Water splitting with silicon p-i-n superlattices suspended in solution.

Photoelectrochemical (PEC) water splitting to produce hydrogen fuel was first reported 50 years ago1, yet artificial photosynthesis has not become a widespread technology. Although planar Si solar cells have become a ubiquitous electrical energy source economically competitive with fossil fuels, analogous PEC devices have not been realized, and standard Si p-type/n-type (p-n) junctions cannot be used for water splitting because the bandgap precludes the generation of the needed photovoltage. An alternative paradigm, the particle suspension reactor (PSR), forgoes the rigid design in favour of individual PEC particles suspended in solution, a potentially low-cost option compared with planar systems2,3. Here we report Si-based PSRs by synthesizing high-photovoltage multijunction Si nanowires (SiNWs) that are co-functionalized to catalytically split water. By encoding a p-type-intrinsic-n-type (p-i-n) superlattice within single SiNWs, tunable photovoltages exceeding 10 V were observed under 1 sun illumination. Spatioselective photoelectrodeposition of oxygen and hydrogen evolution co-catalysts enabled water splitting at infrared wavelengths up to approximately 1,050 nm, with the efficiency and spectral dependence of hydrogen generation dictated by the photonic characteristics of the sub-wavelength-diameter SiNWs. Although initial energy conversion efficiencies are low, multijunction SiNWs bring the photonic advantages of a tunable, mesoscale geometry and the material advantages of Si-including the small bandgap and economies of scale-to the PSR design, providing a new approach for water-splitting reactors.

Monolayer-like Exciton Recombination Dynamics of Multilayer MoSe2 Observed by Pump-Probe Microscopy.

Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.g., >10 layers) flakes is still absent. Recent computational studies have suggested that excitons in bulk TMDCs are confined to individual layers, leading to room-temperature stable exciton populations. Using this new context, we explore the carrier dynamics in MoSe2 flakes that are between ∼16 and ∼125 layers thick. We assign the kinetics to exciton-exciton annihilation (EEA) and Shockley-Read-Hall recombination of free carriers. Interestingly, the average observed EEA rate constant (0.003 cm2/s) is nearly independent of flake thickness and 2 orders of magnitude smaller than that of an unencapsulated monolayer (0.33 cm2/s) but very similar to values observed in encapsulated monolayers. Thus, we posit that strong intralayer interactions minimize the effect of layer thickness on recombination dynamics, causing the multilayer to behave like the monolayer and exhibit an apparent EEA rate intrinsic to MoSe2.

Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions.

Photovoltages for hydrogen-terminated p-Si(111) in an acetonitrile electrolyte were quantified with methyl viologen [1,1'-(CH3)2-4,4'-bipyridinium](PF6)2, abbreviated MV2+, and [Ru(bpy)3](PF6)2, where bpy is 2,2'-bipyridine, that respectively undergo two and three one-electron transfer reductions. The reduction potentials, E°, of the two MV2+ reductions occurred at energies within the forbidden bandgap, while the three [Ru(bpy)3]2+ reductions occurred within the continuum of conduction band states. Bandgap illumination resulted in reduction that was more positive than that measured with a degenerately doped n+-Si demonstrative of a photovoltage, Vph, that increased in the order MV2+/+ (260 mV) < MV+/0 (400 mV) < Ru2+/+ (530 mV) ∼ Ru+/0 (540 mV) ∼ Ru0/- (550 mV). Pulsed 532 nm excitation generated electron-hole pairs whose dynamics were nearly constant under depletion conditions and increased markedly as the potential was raised or lowered. A long wavelength absorption feature assigned to conduction band electrons provided additional evidence for the presence of an inversion layer. Collectively, the data reveal that the most optimal photovoltage, as well as the longest electron-hole pair lifetime and the highest surface electron concentration, occurs when E° lies energetically within the unfilled conduction band states where an inversion layer is present. The bell-shaped dependence for electron-hole pair recombination with the surface potential was predicted by the time-honored SRH model, providing a clear indication that this interface provides access to all four bias conditions, i.e., accumulation, flat band, depletion, and inversion. The implications of these findings for photocatalysis applications and solar energy conversion are discussed.

Synthesis and Surface Attachment of Molecular Re(I) Complexes Supported by Functionalized Bipyridyl Ligands.

