Search

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 and 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.

Conjugated organic chromophores composed of linked donor (D) and acceptor (A) moieties have attracted considerable attention for photoelectrochemical applications. In this work, we compare the optoelectronic properties and photoelectrochemical performance of two D-A-D structural isomers with thiophene-X-carboxylic acid (X denotes 3 and 2 positions) derivatives and 2,1,3-benzothiadiazole as the D and A moieties, respectively. 5,5'-(Benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-3-carboxylic acid), BTD1, and 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxylic acid), BTD2, were employed in the study to understand how structural isomers affect surface attachments within chromophore-catalyst assemblies and their influence on charge-transfer dynamics. Crystal structures revealed that varying the position of the -COOH anchoring group causes the molecules to either contort out of a plane (BTD1) or adopt a near-perfect planar conformation (BTD2). BTD1 and BTD2 were co-loaded with either a water oxidation catalyst, [Ru(2,6-bis(1-methylbenzimidazol-2-yl)pyridine)-(4,4'-((HO)2OPCH2)2-2,2'-bipyridine)(OH2)]2, RuCt2+, or proton reduction catalyst [Ni(P2PhN2C6H4CH2PO3H2)2]2+, NiCt2+, on oxide electrodes to facilitate photodriven water splitting reactions. Emission quenching measurements indicate that both BTD1 and BTD2 inject electrons into n-type SnO2|TiO2 electrodes and holes into p-type NiO semiconductors from their respective excited states at high efficiencies >60%. Photocurrent densities of chromophore-catalyst assemblies obtained using linear sweep voltammetry (LSV) show that BTD2-sensitized photoanodes generate significantly more photocurrent than BTD1-sensitized electrodes; however, both exhibit similar performances at the photocathode. Photoelectrocatyltic measurements demonstrate that both BTD1 and BTD2 performed similarly, generating Faradaic efficiencies of 39 and 38% at the anode or 61 and 79% at the cathode. Transient absorption measurements suggest that the differences between the LSV and photoelectrocatalytic measurements result from the differences in quantum yields of the photogenerated redox equivalents, which is also a reflection of the varying metal oxide surface conformation. Our findings suggest that BTD2 should be investigated further in photocathodic studies since it has the structural advantage of being incorporated into diverse types of chromophore-catalyst assemblies.

Driven by the exceptional optoelectronic performance and prospective applications of organic–inorganic hybrid perovskites (HPs), an array of methods to synthesize and process HPs has been developed...

Photoelectrodes consisting of wide-band gap metal oxides functionalized with chromophores and catalysts are a potential low-cost solution to generate solar fuels from aqueous solution. NiO is a com...

The power conversion efficiency of tandem dye-sensitized photoelectrosynthesis cells is limited by the number of p-type metal oxide semiconductors and chromophores available for the photocathode. H...

Significance Modulation of cellular electrophysiology helps develop an understanding of cellular development and function in healthy and diseased states. We modulate the electrophysiology of neuronal cells in two-dimensional (2D) and 3D assemblies with subcellular precision via photothermal stimulation using a multiscale fuzzy graphene nanostructure. Nanowire (NW)-templated 3D fuzzy graphene (NT-3DFG) nanostructures enable remote, nongenetic photothermal stimulation with laser energies as low as subhundred nanojoules without generating cellular stress. NT-3DFG serves as a powerful toolset for studies of cell signaling within and between in vitro 3D models (human-based organoids and spheroids) and can enable therapeutic interventions., 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.

Bottom-up synthesis of semiconductor nanowires (NWs) by the vapor-liquid-solid (VLS) mechanism has enabled diverse technological applications for these nanomaterials. Unlike metallic NWs, however, it has been challenging to form large-area interconnected NW networks. Here, we generate centimeter-scale meshes of mechanically and electrically interconnected Si NWs by sequentially growing, collapsing, and joining the NWs using a capillarity-driven welding mechanism. We fabricate meshes from VLS-grown NWs ranging in diameter from 20 to 100 nm and find that the meshes are three-dimensional with a thickness ranging from ~ 1 to ~ 10 microns depending on the NW diameter. Optical extinction measurements reveal that the networks are semi-transparent with a color that depends on the absorption and scattering characteristics of individual NWs. Moreover, active voltage contrast imaging of both centimeter- and micron-scale meshes reveals widespread electrical connectivity. Using a sacrificial layer, we demonstrate that the mesh can be liberated from the growth substrate, yielding a highly flexible and transparent film. Electrical transport measurements both on the growth substrate and on liberated, flexible films reveal electrical conduction across a centimeter scale with a sheet resistance of ~ 160–180 kΩ/square that does not change significantly upon bending. Given the ability to encode complex functionality in semiconductor NWs through the VLS process, we believe these meshes of networked NWs could find application as neuromorphic memory, electrode scaffolds, and bioelectronic interfaces.

