Unveiling Nanoscale Heterogeneities at the Bias-Dependent Gold-Electrolyte Interface.

Electrified solid-liquid interfaces (SLIs) are extremely complex and dynamic, affecting both the dynamics and selectivity of reaction pathways at electrochemical interfaces. Enabling access to the structure and arrangement of interfacial water in situ with nanoscale resolution is essential to develop efficient electrocatalysts. Here, we probe the SLI energy of a polycrystalline Au(111) electrode in a neutral aqueous electrolyte through in situ electrochemical atomic force microscopy. We acquire potential-dependent maps of the local interfacial adhesion forces, which we associate with the formation energy of the electric double layer. We observe nanoscale inhomogeneities of interfacial adhesion force across the entire map area, indicating local differences in the ordering of the solvent/ions at the interface. Anion adsorption has a clear influence on the observed interfacial adhesion forces. Strikingly, the adhesion forces exhibit potential-dependent hysteresis, which depends on the local gold grain curvature. Our findings on a model electrode extend the use of scanning probe microscopy to gain insights into the local molecular arrangement of the SLI in situ, which can be extended to other electrocatalysts.

High Aspect Ratio Silver Nanogrids by Bottom-Up Electrochemical Growth as Transparent Electrode.

A scalable selective-area electrochemical method is reported for the fabrication of interconnected metal nanostructures. In this work, the fabrication of silver nanowire grids for the application of transparent electrodes is explored. The presented method is based on a through-the-mask electrodeposition method, where the mask is made by using substrate conformal imprint lithography. We find that the nucleation density of the silver nanoparticles is the key parameter for successful homogeneous void-free filling of the template. We independently controlled the density of the silver nuclei and their growth by using a double potential pulse. The silver nanowire grids show high transmission (95.9%) and low sheet resistance (as low as 3.7 Ω/sq), resulting in a superior figure of merit (FoM). Due to the bottom-up nature of this technique, arbitrarily high aspect ratio nanowires can be achieved, therefore decreasing the sheet resistance without affecting transmittance and carrier collection. The presented method can be generalized to the large-area nanofabrication of any well-defined nanostructure design of any metal transparent electrode for multiple applications.

Optical Characterization of Plasmonic Indium Lattices Fabricated via Electrochemical Deposition.

The optical properties of periodic metallic nanoparticle lattices have found many exciting applications. Indium is an emerging plasmonic material that offers to extend the plasmonic applications given by gold and silver from the visible to the ultraviolet spectral range, with applications in imaging, sensing, and lasing. Due to the high vapor pressure/low melting temperature of indium, nanofabrication of ordered metallic nanoparticles is nontrivial. In this work, we show the potential of selective area electrochemical deposition to generate large-area lattices of In pillars for plasmonic applications. We study the optical response of the In lattices by means of angle-dependent extinction measurements demonstrating strong plasmonic surface lattice resonances and a good agreement with numerical simulations. The results open avenues toward high-quality lattices of plasmonic indium nanoparticles and can be extended to other promising plasmonic materials that can be electrochemically grown.

The role of Pb oxidation state of the precursor in the formation of 2D perovskite microplates.

Two-dimensional (2D) lead halide perovskites are an exciting class of materials currently being extensively explored for photovoltaics and other optoelectronic applications. Their ionic nature makes them ideal candidates for solution processing into both thin films and nanostructured crystals. Understanding how 2D lead halide perovskite crystals form is key towards full control over their physical properties, which may enable new physical phenomena and devices. Here, we investigate the effects of the Pb oxidation state of the initial inorganic precursor on the growth of pure-phase (n = 1) - Popper 2D perovskite BA2PbI4 in single-step synthesis. We examine the different crystallisation routes in exposing PbO2 and PbI2 powders to a BAI : IPA organo-halide solution, by combining in situ optical microscopy, UV-VIS spectroscopy and time-resolved high performance liquid chromatography. So far, works using PbO2 to synthesise 3D LHPs introduce a preceding step to reduce PbO2 into either PbO or PbI2. In this work, we find that BA2PbI4 is directly formed when exposing PbO2 to BAI : IPA without the need for an external reducing agent. We explain this phenomenon by the spontaneous reduction/oxidation of PbO2/BAI that occurs under iodine-rich conditions. We observe differences in the final morphology (rectangles vs. octagons) and nanocrystal growth rate, which we explain through the different chemistry and iodoplumbate complexes involved in each case. As such, this work spans the horizon of usable lead precursors and offers a new turning knob to control crystal growth in single-step LHP synthesis.