Eleven 2,2'-bipyridine (bpy) ligands functionalized with attachment groups for covalent immobilization on silicon surfaces were prepared. Five of the ligands feature silatrane functional groups for attachment to metal oxide coatings on the silicon surfaces, while six contain either alkene or alkyne functional groups for attachment to hydrogen-terminated silicon surfaces. The bpy ligands were coordinated to Re(CO)5Cl to form complexes of the type Re(bpy)(CO)3Cl, which are related to known catalysts for CO2 reduction. Six of the new complexes were characterized using X-ray crystallography. As proof of principle, four molecular Re complexes were immobilized on either a thin layer of TiO2 on silicon or hydrogen-terminated silicon. The surface-immobilized complexes were characterized using X-ray photoelectron spectroscopy, IR spectroscopy, and cyclic voltammetry (CV) in the dark and for one representative example in the light. The CO stretching frequencies of the attached complexes were similar to those of the pure molecular complexes, but the CVs were less analogous. For two of the complexes, comparison of the electrocatalytic CO2 reduction performance showed lower CO Faradaic efficiencies for the immobilized complexes than the same complex in solution under similar conditions. In particular, a complex containing a silatrane linked to bpy with an amide linker showed poor catalytic performance and control experiments suggest that amide linkers in conjugation with a redox-active ligand are not stable under highly reducing conditions and alkyl linkers are more stable. A conclusion of this work is that understanding the behavior of molecular Re catalysts attached to semiconducting silicon is more complicated than related complexes, which have previously been immobilized on metallic electrodes.

Remote nongenetic optical modulation of neuronal activity using fuzzy graphene.

The ability to modulate cellular electrophysiology is fundamental to the investigation of development, function, and disease. Currently, there is a need for remote, nongenetic, light-induced control of cellular activity in two-dimensional (2D) and three-dimensional (3D) platforms. Here, we report a breakthrough hybrid nanomaterial for remote, nongenetic, photothermal stimulation of 2D and 3D neural cellular systems. We combine one-dimensional (1D) nanowires (NWs) and 2D graphene flakes grown out-of-plane for highly controlled photothermal stimulation at subcellular precision without the need for genetic modification, with laser energies lower than a hundred nanojoules, one to two orders of magnitude lower than Au-, C-, and Si-based nanomaterials. Photothermal stimulation using NW-templated 3D fuzzy graphene (NT-3DFG) is flexible due to its broadband absorption and does not generate cellular stress. Therefore, it serves as a powerful toolset for studies of cell signaling within and between tissues and can enable therapeutic interventions.

Aqueous Photoelectrochemical CO2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst.

We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3-aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of -0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s-1 . To date, this is the only molecular catalyst-based photoelectrode that is active for the six-electron reduction of CO2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p-type semiconductors and demonstrates state-of-the-art performance for photoelectrochemical CO2 reduction to CO and methanol.

Electrostatic tip effects in scanning probe microscopy of nanostructures.

Electrical scanning probe microscopies (SPM) use ultrasharp metallic tips to obtain nanometer spatial resolution and are a key tool for characterizing nanoscale semiconducting materials and systems. However, these tips are not passive probes; their high work functions can induce local band bending whose effects depend sensitively on the local geometry and material properties and thus are inherently difficult to quantify. We use sequential finite element simulations to first explore the magnitude and spatial distribution of charge reorganization due to tip-induced band bending (TIBB) for planar and nanostructured geometries. We demonstrate that tip-induced depletion and accumulation of carriers can be significantly modified in confined geometries such as nanowires compared to a bulk planar response. This charge reorganization is due to finite size effects that arise as the nanostructure size approaches the Debye length, with significant implications for a range of SPM techniques. We then use the reorganized charge distribution from our model to describe experimentally measured quantities, using in operando scanning microwave impedance microscopy measurements on axial p-i-n silicon nanowire devices as a specific example. By incorporating TIBB, we reveal that our experimentally observed enhancement (absence) of contrast at the p-i (i-n) junction is explained by the tip-induced accumulation (depletion) of carriers at the interface. Our results demonstrate that the inclusion of TIBB is critical for an accurate interpretation of electrical SPM measurements, and is especially important for weakly screening or low-doped materials, as well as the complex doping patterns and confined geometries commonly encountered in nanoscale systems.

Geometric Nanophotonics: Light Management in Single Nanowires through Morphology.

