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.

Diazonium-Functionalized Silicon Hybrid Photoelectrodes: Film Thickness and Composition Effects on Photoelectrochemical Behavior.

Aryl diazonium electrografting is a powerful method for imparting molecular functionality onto various substrates by forming a stable carbon-surface covalent bond. While the high reactivity of the aryl radical intermediate makes this method fast and reliable, it can also lead to the formation of an insulating and disordered multilayer film. These thick films affect electrochemical performance, especially for semiconductor substrates used in photoelectrochemical applications. We studied the effects of film thickness and composition by electrografting in situ-generated aminobenzene diazonium salts onto both n-type and p-type silicon electrodes at fixed potentials. Next, we attached ferrocene to the amine-terminated films and probed their (photo)electrochemical behavior. Cyclic voltammetry measurements showed decreased electrochemical reversibility with increasing diazonium film thickness; this reversibility was restored when ferrocene was incorporated throughout the film with a layer-by-layer deposition process. Finally, we compared the behavior of dark p-type electrodes to n-type photoelectrodes and observed differences in the electrochemical reversibility that we attribute to the change in potential drop across the two interfaces.

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.

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 Nonlinearity in Silicon Nanowires Enabled by Bound States in the Continuum.

Intense electromagnetic fields localized within resonant photonic nanostructures provide versatile opportunities for engineering nonlinear optical effects on a subwavelength scale. For dielectric structures, optical bound states in the continuum (BICs, resonant nonradiative modes that exist within the radiation continuum) are an emerging strategy to localize and intensify fields. Here, we report efficient second and third harmonic generation from Si nanowires (NWs) encoded with BIC and quasi-BIC resonances. In situ dopant modulation during vapor-liquid-solid NW growth was followed by wet-chemical etching to periodically modulate the diameter of the Si NWs and create cylindrically symmetric geometric superlattices (GSLs) with precisely defined axial and radial dimensions. By variation of the GSL structure, BIC and quasi-BIC resonant conditions were created to span visible and near-infrared optical frequencies. To probe the optical nonlinearity of these structures, we collected linear extinction spectra and nonlinear spectra from single-NW GSLs, demonstrating that quasi-BIC spectral positions at the fundamental frequency are directly correlated with enhanced harmonic generation at second and third harmonic frequencies. Interestingly, we find that deliberate geometric detuning from the BIC condition leads to a quasi-BIC resonance with maximal harmonic generation efficiency by providing a balance between the capacity to trap light and the capacity to couple to the external radiation continuum. Moreover, under focused illumination, as few as 30 geometric unit cells are required to achieve more than 90% of the approximate maximum theoretical efficiency of an infinite structure, indicating that nanostructures with projected areas smaller than ∼10 µm2 can support quasi-BICs for efficient harmonic generation. The results represent an important step toward the design of efficient harmonic generation at the nanoscale and further highlight the photonic utility of BICs at optical frequencies in ultracompact one-dimensional nanostructures.

Ratcheting quasi-ballistic electrons in silicon geometric diodes at room temperature.

Ratcheting effects play an important role in systems ranging from mechanical socket wrenches to biological motor proteins. The underlying principle is to convert a fluctuating, unbiased force into unidirectional motion. Here, we report the ratcheting of electrons at room temperature using a semiconductor nanowire with precisely engineered asymmetry. Modulation of the nanowire diameter creates a cylindrical sawtooth geometry with broken inversion symmetry on a nanometer-length scale. In a two-terminal device, this structure responded as a three-dimensional geometric diode that funnels electrons preferentially in one direction through specular reflection of quasi-ballistic electrons at the nanowire surface. The ratcheting effect causes charge rectification at frequencies exceeding 40 gigahertz, demonstrating the potential for applications such as high-speed data processing and long-wavelength energy harvesting.

Interplay of Surface Recombination and Diode Geometry for the Performance of Axial p-i-n Nanowire Solar Cells.

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 might be expected to produce higher ISC, yet at high values of S the ISC declines because of decreases in IQE. Moreover, longer Li produces a concurrent decline in VOC regardless of S due to increases in I0. We also find that ISC and VOC trends are radius independent, yet I0 is directly proportional to R, causing NWs with smaller R to display higher turn-on voltages. The analysis regarding the interplay of these parameters, verified by experimental measurements with various p-i-n geometries and surface treatments, provides clear guidance for the rational design of performance metrics for photodiode and photovoltaic devices.

Encoding Highly Nonequilibrium Boron Concentrations and Abrupt Morphology in p-Type/n-Type Silicon Nanowire Superlattices.

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 × 1019 cm-3, which is comparable to the phosphorus (P) doping level of n-type segments. Because the B and P dopants are in sufficiently high concentrations for the Si to be degenerately doped, both segments inhibit the etching of Si in aqueous potassium hydroxide (KOH) solution. Moreover, we find that the dopant transitions are abrupt, facilitating nanoscale morphological control in both B- and P-doped segments through selective KOH etching of the NW with a spatial resolution of ∼10 nm. The results presented herein enable the growth of complex, degenerately doped p-n junction nanostructures that can be explored for a variety of advanced applications, such as Esaki diodes, multijunction solar cells, and tunneling field-effect transistors.