Influence of the crystallographic texture of ITO on the electrodeposition of silver nanoparticles.

The electrochemical control over nucleation and growth of metal nanoparticles on foreign substrates is an active field of research, where the surface properties of the substrate have a key role in nucleation dynamics. Polycrystalline indium tin oxide (ITO) films are highly desired substrates for many optoelectronic applications, for which the only parameter that is often specified is the sheet resistance. As a result, growth on ITO is highly irreproducible. Here, we show that ITO substrates with same technical specifications (i.e. sheet resistance, light transmittance and roughness) and supplier may still have different crystalline texture, which we find it has a strong impact on the nucleation and growth of silver nanoparticles during electrodeposition. We find that the preferential presence of lower index surfaces leads to few orders of magnitude lower island density, which is strongly dependent on the nucleation pulse potential. By contrast, the island density on ITO with preferential 〈111〉 orientation is barely affected by the nucleation pulse potential. This work highlights the importance of reporting the surface properties of polycrystalline substrates when presenting nucleation studies and metal nanoparticle electrochemical growth.

Ion Current Rectification and Long-Range Interference in Conical Silicon Micropores.

Fluidic devices exhibiting ion current rectification (ICR), or ionic diodes, are of broad interest for applications including desalination, energy harvesting, and sensing, among others. For such applications a large conductance is desirable, which can be achieved by simultaneously using thin membranes and wide pores. In this paper we demonstrate ICR in micrometer sized conical channels in a thin silicon membrane with pore diameters comparable to the membrane thickness but both much larger than the electrolyte screening length. We show that for these pores the entrance resistance is key not only to Ohmic conductance around 0 V but also for understanding ICR, both of which we measure experimentally and capture within a single analytic theoretical framework. The only fit parameter in this theory is the membrane surface potential, for which we find that it is voltage dependent and its value is excessively large compared to the literature. From this we infer that surface charge outside the pore strongly contributes to the observed Ohmic conductance and rectification by a different extent. We experimentally verify this hypothesis in a small array of pores and find that ICR vanishes due to pore-pore interactions mediated through the membrane surface, while Ohmic conductance around 0 V remains unaffected. We find that the pore-pore interaction for ICR is set by a long-ranged decay of the concentration which explains the surprising finding that the ICR vanishes for even a sparsely populated array with a pore-pore spacing as large as 7 µm.

Over 65% Sunlight Absorption in a 1 µm Si Slab with Hyperuniform Texture.

Thin, flexible, and invisible solar cells will be a ubiquitous technology in the near future. Ultrathin crystalline silicon (c-Si) cells capitalize on the success of bulk silicon cells while being lightweight and mechanically flexible, but suffer from poor absorption and efficiency. Here we present a new family of surface texturing, based on correlated disordered hyperuniform patterns, capable of efficiently coupling the incident spectrum into the silicon slab optical modes. We experimentally demonstrate 66.5% solar light absorption in free-standing 1 µm c-Si layers by hyperuniform nanostructuring for the spectral range of 400 to 1050 nm. The absorption equivalent photocurrent derived from our measurements is 26.3 mA/cm2, which is far above the highest found in literature for Si of similar thickness. Considering state-of-the-art Si PV technologies, we estimate that the enhanced light trapping can result in a cell efficiency above 15%. The light absorption can potentially be increased up to 33.8 mA/cm2 by incorporating a back-reflector and improved antireflection, for which we estimate a photovoltaic efficiency above 21% for 1 µm thick Si cells.