Comprehensive control of light-matter interactions at the nanoscale is increasingly important for the development of miniaturized light-based technologies that have applications ranging from information processing to sensing. Control of light in nanoscale structures-the realm of nanophotonics-requires precise control of geometry on a few-nanometer length scale. From a chemist's perspective, bottom-up growth of nanoscale materials from chemical precursors offers a unique opportunity to design structures atom-by-atom that exhibit desired properties. In this Account, we describe our efforts to create chemically and morphologically precise Si nanowires (NWs) with designed nanophotonic properties using a vapor-liquid-solid (VLS) growth process. A synthetic technique termed "Encoded Nanowire Growth and Appearance through VLS and Etching" (ENGRAVE) combines optimized VLS growth, dopant modulation, and dopant-dependent wet-chemical etching to produce NWs with precisely designed diameter modulations, yielding lithographic-like morphological control that can vary from sinusoids to fractals. The ENGRAVE NWs thus provide a versatile playground for coupling, trapping, and directing light in a nanoscale geometry. Previously, the nanophotonic functionality of NWs primarily relied on uniform-diameter structures that exhibit Mie scattering resonances and longitudinally oriented guided modes, two key photonic properties that typically cannot be utilized simultaneously due to their orthogonality. However, when the NW diameter is controllably modulated along the longitudinal axis on a scale comparable to the wavelength of light-a geometry we term a geometric superlattice (GSL)-we found that NWs can exhibit a much richer and tunable set of nanophotonic properties, as described herein. To understand these unique properties, we first summarize the basic optical properties of uniform-diameter NWs using Mie scattering theory and dispersion relations, and we describe both conventional and relatively new microscopy methods that experimentally probe the optical properties of single NWs. Next, delving into the properties of NW GSLs, we summarize their ability to couple a Mie resonance with a guided mode at a select wavevector (or wavelength) dictated by their geometric pitch. The coupling forms a bound guided state (BGS) with a standing wave profile, which allows a NW GSL to serve as a spectrally selective light coupler and to act as optical switch or sensor. We also summarize the capacity of a GSL to trap light by serving as an ultrahigh (theoretically infinite) quality factor optical cavity with an optical bound state in the continuum (BIC), in which destructive interference prevents coupling to and from the far field. Finally, we discuss a future research outlook for using ENGRAVE NWs for nanoscale light control. For instance, we highlight research avenues that could yield light-emitting devices by interfacing a NW-based BIC with emissive materials such as quantum dots, 2D materials, and hybrid perovskite. We also discuss the design of photonic band gaps, generation of high-harmonics with quasi-BIC structures, and the possibility for undiscovered nanophotonic properties and phenomena through more complex ENGRAVE geometric designs.

Abrupt degenerately-doped silicon nanowire tunnel junctions.

We have confirmed the presence of narrow, degenerately-doped axial silicon nanowire (SiNW) p-n junctions via off-axis electron holography (EH). SiNWs were grown via the vapor-solid-liquid (VLS) mechanism using gold (Au) as the catalyst, silane (SiH4), diborane (B2H6) and phosphine (PH3) as the precursors, and hydrochloric acid (HCl) to stabilize the growth. Two types of growth were carried out, and in each case we explored growth with both n/p and p/n sequences. In the first type, we abruptly switched the dopant precursors at the desired junction location, and in the second type we slowed the growth rate at the junction to allow the dopants to readily leave the Au catalyst. We demonstrate degenerately-doped p/n and n/p nanowire segments with abrupt potential profiles of 1.02 ± 0.02 and 0.86 ± 0.3 V, and depletion region widths as narrow as 10 ± 1 nm via EH. Low temperature current-voltage measurements show an asymmetric curvature in the forward direction that resemble planar gold-doped tunnel junctions, where the tunneling current is hidden by a large excess current. The results presented herein show that the direct VLS growth of degenerately-doped axial SiNW p-n junctions is feasible, an essential step in the fabrication of more complex SiNW-based devices for electronics and solar energy.

Optical Bound States in the Continuum with Nanowire Geometric Superlattices.

Perfect trapping of light in a subwavelength cavity is a key goal in nanophotonics. Perfect trapping has been realized with optical bound states in the continuum (BIC) in waveguide arrays and photonic crystals; yet the formal requirement of infinite periodicity has limited the experimental realization to structures with macroscopic planar dimensions. We characterize BICs in a silicon nanowire (NW) geometric superlattice (GSL) that exhibits one-dimensional periodicity in a compact cylindrical geometry with a subwavelength diameter. We analyze the scattering behavior of NW GSLs by formulating temporal coupled mode theory to include Lorenz-Mie scattering, and we show that GSL-based BICs can trap electromagnetic energy for an infinite lifetime and exist over a broad range of geometric parameters. Using synthesized NW GSLs tens of microns in length and with variable pitch, we demonstrate the progressive spectral shift and disappearance of Fano resonances in experimental single-NW extinction spectra as a manifestation of BIC GSL modes.