The performance of dye-sensitized solar cells (DSSCs) depends on the properties and interactions of three fundamental components: the semiconductor, chromophore, and electrolyte. For the electrolyt...

The in-depth understanding of the reported photoelectrochemical properties of the layered carbon nitride, poly(triazine imide)/LiCl (PTI/LiCl), has been limited by the apparent disorder of the Li/H atoms within its framework. To understand and resolve the current structural ambiguities, an optimized one-step flux synthesis (470 oC, 36 h, LiCl/KCl flux) was used to prepare PTI/LiCl and deuterated-PTI/LiCl in high purity. Its structure was characterized by a combination of neutron/X-ray diffraction and transmission electron microscopy. The range of possible Li/H atomic configurations were enumerated for the first time and, combined with total energy calculations, reveals a more complex energetic landscape than previously considered. Experimental data were fitted against all possible structural models, exhibiting the most consistency with a new orthorhombic model (Sp. Grp. Ama2) that also has the lowest total energy. In addition, a new Cu(I)-containing PTI (PTI/CuCl) was prepared with the more strongly scattering Cu(I) cations in place of Li, and which also most closely matched with the partially-disorded structure in Cmc21. Thus, a complex configurational landscape of PTI is revealed to consist of a number of ordered crystalline structures that are new potential synthetic targets, such as with the use of metal-exchange reactions.

The excited-state dynamics in individual Ge nanowires (NWs) are imaged using ultrafast pump–probe microscopy with high spatial (∼600 nm) and temporal (∼500 fs) resolution. Photoexcitation of the NW...

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.

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 (SiH$_{4}$), diborane (B$_{2}$H$_{6}$) and phosphine (PH$_{3}$) 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 $1.02\pm0.02$ and $0.86\pm0.3$ V, and depletion region widths as narrow as $10\pm1$ 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., Comment: 18 pages, 8 figures

Nanoscale materials are frequently coated with surface stabilization layers during growth that prevent flocculation in solution and facilitate processing technologies such as ink-jet device printing. Here, we show that few-nanometer-thick stabilization layers typically used swell in the presence of certain solvents and impart significant stresses to the nanomaterial that remains even after the solvent has evaporated. Solvent swelling of the surface layer dramatically enhances nanomaterial-substrate adhesion via the collapse of the stabilization layer during solvent evaporation, preventing stress relaxation. We demonstrate the stress modulation of Ag, Au, and Si nanowires functionalised with surface polymers and surfactant layers and detect strain levels between 0.1 and 0.6% using atomic force microscopy mechanical measurement and Raman spectroscopy. Dry-transferred nanowires exhibit poor adhesion and show no evidence of incorporated stress but become stressed immediately following solvent exposure. Strain engineering is demonstrated by coating nanowires with few-nanometer-thick solvent-responsive polymer layers.

The combination of Moore's law and Dennard's scaling rules have constituted the fundamental guidelines for the silicon-based semiconductor industry for decades. Furthermore, the enormous growth of global data volume has pushed the demand for complex and densely packed devices. In recent years, it has become clear that wired interconnects impose increasingly severe speed and power limitations onto integrated circuits as scaling slows toward a halt. To overcome these limitations, there is a clear need for optical data processing. Despite significant progress in the development of silicon photonics, light sources remain challenging owing to the indirect bandgap of group IV materials. It is therefore highly desirable to develop new concepts for a silicon light source that meets efficiency and footprint requirements similar to their electronic counterparts. Here, we demonstrate an electrically driven and tunable silicon light source by matching the resonant modes of a silver nanocavity with the hot luminescence spectrum of an avalanching p-n junction. The cavity significantly enhances phonon-assisted recombination of hot carriers by tailoring the local density of states at the size-tunable resonance. Such tunable nanoscale emitter may be of great interest for short-reach communications, microdisplays or lab-on-chip applications.