Confined pulsed diffuse layer charging for nanoscale electrodeposition with an STM.

Regulating the state of the solid-liquid interface by means of electric fields is a powerful tool to control electrochemistry. In scanning probe systems, this can be confined closely to a scanning (nano)electrode by means of fast potential pulses, providing a way to probe the interface and control electrochemical reactions locally, as has been demonstrated in nanoscale electrochemical etching. For this purpose, it is important to know the spatial extent of the interaction between pulses applied to the tip, and the substrate. In this paper we use a framework of diffuse layer charging to describe the localization of electrical double layer charging in response to a potential pulse at the probe. Our findings are in good agreement with literature values obtained in electrochemical etching. We show that the pulse can be much more localized by limiting the diffusivity of the ions present in solution, by confined electrodeposition of cobalt in a dimethyl sulfoxide solution, using an electrochemical scanning tunnelling microscope. Finally, we demonstrate the deposition of cobalt nanostructures (<100 nm) using this method. The presented framework therefore provides a general route for predicting and controlling the time-dependent region of interaction between an electrochemical scanning probe and the surface.

Directional quantum dot emission by soft-stamping on silicon Mie resonators.

We present a soft-stamping method to selectively print a homogenous layer of CdSeTe/ZnS core-shell quantum dots (QDs) on top of an array of Si nanocylinders with Mie-type resonant modes. Using this new method, we gain accurate control of the quantum dot's angular emission through engineered coupling of the QDs to these resonant modes. Using numerical simulations we show that the emission into or away from the Si substrate can be precisely controlled by the QD position on the nanocylinder. QDs centered on a 400 nm diameter nanocylinder surface show 98% emission directionality into the Si substrate. Alternatively, for homogenous ensembles placed over the nanocylinder top-surface, the upward emission is enhanced 10-fold for 150 nm diameter cylinders. Experimental PL intensity measurements corroborate the simulated trends with cylinder diameter. PL lifetime measurements reflect well the variations of the local density of states at the QD position due to coupling to the resonant cylinders. These results demonstrate that the soft imprint technique provides a unique manner to directly integrate optical emitters with a wide range of nanophotonic geometries, with potential applications in LEDs, luminescent solar concentrators, and up- and down-conversion schemes for improved photovoltaics.

Photonics for Photovoltaics: Advances and Opportunities.

Photovoltaic systems have reached impressive efficiencies, with records in the range of 20-30% for single-junction cells based on many different materials, yet the fundamental Shockley-Queisser efficiency limit of 34% is still out of reach. Improved photonic design can help approach the efficiency limit by eliminating losses from incomplete absorption or nonradiative recombination. This Perspective reviews nanopatterning methods and metasurfaces for increased light incoupling and light trapping in light absorbers and describes nanophotonics opportunities to reduce carrier recombination and utilize spectral conversion. Beyond the state-of-the-art single junction cells, photonic design plays a crucial role in the next generation of photovoltaics, including tandem and self-adaptive solar cells, and to extend the applicability of solar cells in many different ways. We address the exciting research opportunities and challenges in photonic design principles and fabrication that will accelerate the massive upscaling and (invisible) integration of photovoltaics into every available surface.

Directed nanoscale metal deposition by the local perturbation of charge screening at the solid-liquid interface.

Understanding and directing electrochemical reactions below the micrometer scale is a long-standing challenge in electrochemistry. Confining reactions to nanoscale areas paradoxically requires both isolation from and communication with the bulk electrolyte in terms of electrochemical potential and access of ions, respectively. Here, we demonstrate the directed electrochemical deposition of copper nanostructures by using an oscillating nanoelectrode operated with an atomic force microscope (AFM). Strikingly, the writing is only possible in highly dilute electrolytes and for a particular combination of AFM and electrochemical parameters. We propose a mechanism based on cyclic charging and discharging of the electrical double layer (EDL). The extended screening length and slower charge dynamics in dilute electrolytes allow the nanoelectrode to operate inside, and disturb, the EDL even for large oscillation amplitudes (∼100 nm). Our unique approach can not only be used for controlled additive nano-fabrication but also provides insights into ion behavior and EDL dynamics at the solid-liquid interface.

