Semiconductor nanoplatelets exhibit spectrally pure, directional fluorescence. To make polarized light emission accessible and the charge transport effective, nanoplatelets have to be collectively oriented in the solid state. We discovered that the collective nanoplatelets orientation in monolayers can be controlled kinetically by exploiting the solvent evaporation rate in self-assembly at liquid interfaces. Our method avoids insulating additives such as surfactants, making it ideally suited for optoelectronics. The monolayer films with controlled nanoplatelets orientation (edge-up or face-down) exhibit long-range ordering of transition dipole moments and macroscopically polarized light emission. Furthermore, we unveil that the substantial in-plane electronic coupling between nanoplatelets enables charge transport through a single nanoplatelets monolayer, with an efficiency that strongly depends on the orientation of the nanoplatelets. The ability to kinetically control the assembly of nanoplatelets into ordered monolayers with tunable optical and electronic properties paves the way for new applications in optoelectronic devices.
Hole-transporting material (HTM) is an indispensable constituent in organic electronic devices, generally comprising a donor/dopant combination. We report that a disodium salt of substituted benzo[1,2- b:4,5- b']dipyrrole bearing two racemic alkanediylsulfonate anion side chains (BDPSOs) serves as a neutral, nonhygroscopic, dopant-free HTM for lead perovskite (MAPbI) solar cells. These organic/inorganic hybrid molecules are useful for tunable orbital level and controllable solubility. A fluorinated BDPSO has an energy level matched with MAPbI, affording an inverted-structure solar cell that performs with 17.2% efficiency with minimal hysteresis. The solar cell devices fabricated using BDPSOs showed remarkable storage and operational stability.
Solar cells made of lead perovskite crystals have attracted much attention for their high performance, but far less attention as a subject of crystal engineering. Here, we report that citric acid (CA) and chloride anion, working together, modulate crystal growth of CHNHPbI, producing sub-mm-sized cuboid crystals-a morphology more suitable for close packing in a thin film than the commonly observed elongated dodecahedral morphology. By using a 15 wt % CA-doped precursor solution, we formed a single layer of large, flat, and oriented cuboid crystals with minimum crystal domain boundaries and maximum contact with neighboring layers, and fabricated an archetypal inverted-structured device of 4 mm area, which showed, reproducibly and with little hysteresis, 16.75% power conversion efficiency (PCE), 26% higher than the PCE obtained for a polycrystalline film made without CA doping. Under weaker irradiation of a 1 cm device, the PCE improved from 14.52% (one sun) to 20.4% (0.087 suns). Under illumination with white light emitting diode, a 10 wt % CA-doped device showed PCE of 28.1%, suggesting an advantage of PVK-SCs for indoor applications. Further studies on crystal growth modulation will be beneficial for manufacturing efficient and stable lead perovskite solar cells.
Water-dispersed quasi-two dimensional core/shell semiconductor nanoplatelets exhibit high fluorescence brightness, making them promising for various applications including bioimaging.
Two-photon polymerization stereolithographic three-dimensional (3D) printing is used for manufacturing a variety of structures ranging from microdevices to refractive optics. Incorporation of nanoparticles in 3D printing offers huge potential to create even more functional nanocomposite structures. However, this is difficult to achieve since the agglomeration of the nanoparticles can occur. Agglomeration not only leads to an uneven distribution of nanoparticles in the photoresin but also induces scattering of the excitation beam and altered absorption profiles due to interparticle coupling. Thus, it is crucial to ensure that the nanoparticles do not agglomerate during any stage of the process. To achieve noninteracting and well-dispersed nanoparticles on the 3D printing process, first, the stabilization of nanoparticles in the 3D printing resin is indispensable. We achieve this by functionalizing the nanoparticles with surface-bound ligands that are chemically similar to the photoresin that allows increased nanoparticle loadings without inducing agglomeration. By systematically studying the effect of different nanomaterials (Au nanoparticles, Ag nanoparticles, and CdSe/CdZnS nanoplatelets) in the resin on the 3D printing process, we observe that both, material-specific (absorption profiles) and unspecific (radical quenching at nanoparticle surfaces) pathways co-exist by which the photopolymerization procedure is altered. This can be exploited to increase the printing resolution leading to a reduction of the minimum feature size.
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