Epitaxially Grown Silicon Nanowires with a Gold Molecular Adhesion Layer for Core/Shell Structures with Compact Mie and Plasmon Resonances.

Noble-metal plasmonic nanostructures have attracted much attention because they can support deep-subwavelength optical resonances, yet their performance tends to be limited by high Ohmic absorption losses. In comparison, high-index dielectric materials can support low-loss optical resonances but do not tend to yield the same subwavelength optical confinement. Here, we combine these two approaches and examine the dielectric-plasmonic resonances in dielectric/metal core/shell nanowires. Si nanowires were grown epitaxially from (111) substrates, and direct deposition of Au on these structures by physical vapor deposition yielded nonconformal Au islands. However, by introduction of a molecular adhesion layer prior to deposition, cylindrical Si/Au core/shell nanostructures with conformal metal shells were successfully fabricated. Examining these structures as optical cavities using both optical simulations and experimental extinction measurements, we found that the structures support Mie resonances with quality factors enhanced up to ∼30 times compared with pure dielectric structures and plasmon resonances with optical confinement enhanced up to ∼5 times compared with pure metallic structures. Interestingly, extinction spectra of both Mie and plasmon resonances yield Fano line shapes, whose manifestation can be attributed to the combination of high quality factor resonances, Mie-plasmon coupling, and phase delay of the background optical field. This work demonstrates a bottom-up synthetic method for the production of freestanding, cylindrically symmetric semiconductor/metal core/shell nanowires that enables the efficient trapping of light on deep-subwavelength length scales for varied applications in photonics and optoelectronics.

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.

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.

Insight into refractive index modulation as route to enhanced light coupling in semiconductor nanowires.

Recent developments in chemical processes to prepare single-crystalline nanowire (NW) superlattices (SLs) have discovered a range of unique nanophotonic properties. In particular, diameter-modulated silicon NW geometric SLs (GSLs) have shown their ability to produce complex interference effects through which enhanced light manipulation is achieved. Here, we re-imagine the origin of the complex interference effects occurring in shallow-modulated GSLs and present a refractive index modulation as a key deciding factor. We introduce the design of a NW refractive index SL (ISL), a hypothetical uniform-diameter NW in which the refractive index is periodically modulated, and explain the coupling effect between Mie resonance and bound guided state. We apply the ISL concept to other NW SL systems and suggest potential routes to bring substantial enhancements in lasing activities.

Large-Area, Highly Crystalline DNA-Assembled Metasurfaces Exhibiting Widely Tunable Epsilon-Near-Zero Behavior.

Metasurfaces prepared via bottom-up nanoparticle assembly enable the deliberate manipulation of light in the optical regime, resulting in media with various engineered optical responses. Here, we report a scalable method to grow highly crystalline 2D metasurfaces composed of colloidal gold nanocubes, over macroscopic areas, using DNA-mediated assembly under equilibrium conditions. Using an effective medium description, we predict that these plasmonic metasurfaces behave as dielectric media with high refractive indices that can be dynamically tuned by tuning DNA length. Furthermore, we predict that, when coupled with an underlying thin gold film, the real permittivity of these metasurfaces exhibits a crossover region between positive and negative values, known as the epsilon-near-zero (ENZ) condition, which can be tuned between 1.5 and 2.6 µm by changing DNA length. Optical characterization performed on the DNA-assembled metasurfaces reveals that the predicted optical properties agree well with the measured response. Overall, we propose an efficient method for realizing large-area plasmonic metasurfaces that enable dynamic control over optical characteristics. High-index and ENZ metasurfaces operating in the telecommunications regime could have significant implications in high-speed optical computing, optical communications, optical imaging, and other areas.

Mie-Resonant Three-Dimensional Metacrystals.

Optical metamaterials, engineered to exhibit electromagnetic properties not found in natural materials, may enable new light-based applications including cloaking and optical computing. While there have been significant advances in the fabrication of two-dimensional metasurfaces, planar structures create nontrivial angular and polarization sensitivities, making omnidirectional operation impossible. Although three-dimensional (3D) metamaterials have been proposed, their fabrication remains challenging. Here, we use colloidal crystal engineering with DNA to prepare isotropic 3D metacrystals from Au nanocubes. We show that such structures can exhibit refractive indices as large as ∼8 in the mid-infrared, far greater than that of common high-index dielectrics. Additionally, we report the first observation of multipolar Mie resonances in metacrystals with well-formed habits, occurring in the mid-infrared for submicrometer metacrystals, which we measured using synchrotron infrared microspectroscopy. Finally, we predict that arrays of metacrystals could exhibit negative refraction. The results present a promising platform for engineering devices with unnatural optical properties.