Mapping Free-Carriers in Multijunction Silicon Nanowires Using Infrared Near-Field Optical Microscopy.

We report the use of infrared (IR) scattering-type scanning near-field optical microscopy (s-SNOM) as a nondestructive method to map free-carriers in axially modulation-doped silicon nanowires (SiNWs) with nanoscale spatial resolution. Using this technique, we can detect local changes in the electrically active doping concentration based on the infrared free-carrier response in SiNWs grown using the vapor-liquid-solid (VLS) method. We demonstrate that IR s-SNOM is sensitive to both p-type and n-type free-carriers for carrier densities above ∼1 × 1019 cm-3. We also resolve subtle changes in local conductivity properties, which can be correlated with growth conditions and surface effects. The use of s-SNOM is especially valuable in low mobility materials such as boron-doped p-type SiNWs, where optimization of growth has been difficult to achieve due to the lack of information on dopant distribution and junction properties. s-SNOM can be widely employed for the nondestructive characterization of nanostructured material synthesis and local electronic properties without the need for contacts or inert atmosphere.

Probing Intrawire, Interwire, and Diameter-Dependent Variations in Silicon Nanowire Surface Trap Density with Pump-Probe Microscopy.

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.

All-in-One Derivatized Tandem p+n-Silicon-SnO2/TiO2 Water Splitting Photoelectrochemical Cell.

Mesoporous metal oxide film electrodes consisting of derivatized 5.5 µm thick SnO2 films with an outer 4.3 nm shell of TiO2 added by atomic layer deposition (ALD) have been investigated to explore unbiased water splitting on p, n, and p+n type silicon substrates. Modified electrodes were derivatized by addition of the water oxidation catalyst, [Ru(bda)(4-O(CH2)3PO3H2)-pyr)2], 1, (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate), and chromophore, [Ru(4,4'-PO3H2-bpy) (bpy)2]2+, RuP2+, (bpy = 2,2'-bipyridine), which form 2:1 RuP2+/1 assemblies on the surface. At pH 5.7 in 0.1 M acetate buffer, these electrodes with a fluorine-doped tin oxide (FTO) back contact under ∼1 sun illumination (100 mW/cm2; white light source) perform efficient water oxidation with a photocurrent of 1.5 mA/cm2 with an 88% Faradaic efficiency (FE) for O2 production at an applied bias of 600 mV versus RHE ( ACS Energy Lett. , 2016 , 1 , 231 - 236 ). The SnO2/TiO2-chromophore-catalyst assembly was integrated with the Si electrodes by a thin layer of titanium followed by an amorphous TiO2 (Ti/a-TiO2) coating as an interconnect. In the integrated electrode, p+n-Si-Ti/a-TiO2-SnO2/TiO2|-2RuP2+/1, the p+n-Si junction provided about 350 mV in added potential to the half cell. In photolysis experiments at pH 5.7 in 0.1 M acetate buffer, bias-free photocurrents approaching 100 µA/cm2 were obtained for water splitting, 2H2O → 2H2 + O2. The FE for water oxidation was 79% with a hydrogen efficiency of ∼100% at the Pt cathode.

Self-Catalyzed Vapor-Liquid-Solid Growth of Lead Halide Nanowires and Conversion to Hybrid Perovskites.

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 ⟨1̅21̅0⟩ 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) perovskite while maintaining the NW morphology. Single-NW experiments comparing measured extinction spectra with optical simulations show that the NWs exhibit a strong optical antenna effect, leading to substantially enhanced scattering efficiencies and to absorption efficiencies that can be more than twice that of thin films of the same thickness. Further development of the self-catalyzed VLS mechanism for lead halide and perovskite NWs should enable the rational design of nanostructures for various optoelectronic technologies, including potentially unique applications such as hot-carrier solar cells.

Enhancement of Light Absorption in Silicon Nanowire Photovoltaic Devices with Dielectric and Metallic Grating Structures.

We report the enhancement of light absorption in Si nanowire photovoltaic devices with one-dimensional dielectric or metallic gratings that are fabricated by a damage-free, precisely aligning, polymer-assisted transfer method. Incorporation of a Si3N4 grating with a Si nanowire effectively enhances the photocurrents for transverse-electric polarized light. The wavelength at which a maximum photocurrent is generated is readily tuned by adjusting the grating pitch. Moreover, the electrical properties of the nanowire devices are preserved before and after transferring the Si3N4 gratings onto Si nanowires, ensuring that the quality of pristine nanowires is not degraded during the transfer. Furthermore, we demonstrate Si nanowire photovoltaic devices with Ag gratings using the same transfer method. Measurements on the fabricated devices reveal approximately 27.1% enhancement in light absorption compared to that of the same devices without the Ag gratings without any degradation of electrical properties. We believe that our polymer-assisted transfer method is not limited to the fabrication of grating-incorporated nanowire photovoltaic devices but can also be generically applied for the implementation of complex nanoscale structures toward the development of multifunctional optoelectronic devices.