Combining 1D and 2D waveguiding in an ultrathin GaAs NW/Si tandem solar cell.

As an effective means to surpass the Shockley-Queisser efficiency limit, tandem solar cells have been successfully designed and used for years. However, there are still economical and design set-backs hampering the terrestrial implementation of tandem solar cells. Introducing high efficiency, thin Si-based tandem cells that are flexible in design (shape and curvature) will be the next major step towards integrating highly efficient solar cells into fashionable designs of today's buildings and technologies. In this work we present an optically coupled tandem cell that consists of a GaAs nanowire array on a 2µm-thick Si film as the top and bottom cells, respectively. By performing FDTD simulations, we show that coupling the incident light to guided modes of the 1D wires not only boosts the absorption in the wires, but also efficiently transfers the below bandgap photons to the Si bottom cell. Due to diffraction by the nanowire array the momentum of the transmitted light is matched to that of guided modes of the 2D Si thin film. Consequently, infrared light is up to four times more efficiently trapped in the Si bottom cell compared to when the film is not covered by the nanowires.

Visual Understanding of Light Absorption and Waveguiding in Standing Nanowires with 3D Fluorescence Confocal Microscopy.

Semiconductor nanowires are promising building blocks for next-generation photonics. Indirect proofs of large absorption cross sections have been reported in nanostructures with subwavelength diameters, an effect that is even more prominent in vertically standing nanowires. In this work we provide a three-dimensional map of the light around vertical GaAs nanowires standing on a substrate by using fluorescence confocal microscopy, where the strong long-range disruption of the light path along the nanowire is illustrated. We find that the actual long-distance perturbation is much larger in size than calculated extinction cross sections. While the size of the perturbation remains similar, the intensity of the interaction changes dramatically over the visible spectrum. Numerical simulations allow us to distinguish the effects of scattering and absorption in the nanowire leading to these phenomena. This work provides a visual understanding of light absorption in semiconductor nanowire structures, which is of high interest for solar energy conversion applications.

Morphology and composition of oxidized InAs nanowires studied by combined Raman spectroscopy and transmission electron microscopy.

Any device exposed to ambient conditions will be prone to oxidation. This may be of particular importance for semiconductor nanowires because of the high surface-to-volume ratio and only little is known about the consequences of oxidation for these systems. Here, we study the properties of indium arsenide nanowires which were locally oxidized using a focused laser beam. Polarization dependent micro-Raman measurements confirmed the presence of crystalline arsenic, and transmission electron microscopy diffraction showed the presence of indium oxide. The surface dependence of the oxidation was investigated in branched nanowires grown along the [Formula: see text] and [Formula: see text] wurtzite crystal directions exhibiting different surface facets. The oxidation did not occur at the [Formula: see text] direction. The origin of this selectivity is discussed in terms transition state kinetics of the free surfaces of the different crystal families of the facets and numerical simulations of the laser induced heating.

From Twinning to Pure Zincblende Catalyst-Free InAs(Sb) Nanowires.

III-V nanowires are candidate building blocks for next generation electronic and optoelectronic platforms. Low bandgap semiconductors such as InAs and InSb are interesting because of their high electron mobility. Fine control of the structure, morphology, and composition are key to the control of their physical properties. In this work, we present how to grow catalyst-free InAs1-xSbx nanowires, which are stacking fault and twin defect-free over several hundreds of nanometers. We evaluate the impact of their crystal phase purity by probing their electrical properties in a transistor-like configuration and by measuring the phonon-plasmon interaction by Raman spectroscopy. We also highlight the importance of high-quality dielectric coating for the reduction of hysteresis in the electrical characteristics of the nanowire transistors. High channel carrier mobilities and reduced hysteresis open the path for high-frequency devices fabricated using InAs1-xSbx nanowires.