Interface dynamics of nanocrystalline NiO thin films sensitized with two ruthenium polypyridyl chromophores have been investigated to examine the influence that excited-state dipole orientation and the position of the bipyridine radical formed in the charge-separated state have on interfacial electron transfer yields. In ultrafast transient absorption experiments, the charge separated state is observed on the nanosecond timescale for the trifluoromethyl-substituted chromophore, [Ru(flpy)2(dcb)]2+ (flpy = 4,4′-bis(trifluoromethyl)-2,2′-bipyridine, dcb = 4,4′-dicarboxy-2,2′-bipyridine), but not for [Ru(bpy)2(dcb)]2+ (bpy = 2,2′-bipyridine). Differences are attributed to the positioning of the bipyridine radical formed in the charge separated state; for [Ru(flpy)2(dcb)]2+, the electron is localized on the flpy ligand distal to the surface, whereas for [Ru(bpy)2(dcb)]2+, the electron is localized on the dcb ligand, proximal to the NiO surface. Enhanced photovoltaic performance is observed for dye-sensitized solar cell devices prepared with [Ru(flpy)2(dcb)]2+, demonstrating that enhanced charge separation can be correlated with device efficiency.

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

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 nanostructur...

Although silicon (Si) nanowires (NWs) grown by a vapor-liquid-solid (VLS) mechanism have been demonstrated for a range of photonic, electronic, and solar-energy applications, continued progress with these NW-based technologies requires increasingly precise compositional and morphological control of the growth process. However, VLS growth typically encounters problems such as nonselective deposition on sidewalls, inadvertent kinking, unintentional or inhomogeneous doping, and catalyst-induced compositional gradients. Here, we overcome several of these difficulties and report the synthesis of uniform, linear, and degenerately doped Si NW superlattices with abrupt transitions between p-type, intrinsic, and n-type segments. The synthesis of these structures is enabled by in situ chlorination of the NW surface with hydrochloric acid (HCl) at temperatures ranging from 500 to 700 °C, yielding uniform NWs with minimal nonselective growth. Surprisingly, we find the boron (B) doping level in p-type segments to be at least 1 order of magnitude above the solid solubility limit, an effect that we attribute to a high incorporation of B in the liquid catalyst and kinetic trapping of B during crystallization at the liquid-solid interface to yield a highly nonequilibrium concentration. For growth at 510 °C, four-point-probe measurements yield active doping levels of at least 4.5 × 10

Vertically aligned semiconductor nanowires (NWs) have many potential applications for NW-based technologies, ranging from solar cells to intracellular sensors. Aligned NWs can be fabricated by top-down etching of planar wafers or synthesized from the bottom up using the vapor–liquid–solid (VLS) mechanism to induce epitaxial growth on lattice-matched substrates. The VLS process permits the modulation of dopants along the NW growth axis, which if combined with dopant-dependent wet-chemical etching, can be used to encode precise morphology. However, the synthesis of vertical and linear NWs with complex morphology is nontrivial, requiring control over multiple interdependent aspects of the VLS process. Here, we demonstrate sub-10 nm morphology in ⟨111⟩ epitaxial silicon (Si) NWs grown by the VLS mechanism on (111) Si substrates with gold (Au) catalysts. Using silane (SiH4), phosphine (PH3), and hydrochloric acid (HCl) precursor gases at 480 °C, precise morphology is encoded through abrupt phosphorus (P) dopan...

Localized trap states, which are deleterious to the performance of many solar-energy materials, often originate from the under-coordinated bonding associated with defects. Recently, the concept of targeted atomic deposition (TAD) was introduced as a process that permits the passivation of trap states using a vapor-phase precursor that selectively reacts with only the surface defect sites. Here, we demonstrate the passivation of nickel oxide (NiO) with the TAD process using diborane gas for selective, low-temperature deposition of boron (B) under continuous flow in a chemical vapor deposition (CVD) system. NiO is a ubiquitous cathode material used in dye-sensitized solar cells (DSSCs), organic photovoltaic devices, and organo-lead halide perovskite solar cells. The deposition of B at 100 °C is shown to follow first-order kinetics, exhibiting saturation at a B to Ni atomic ratio of ∼10%. Electrochemical measurements, combined with first-principles calculations, indicate that B passivates Ni vacancy defects ...

For nanomaterials, surface chemistry can dictate fundamental material properties, including charge-carrier lifetimes, doping levels, and electrical mobilities. In devices, surface defects are usually the key limiting factor for performance, particularly in solar-energy applications. Here, we develop a strategy to uniformly and selectively passivate defect sites in semiconductor nanomaterials using a vapor-phase process termed targeted atomic deposition (TAD). Because defects often consist of atomic vacancies and dangling bonds with heightened reactivity, we observe-for the widely used p-type cathode nickel oxide-that a volatile precursor such as trimethylaluminum can undergo a kinetically limited selective reaction with these sites. The TAD process eliminates all measurable defects in NiO, leading to a nearly 3-fold improvement in the performance of dye-sensitized solar cells. Our results suggest that TAD could be implemented with a range of vapor-phase precursors and be developed into a general strategy to passivate defects in zero-, one-, and two-dimensional nanomaterials.