Capillarity-Driven Welding of Semiconductor Nanowires for Crystalline and Electrically Ohmic Junctions.

Semiconductor nanowires (NWs) have been demonstrated as a potential platform for a wide-range of technologies, yet a method to interconnect functionally encoded NWs has remained a challenge. Here, we report a simple capillarity-driven and self-limited welding process that forms mechanically robust and Ohmic inter-NW connections. The process occurs at the point-of-contact between two NWs at temperatures 400-600 °C below the bulk melting point of the semiconductor. It can be explained by capillarity-driven surface diffusion, inducing a localized geometrical rearrangement that reduces spatial curvature. The resulting weld comprises two fused NWs separated by a single, Ohmic grain boundary. We expect the welding mechanism to be generic for all types of NWs and to enable the development of complex interconnected networks for neuromorphic computation, battery and solar cell electrodes, and bioelectronic scaffolds.

Imaging Spatial Variations in the Dissipation and Transport of Thermal Energy within Individual Silicon Nanowires Using Ultrafast Microscopy.

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.

Doubling absorption in nanowire solar cells with dielectric shell optical antennas.

Semiconductor nanowires (NWs) often exhibit efficient, broadband light absorption despite their relatively small size. This characteristic originates from the subwavelength dimensions and high refractive indices of the NWs, which cause a light-trapping optical antenna effect. As a result, NWs could enable high-efficiency but low-cost solar cells using small volumes of expensive semiconductor material. Nevertheless, the extent to which the antenna effect can be leveraged in devices will largely determine the economic viability of NW-based solar cells. Here, we demonstrate a simple, low-cost, and scalable route to dramatically enhance the optical antenna effect in NW photovoltaic devices by coating the wires with conformal dielectric shells. Scattering and absorption measurements on Si NWs coated with shells of SiN(x) or SiO(x) exhibit a broadband enhancement of light absorption by ∼ 50-200% and light scattering by ∼ 200-1000%. The increased light-matter interaction leads to a ∼ 80% increase in short-circuit current density in Si photovoltaic devices under 1 sun illumination. Optical simulations reproduce the experimental results and indicate the dielectric-shell effect to be a general phenomenon for groups IV, II-VI, and III-V semiconductor NWs in both lateral and vertical orientations, providing a simple route to approximately double the efficiency of NW-based solar cells.

Coaxial multishell nanowires with high-quality electronic interfaces and tunable optical cavities for ultrathin photovoltaics.

Silicon nanowires (NWs) could enable low-cost and efficient photovoltaics, though their performance has been limited by nonideal electrical characteristics and an inability to tune absorption properties. We overcome these limitations through controlled synthesis of a series of polymorphic core/multishell NWs with highly crystalline, hexagonally-faceted shells, and well-defined coaxial (p/n) and p/intrinsic/n (p/i/n) diode junctions. Designed 200-300 nm diameter p/i/n NW diodes exhibit ultralow leakage currents of approximately 1 fA, and open-circuit voltages and fill-factors up to 0.5 V and 73%, respectively, under one-sun illumination. Single-NW wavelength-dependent photocurrent measurements reveal size-tunable optical resonances, external quantum efficiencies greater than unity, and current densities double those for silicon films of comparable thickness. In addition, finite-difference-time-domain simulations for the measured NW structures agree quantitatively with the photocurrent measurements, and demonstrate that the optical resonances are due to Fabry-Perot and whispering-gallery cavity modes supported in the high-quality faceted nanostructures. Synthetically optimized NW devices achieve current densities of 17 mA/cm(2) and power-conversion efficiencies of 6%. Horizontal integration of multiple NWs demonstrates linear scaling of the absolute photocurrent with number of NWs, as well as retention of the high open-circuit voltages and short-circuit current densities measured for single NW devices. Notably, assembly of 2 NW elements into vertical stacks yields short-circuit current densities of 25 mA/cm(2) with a backside reflector, and simulations further show that such stacking represents an attractive approach for further enhancing performance with projected efficiencies of > 15% for 1.2 µm thick 5 NW stacks.

Reversible strain-induced electron-hole recombination in silicon nanowires observed with femtosecond pump-probe microscopy.

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.