Modulation of fluorescence signals from biomolecules along nanowires due to interaction of light with oriented nanostructures.

High aspect ratio nanostructures have gained increasing interest as highly sensitive platforms for biosensing. Here, well-defined biofunctionalized vertical indium arsenide nanowires are used to map the interaction of light with nanowires depending on their orientation and the excitation wavelength. We show how nanowires act as antennas modifying the light distribution and the emitted fluorescence. This work highlights an important optical phenomenon in quantitative fluorescence studies and constitutes an important step for future studies using such nanostructures.

Efficient Multiterminal Spectrum Splitting via a Nanowire Array Solar Cell.

Nanowire-based solar cells opened a new avenue for increasing conversion efficiency and rationalizing material use by growing different III-V materials on silicon substrates. Here, we propose a multiterminal nanowire solar cell design with a theoretical conversion efficiency of 48.3% utilizing an efficient lateral spectrum splitting between three different III-V material nanowire arrays grown on a flat silicon substrate. This allows choosing an ideal material combination to achieve the proper spectrum splitting as well as fabrication feasibility. The high efficiency is possible due to an enhanced absorption cross-section of standing nanowires and optimization of the geometric parameters. Furthermore, we propose a multiterminal contacting scheme that can be fabricated with a technology close to standard CMOS. As an alternative we also consider a single power source with a module level voltage matching. These new concepts open avenues for next-generation solar cells for terrestrial and space applications.

Light generation and harvesting in a van der Waals heterostructure.

Two-dimensional (2D) materials are a new type of materials under intense study because of their interesting physical properties and wide range of potential applications from nanoelectronics to sensing and photonics. Monolayers of semiconducting transition metal dichalcogenides MoS2 or WSe2 have been proposed as promising channel materials for field-effect transistors. Their high mechanical flexibility, stability, and quality coupled with potentially inexpensive production methods offer potential advantages compared to organic and crystalline bulk semiconductors. Due to quantum mechanical confinement, the band gap in monolayer MoS2 is direct in nature, leading to a strong interaction with light that can be exploited for building phototransistors and ultrasensitive photodetectors. Here, we report on the realization of light-emitting diodes based on vertical heterojunctions composed of n-type monolayer MoS2 and p-type silicon. Careful interface engineering allows us to realize diodes showing rectification and light emission from the entire surface of the heterojunction. Electroluminescence spectra show clear signs of direct excitons related to the optical transitions between the conduction and valence bands. Our p-n diodes can also operate as solar cells, with typical external quantum efficiency exceeding 4%. Our work opens up the way to more sophisticated optoelectronic devices such as lasers and heterostructure solar cells based on hybrids of 2D semiconductors and silicon.

BiVO4 thin film photoanodes grown by chemical vapor deposition.

BiVO4 thin film photoanodes were grown by vapor transport chemical deposition on FTO/glass substrates. By controlling the flow rate, the temperatures of the Bi and V sources (Bi metal and V2O5 powder, respectively), and the temperature of the deposition zone in a two-zone furnace, single-phase monoclinic BiVO4 thin films can be obtained. The CVD-grown films produce global AM1.5 photocurrent densities up to 1 mA cm(-2) in aqueous conditions in the presence of a sacrificial reagent. Front illuminated photocatalytic performance can be improved by inserting either a SnO2 hole blocking layer and/or a thin, extrinsically Mo doped BiVO4 layer between the FTO and the CVD-grown layer. The incident photon to current efficiency (IPCE), measured under front illumination, for BiVO4 grown directly on FTO/glass is about 10% for wavelengths below 450 nm at a bias of +0.6 V vs. Ag/AgCl. For BiVO4 grown on a 40 nm SnO2/20 nm Mo-doped BiVO4 back contact, the IPCE is increased to over 40% at wavelengths below 420 nm.