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.

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.

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.

Mie-coupled bound guided states in nanowire geometric superlattices.

All-optical operation holds promise as the future of computing technology, and key components include miniaturized waveguides (WGs) and couplers that control narrow bandwidths. Nanowires (NWs) offer an ideal platform for nanoscale WGs, but their utility has been limited by the lack of a comprehensive coupling scheme with band selectivity. Here, we introduce a NW geometric superlattice (GSL) that allows narrow-band guiding in Si NWs through coupling of a Mie resonance with a bound-guided state (BGS). Periodic diameter modulation creates a Mie-BGS-coupled excitation that manifests as a scattering dark state with a pronounced scattering dip in the Mie resonance. The frequency of the coupled mode, tunable from the visible to near-infrared, is determined by the pitch of the GSL. Using a combined GSL-WG system, we demonstrate spectrally selective guiding and optical switching and sensing at telecommunication wavelengths, highlighting the potential to use NW GSLs for the design of on-chip optical components.

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.

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.

Designing Morphology in Epitaxial Silicon Nanowires: The Role of Gold, Surface Chemistry, and Phosphorus Doping.

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) dopant transitions, which are found to be less than 5 nm in width. The results highlight three mechanistic attributes of the process. First, NW growth in the ⟨111⟩ direction is found to be unstable at high SiH4 partial pressures and growth rates unless using HCl, which stabilizes NW growth through chlorination of the NW sidewall. Second, aggregated Au deposited on the NW surface by the VLS catalyst is found to be immobile on the chlorinated surface and to impede selective wet-chemical etching by potassium hydroxide (KOH) solution, preventing the design of precise morphology. Third, the aggregation of Au is found to be strongly dependent on the SiH4 partial pressure and NW growth rate, and values exceeding ∼100 mTorr and ∼150 nm/min, respectively, are required to minimize Au and thereby enable selective wet-chemical etching. Under optimized growth conditions, we find that abrupt, complex, and arbitrary dopant profiles and morphologies can be encoded in vertical Si NWs, and we expect that a variety of electronic and photonic applications can be realized with these designed nanostructures.

Plasmonic Solar Cells: From Rational Design to Mechanism Overview.

Plasmonic effects have been proposed as a solution to overcome the limited light absorption in thin-film photovoltaic devices, and various types of plasmonic solar cells have been developed. This review provides a comprehensive overview of the state-of-the-art progress on the design and fabrication of plasmonic solar cells and their enhancement mechanism. The working principle is first addressed in terms of the combined effects of plasmon decay, scattering, near-field enhancement, and plasmonic energy transfer, including direct hot electron transfer and resonant energy transfer. Then, we summarize recent developments for various types of plasmonic solar cells based on silicon, dye-sensitized, organic photovoltaic, and other types of solar cells, including quantum dot and perovskite variants. We also address several issues regarding the limitations of plasmonic nanostructures, including their electrical, chemical, and physical stability, charge recombination, narrowband absorption, and high cost. Next, we propose a few potentially useful approaches that can improve the performance of plasmonic cells, such as the inclusion of graphene plasmonics, plasmon-upconversion coupling, and coupling between fluorescence resonance energy transfer and plasmon resonance energy transfer. This review is concluded with remarks on future prospects for plasmonic solar cell use.

Chemically Engraving Semiconductor Nanowires: Using Three-Dimensional Nanoscale Morphology to Encode Functionality from the Bottom Up.

The patterning of semiconductors with nanometer-scale precision is a cornerstone of modern technology. Top-down methods, ranging from photolithography to focused-ion beam milling, are typically used to fabricate complex nanostructures. In this Perspective, we discuss an alternative bottom-up method to encode similar high-resolution morphology in semiconductor nanowires (NWs). This process, termed ENGRAVE for "Encoded Nanowire GRowth and Appearance through VLS and Etching", combines fast modulation of nanowire composition during vapor-liquid-solid (VLS) growth with composition-dependent wet-chemical etching. This method produces cylindrically symmetric structures in which the diameter is modulated on a sub-10 nm axial length scale. The process can produce patterns that range from periodic, centrosymmetric to nonperiodic, asymmetric structures, including gratings, fractals, tapers, ratchets, sinusoids, nanogaps, and nanodots. We discuss the prospect for the ENGRAVE process to become a complementary method of lithographic-like patterning that encodes unique morphologies and physical properties in semiconductors for a range of technologies.