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Lead halide perovskites (LHPs) have shown remarkable promise for use in photovoltaics, photodetectors, light-emitting diodes, and lasers. Although solution-processed polycrystalline films are the most widely studied morphology, LHP nanowires (NWs) grown by vapor-phase processes offer the potential for precise control over crystallinity, phase, composition, and morphology. Here, we report the first demonstration of self-catalyzed vapor–liquid–solid (VLS) growth of lead halide (PbX2; X = Cl, Br, or I) NWs and conversion to LHP. We present a kinetic model of the PbX2 NW growth process in which a liquid Pb catalyst is supersaturated with halogen X through vapor-phase incorporation of both Pb and X, inducing growth of a NW. For PbI2, we show that the NWs are single-crystalline, oriented in the ⟨1210⟩ direction, and composed of a stoichiometric PbI2 shaft with a spherical Pb tip. Low-temperature vapor-phase intercalation of methylammonium iodide converts the NWs to methylammonium lead iodide (MAPbI3) perovski...

Surface trap density in silicon nanowires (NWs) plays a key role in the performance of many semiconductor NW-based devices. We use pump-probe microscopy to characterize the surface recombination dynamics on a point-by-point basis in 301 silicon NWs grown using the vapor-liquid-solid (VLS) method. The surface recombination velocity (S), a metric of the surface quality that is directly proportional to trap density, is determined by the relationship S = d/4τ from measurements of the recombination lifetime (τ) and NW diameter (d) at distinct spatial locations in individual NWs. We find that S varies by as much as 2 orders of magnitude between NWs grown at the same time but varies only by a factor of 2 or three within an individual NW. Although we find that, as expected, smaller-diameter NWs exhibit shorter τ, we also find that smaller wires exhibit higher values of S; this indicates that τ is shorter both because of the geometrical effect of smaller d and because of a poorer quality surface. These results highlight the need to consider interwire heterogeneity as well as diameter-dependent surface effects when fabricating NW-based devices.

We have developed a pump-probe microscope capable of exciting a single semiconductor nanostructure in one location and probing it in another with both high spatial and temporal resolution. Experiments performed on Si nanowires enable a direct visualization of the charge cloud produced by photoexcitation at a localized spot as it spreads along the nanowire axis. The time-resolved images show clear evidence of rapid diffusional spreading and recombination of the free carriers, which is consistent with ambipolar diffusion and a surface recombination velocity of ∼10(4) cm/s. The free carrier dynamics are followed by trap carrier migration on slower time scales.

Thermal management is an important consideration for most nanoelectronic devices, and an understanding of the thermal conductivity of individual device components is critical for the design of thermally efficient systems. However, it can be difficult to directly probe local changes in thermal conductivity within a nanoscale system. Here, we utilize the time-resolved and diffraction-limited imaging capabilities of ultrafast pump-probe microscopy to determine, in a contact-free configuration, the local thermal conductivity in individual Si nanowires (NWs). By suspending single NWs across microfabricated trenches in a quartz substrate, the properties of the same NW both on and off the substrate are directly compared. We find the substrate has no effect on the recombination lifetime or diffusion length of photogenerated charge carriers; however, it significantly impacts the thermal relaxation properties of the NW. In substrate-supported regions, thermal energy deposited into the lattice by the ultrafast laser pulse dissipates within ∼10 ns through thermal diffusion and coupling to the substrate. In suspended regions, the thermal energy persists for over 100 ns, and we directly image the time-resolved spatial motion of the thermal signal. Quantitative analysis of the transient images permits direct determination of the NW's local thermal conductivity, which we find to be a factor of ∼4 smaller than in bulk Si. Our results point to the strong potential of pump-probe microscopy to be used as an all-optical method to quantify the effects of localized environment and morphology on the thermal transport characteristics of individual nanostructured components.

Strain-induced changes to the electronic structure of nanoscale materials provide a promising avenue for expanding the optoelectronic functionality of semiconductor nanostructures in device applications. Here we use pump-probe microscopy with femtosecond temporal resolution and submicron spatial resolution to characterize charge-carrier recombination and transport dynamics in silicon nanowires (NWs) locally strained by bending deformation. The electron-hole recombination rate increases with strain for values above a threshold of ∼1% and, in highly strained (∼5%) regions of the NW, increases 6-fold. The changes in recombination rate are independent of NW diameter and reversible upon reduction of the applied strain, indicating the effect originates from alterations to the NW bulk electronic structure rather than introduction of defects. The results highlight the strong relationship between strain, electronic structure, and charge-carrier dynamics in low-dimensional semiconductor systems, and we anticipate the results will assist the development of strain-enabled optoelectronic devices with indirect-bandgap materials such as silicon.

Silicon nanowires incorporating p-type/n-type (p-n) junctions have been introduced as basic building blocks for future nanoscale electronic components. Controlling charge flow through these doped nanostructures is central to their function, yet our understanding of this process is inferred from measurements that average over entire structures or integrate over long times. Here, we have used femtosecond pump-probe microscopy to directly image the dynamics of photogenerated charge carriers in silicon nanowires encoded with p-n junctions along the growth axis. Initially, motion is dictated by carrier-carrier interactions, resulting in diffusive spreading of the neutral electron-hole cloud. Charge separation occurs at longer times as the carrier distribution reaches the edges of the depletion region, leading to a persistent electron population in the n-type region. Time-resolved visualization of the carrier dynamics yields clear, direct information on fundamental drift, diffusion, and recombination processes in these systems, providing a powerful tool for understanding and improving materials for nanotechnology.

Si nanowires (NWs) have been widely explored as a platform for photonic and electronic technologies. Here, we report a bottom-up method to break the conventional "wire" symmetry and synthetically encode a high-resolution array of arbitrary shapes, including nanorods, sinusoids, bowties, tapers, nanogaps, and gratings, along the NW growth axis. Rapid modulation of phosphorus doping combined with selective wet-chemical etching enabled morphological features as small as 10 nm to be patterned over wires more than 50 μm in length. This capability fundamentally expands the set of technologies that can be realized with Si NWs, and as proof-of-concept, we demonstrate two distinct applications. First, nanogap-encoded NWs were used as templates for Noble metals, yielding plasmonic structures with tunable resonances for surface-enhanced Raman imaging. Second, core/shell Si/SiO2 nanorods were integrated into electronic devices that exhibit resistive switching, enabling nonvolatile memory storage. Moving beyond these initial examples, we envision this method will become a generic route to encode new functionality in semiconductor NWs.