A new generation of solid-state photovoltaics is being made possible by the use of organometal-trihalide perovskite materials. While some of these materials are expected to be ferroelectric, almost nothing is known about their ferroelectric properties experimentally. Using piezoforce microscopy (PFM), here we show unambiguously, for the first time, the presence of ferroelectric domains in high-quality β-CH3NH3PbI3 perovskite thin films that have been synthesized using a new solution-processing method. The size of the ferroelectric domains is found to be about the size of the grains (∼100 nm). We also present evidence for the reversible switching of the ferroelectric domains by poling with DC biases. This suggests the importance of further PFM investigations into the local ferroelectric behavior of hybrid perovskites, in particular in situ photoeffects. Such investigations could contribute toward the basic understanding of photovoltaic mechanisms in perovskite-based solar cells, which is essential for the further enhancement of the performance of these promising photovoltaics.
Perovskite solar cells (PSCs) based on thin films of organolead trihalide perovskites (OTPs) hold unprecedented promise for low-cost, high-efficiency photovoltaics (PVs) of the future. While PV performance parameters of PSCs, such as short circuit current, open circuit voltage, and maximum power, are always measured at the macroscopic scale, it is necessary to probe such photoresponses at the nanoscale to gain key insights into the fundamental PV mechanisms and their localized dependence on the OTP thin-film microstructure. Here we use photoconductive atomic force microscopy spectroscopy to map for the first time variations of PV performance at the nanoscale for planar PSCs based on hole-transport-layer free methylammonium lead triiodide (CH3NH3PbI3 or MAPbI3) thin films. These results reveal substantial variations in the photoresponse that correlate with thin-film microstructural features such as intragrain planar defects, grains, grain boundaries, and notably also grain-aggregates. The insights gained into such microstructure-localized PV mechanisms are essential for guiding microstructural tailoring of OTP films for improved PV performance in future PSCs.
Low-intensity pulsed ultrasound (LIPUS) has been shown to be effective for orthopedic fracture repair and nonunion defects, but the specific mechanism behind its efficacy is still unknown. Previously, we have shown a measurable acoustic radiation force at LIPUS intensities traditionally used for clinical treatment and have applied this force to osteoblastic cells encapsulated in type I collagen hydrogels. Our goal in this study is to provide insight and inform the appropriate design of a cell therapy approach to bone repair in which osteoblasts are embedded in collagen hydrogels, implanted into a bony defect, and then transdermally stimulated using LIPUS-derived acoustic radiation force to enhance bone formation at the earliest time points after bone defect repair. To this end, in this study, we demonstrate the ability to measure local hydrogel deformations in response to LIPUS-induced acoustic radiation force and reveal that hydrogel deformation varies with both LIPUS intensity and hydrogel stiffness. Specifically, hydrogel deformation is positively correlated with LIPUS intensity and this deformation is further increased by reducing the stiffness of the hydrogel. We have also shown that encapsulated osteoblastic cells respond to increases in LIPUS intensity by upregulating both cyclooxygenase 2 and prostaglandin E (PGE), both implicated in new bone formation and well-established responses to the application of fluid forces on osteoblast cells. Finally, we demonstrate that combining an increase in LIPUS with a three-dimensional culture environment upregulates both markers beyond their expression noted from either experimental condition alone, suggesting that both LIPUS and hydrogel encapsulation, when combined and modulated appropriately, can enhance osteoblastic response considerably. These studies provide important information toward a clinically relevant cell therapy treatment for bone defects that allows the transdermal application of mechanical loading to bone defects without physically destabilizing the defect site.
Photo-conductive AFM spectroscopy ('pcAFMs') is proposed as a high-resolution approach for investigating nanostructured photovoltaics, uniquely providing nanoscale maps of photovoltaic (PV) performance parameters such as the short circuit current, open circuit voltage, maximum power, or fill factor. The method is demonstrated with a stack of 21 images acquired during in situ illumination of micropatterned polycrystalline CdTe/CdS, providing more than 42 000 I/V curves spatially separated by~5 nm. For these CdTe/CdS microcells, the calculated photoconduction ranges from 0 to 700 picoSiemens (pS) upon illumination with~1.6 suns, depending on location and biasing conditions. Mean short circuit currents of 2 pA, maximum powers of 0.5 pW, and fill factors of 30% are determined. The mean voltage at which the detected photocurrent is zero is determined to be 0.7 V. Significantly, enhancements and reductions in these more commonly macroscopic PV performance metrics are observed to correlate with certain grains and grain boundaries, and are confirmed to be independent of topography. These results demonstrate the benefits of nanoscale resolved PV functional measurements, reiterate the importance of microstructural control down to the nanoscale for 'PV devices, and provide a widely applicable new approach for directly investigating PV materials.
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