelectronics due to their steadily increasing power conversion efficiencies approaching conventional inorganic single-crystal semiconductors. However, further performance improvement requires reducing defect-assisted, nonradiative recombination of charge carriers in the perovskite layers. A deeper understanding of perovskite formation and associated process control is a prerequisite for effective defect reduction. In this study, we analyze the crystallization kinetics of the lead-halide perovskite MAPbI3-xClx during thermal annealing, employing in situ photoluminescence (PL) spectroscopy complemented by lab-based grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ GIWAXS measurements are used to quantify the transition from a crystalline precursor to the perovskite structure. We show that the nonmonotonous character of PL intensity development reflects the perovskite phase volume, as well as the occurrence of the defects states at the perovskite layer surface and grain boundaries. The combined characterization approach enables easy determination of defect kinetics during perovskite formation in real-time.