Bottom-up, chemical methods to control the morphology of semiconductor nanostructures are a promising complement to the top-down fabrication techniques that currently dominate the semiconductor industry. Among bottom-up techniques, nanowire (NW) growth using the vapor–liquid–solid (VLS) mechanism has received great attention. In this Highlight article, we review our recent progress toward understanding the microscopic processes that govern VLS NW growth, doping, and dopant modulation. Quantitative measurements of Si NW growth rates and P dopant profiles under a range of synthetic conditions are interpreted with a kinetic analysis of VLS growth that includes the microscopic reactions of incorporation, evaporation, and crystallization. The analysis allows us to identify synthetic conditions that yield both diameter-independent growth rates and abrupt, diameter-independent dopant transitions. The optimized conditions allow precise, sub-10 nm morphology to be encoded along the growth axis of Si NWs, enabling the bottom-up chemical nanofabrication of complex structures that are typically fabricated by high-resolution, top-down lithography.

The ability to modulate cellular electrophysiology is a fundamental aspect for investigation of tissue development, maturation and function. Currently, there is a need for remote, non-genetic, light-induced control of cellular activity in native-like state, three-dimensional (3D) tissues such as spheroids and organoids. Here, we report a breakthrough hybrid-nanomaterial for remote, non-genetic photostimulation of both two-dimensional (2D) and 3D neural cellular systems. We combine one-dimensional (1D) nanowires (NWs) and 2D graphene flakes grown out-of-plane for highly controlled photostimulation at subcellular precision with laser energies lower than hundred nanojoules, 1-2 orders of magnitude lower than Au-, C- and Si-based photostimulation. Photostimulation using NW-templated 3D fuzzy graphene (NT-3DFG) is flexible due to its broadband absorption and does not generate cellular stress. Therefore, it serves a novel powerful toolset for studies of cell signaling within and between tissues and can enable new therapeutic interventions.

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.

Nanowires (NWs) with axial p–i–n junctions have been widely explored as microscopic diodes for optoelectronic and solar energy applications, and their performance is strongly influenced by charge recombination at the surface. We delineate how the photovoltaic performance of these diodes is dictated not only by the surface but also by the complex and seemingly counterintuitive interplay of diode geometry, that is, radius (R) and intrinsic length (Li), with the surface recombination velocity (S). An analytical model to describe these relationships is developed and compared to finite-element simulations, which verify the accuracy and limitations of the model. The dependence of the dark saturation current (I0), internal quantum efficiency (IQE), short-circuit current (ISC), and open-circuit voltage (VOC) on both geometric and recombination parameters demonstrates that no single set of parameters produces optimal performance; instead, various trade-offs in performance are observed. For instance, longer Li migh...

Silicon nanowires have been widely pursued as a technology for electronic, photonic, and renewable energy devices. We developed a bottom-up method—termed ENGRAVE (Encoded Nanowire GRowth and Appearance using VLS and Etching)—to modulate nanowire shape and composition along the growth axis with sub-10 nanometer spatial resolution. Under precisely controlled synthetic conditions, the rapid modulation of phosphorus or boron incorporation during vapor-liquid-solid (VLS) growth can be used to encode a complex pattern of dopants in the wires. Subsequent solution processing can then be used to selectively etch the wires, creating high-resolution structures such as bow-ties, gratings, sawtooths, fractals, nanorods, sinusoids, and nanogaps. Several examples of the complex morphology in degenerately-doped p-type and n-type silicon are shown in Figure 1A and 1B, respectively.

A solid-state mechanochemical synthesis of ZnxCo3−xO4 was developed with highly tunable Zn concentration. Photovoltaic performance was evaluated in dye-sensitized solar cells and tested with various Zn concentrations, exhibiting maximum performance with ZnCo2O4. Oxidative treatments led to a nearly three-fold increase in dye loading and a significant increase in short-circuit current density.

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 bel...

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.

