Understanding the electronic transport of metal-semiconductor heterojunctions is of utmost importance for a wide range of emerging nanoelectronic devices like adaptive transistors, biosensors, and quantum devices. Here, we provide a comparison and in-depth discussion of the investigated Schottky heterojunction devices based on Si and Ge nanowires contacted with pure single-crystal Al. Key for the fabrication of these devices is the selective solid-state metal-semiconductor exchange of Si and Ge nanowires into Al, delivering void-free, single-crystal Al contacts with flat Schottky junctions, distinct from the bulk counterparts. Thereof, a systematic comparison of the temperature-dependent charge carrier injection and transport in Si and Ge by means of current-bias spectroscopy is visualized by 2D colormaps. Thus, it reveals important insights into the operation mechanisms and regimes that cannot be exploited by conventional single-sweep output and transfer characteristics. Importantly, it was found that the Al-Si system shows symmetric effective Schottky barrier (SB) heights for holes and electrons, whereas the Al-Ge system reveals a highly transparent contact for holes due to Fermi level pinning close to the valence band with charge carrier injection saturation due to a thinned effective SB. Moreover, thermionic field emission limits the overall electron conduction, indicating a distinct SB for electrons.
Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer N-triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl2 molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities. Local structural differences and the copper content, i.e., whether full or partial occupancy of the intralayer cavity occurs, were found to be dependent on the reaction temperature and Cu-containing salt. Crystallites of Cu-coordinated PTI were also found to electrophoretically deposit from aqueous particle suspensions onto either graphite or FTO electrodes. As a result, electrocatalytic current densities for the reduction of CO2 and H2O reached as high as â¼10 to 50 mA cm-2, and remained stable for >2 days. Selectivity for the reduction of CO2 to CO vs. H2 increases for thinner crystals as well as for when two Cu cations coordinate within the intralayer cavities of PTI. Mechanistic calculations have also revealed the electrocatalytic activity for CO2 reduction requires a smaller thermodynamic driving force with two neighboring Cu atoms per cavity as compared to a single Cu atom. These results thus establish a useful synthetic pathway to metal-coordination in a crystalline carbon nitride and show great potential for mediating stable CO2 reduction at sizable current densities.
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 â¼30 times compared with pure dielectric structures and plasmon resonances with optical confinement enhanced up to â¼5 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.
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 â¼10 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.
Overcoming the difficulty in the precise definition of the metal phase of metal-Si heterostructures is among the key prerequisites to enable reproducible next-generation nanoelectronic, optoelectronic, and quantum devices. Here, we report on the formation of monolithic Al-Si heterostructures obtained from both bottom-up and top-down fabricated Si nanostructures and Al contacts. This is enabled by a thermally induced Al-Si exchange reaction, which forms abrupt and void-free metal-semiconductor interfaces in contrast to their bulk counterparts. The selective and controllable transformation of Si NWs into Al provides a nanodevice fabrication platform with high-quality monolithic and single-crystalline Al contacts, revealing resistivities as low as ρ = (6.31 ± 1.17) × 10-8 Ω m and breakdown current densities of Jmax = (1 ± 0.13) × 1012 Ω m-2. Combining transmission electron microscopy and energy-dispersive X-ray spectroscopy confirmed the composition as well as the crystalline nature of the presented Al-Si-Al heterostructures, with no intermetallic phases formed during the exchange process in contrast to state-of-the-art metal silicides. The thereof formed single-element Al contacts explain the robustness and reproducibility of the junctions. Detailed and systematic electrical characterizations carried out on back- and top-gated heterostructure devices revealed symmetric effective Schottky barriers for electrons and holes. Most importantly, fulfilling compatibility with modern complementary metal-oxide semiconductor fabrication, the proposed thermally induced Al-Si exchange reaction may give rise to the development of next-generation reconfigurable electronics relying on reproducible nanojunctions.
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 °C, 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 was 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 most closely matching with the partially-disorder 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 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.
Graphite/chemistry , Nanostructures/chemistry , Neurons/radiation effects , Animals , Electrochemical Techniques , Lasers , Nanowires/chemistry , Neurons/physiology , Photochemical Processes , Rats , Spheroids, Cellular/physiology , Spheroids, Cellular/radiation effects