Mesoporous metal oxide film electrodes consisting of derivatized 5.5 μm thick SnO

Semiconductor nanowires (NWs) are often synthesized by the vapor-liquid-solid (VLS) mechanism, a process in which a liquid droplet-supplied with precursors in the vapor phase-catalyzes the growth of a solid, crystalline NW. By changing the supply of precursors, the NW composition can be altered as it grows to create axial heterostructures, which are applicable to a range of technologies. The abruptness of the heterojunction is mediated by the liquid catalyst, which can act as a reservoir of material and impose a lower limit on the junction width. Here, we demonstrate that this "reservoir effect" is not a fundamental limitation and can be suppressed by selection of specific VLS reaction conditions. For Au-catalyzed Si NWs doped with P, we evaluate dopant profiles under a variety of synthetic conditions using a combination of elemental imaging with energy-dispersive X-ray spectroscopy and dopant-dependent wet-chemical etching. We observe a diameter-dependent reservoir effect under most conditions. However, at sufficiently slow NW growth rates (≤250 nm/min) and low reactor pressures (≤40 Torr), the dopant profiles are diameter independent and radially uniform with abrupt, sub-10 nm axial transitions. A kinetic model of NW doping, including the microscopic processes of (1) P incorporation into the liquid catalyst, (2) P evaporation from the catalyst, and (3) P crystallization in the Si NW, quantitatively explains the results and shows that suppression of the reservoir effect can be achieved when P evaporation is much faster than P crystallization. We expect similar reaction conditions can be developed for other NW systems and will facilitate the development of NW-based technologies that require uniform and abrupt heterostructures.

Tandem dye-sensitized solar cells that use nickel oxide as a hole-transport layer have limited performance due to the poor transport properties of NiO; alternative p-type oxides with the correct band alignment, good hole mobility, and stability in corrosive electrolyte must be identified. In this paper, we present our study on the ternary oxide material (zinc–cobalt–oxide spinel) as a hole conductor in a sensitized architecture. Zinc substitution for cobalt in cobalt(II,III) oxide results in good p-type conductivity and a spinel crystal structure. The flatband potential of Zn–Co–O thin films was determined to be around 0.7 V vs NHE (pH 5) and varies slightly depending on the conducting substrate. The films were used as the hole-transport layer in a dye-sensitized solar cell, and the hole-injection current was generated upon sensitization by coumarin-343. The cells exhibited an IQE of >90% and an open-circuit voltage of around 260 mV. The increase in photon-to-electron conversion efficiency of Zn–Co–O over...

Fischer carbenes are commonly used as reagents in the synthesis of new carbon–carbon bonds, a reaction made possible by the unique chemistry of the formal metal–carbon double bond. Nevertheless, the photoinduced reactions of these complexes are relatively poorly understood. For instance, it has been postulated but not confirmed that visible irradiation leads to photocarbonylation, in which a CO ligand inserts into the metal–carbon bond to form a metal ketene intermediate. Here, we report the first direct observation of this intermediate following 400 nm photoexcitation of the model group 6 Fischer carbene Cr(CO)5[CCH3(OCH3)]. Using ultrafast time-resolved infrared spectroscopy (TRIR), we observe the formation of three distinct metal ketene structures, which we assign as a singlet and two isoenergetic triplet excited-state structures. The singlet relaxes to the ground state on a time scale of ∼35 ps, whereas the two triplets are long-lived (>2 ns). TRIR of the tungsten analogue yields no evidence for a met...

Dark-field microscopy (DFM) is widely used to optically image and spectroscopically analyze nanoscale objects. In a typical DFM configuration, a sample is illuminated at oblique angles and an objective lens collects light scattered by the sample at a range of lower angles. Here, we develop waveguide scattering microscopy (WSM) as an alternative technique to image and analyze photonic nanostructures. WSM uses an incoherent white-light source coupled to a dielectric slab waveguide to generate an evanescent field that illuminates objects located within several hundred nanometers of the waveguide surface. Using standard microscope slides or coverslips as the waveguide, we demonstrate high-contrast dark-field imaging of nanophotonic and plasmonic structures such as Si nanowires, Au nanorods, and Ag nanoholes. Scattering spectra collected in the WSM configuration show excellent signal-to-noise with minimal background signal compared to conventional DFM. In addition, the polarization of the incident field is con...

A p-type metal oxide with high surface area and good charge carrier mobility is of paramount importance for development of tandem solar fuel and dye-sensitized solar cell (DSSC) devices. Here, we report the synthesis, hierarchical morphology, electrical properties, and DSSC performance of mesoscale p-type NiO platelets. This material, which exhibits lateral dimensions of 100 nm but thicknesses less than 10 nm, can be controllably functionalized with a high-density array of vertical pores 4–6, 5–9, or 7–23 nm in diameter depending on exact synthetic conditions. Thin films of this porous but still quasi-two-dimensional material retain a high surface area and exhibit electrical mobilities more than 10-fold higher than comparable films of spherical particles with similar doping levels. These advantages lead to a modest, 20–30% improvement in the performance of DSSC devices under simulated 1-sun illumination. The capability to rationally control morphology provides a route for continued development of NiO as a...