Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO2 Reduction in Aqueous Electrolytes.

We report the light-induced modification of catalytic selectivity for photoelectrochemical CO2 reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO2 reduction on the Cu surface, while charge separation is accomplished by hot-hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts increased selectivity for CO2 reduction over hydrogen evolution in aqueous electrolytes. Specifically, we observed that plasmon-driven CO2 reduction increased the production of carbon monoxide and formate, while simultaneously reducing the evolution of hydrogen. Our results demonstrate an optical route toward steering the selectivity of artificial photosynthetic systems with plasmon-driven photocathodes for photoelectrochemical CO2 reduction in aqueous media.

Radiation Tolerant Nanowire Array Solar Cells.

Space power systems require photovoltaics that are lightweight, efficient, reliable, and capable of operating for years or decades in space environment. Current solar panels use planar multijunction, III-V based solar cells with very high efficiency, but their specific power (power to weight ratio) is limited by the added mass of radiation shielding (e.g., coverglass) required to protect the cells from the high-energy particle radiation that occurs in space. Here, we demonstrate that III-V nanowire-array solar cells have dramatically superior radiation performance relative to planar solar cell designs and show this for multiple cell geometries and materials, including GaAs and InP. Nanowire cells exhibit damage thresholds ranging from ∼10-40 times higher than planar control solar cells when subjected to irradiation by 100-350 keV protons and 1 MeV electrons. Using Monte Carlo simulations, we show that this improvement is due in part to a reduction in the displacement density within the wires arising from their nanoscale dimensions. Radiation tolerance, combined with the efficient optical absorption and the improving performance of nanowire photovoltaics, indicates that nanowire arrays could provide a pathway to realize high-specific-power, substrate-free, III-V space solar cells with substantially reduced shielding requirements. More broadly, the exceptional reduction in radiation damage suggests that nanowire architectures may be useful in improving the radiation tolerance of other electronic and optoelectronic devices.

Quantifying the role of surface plasmon excitation and hot carrier transport in plasmonic devices.

Harnessing photoexcited "hot" carriers in metallic nanostructures could define a new phase of non-equilibrium optoelectronics for photodetection and photocatalysis. Surface plasmons are considered pivotal for enabling efficient operation of hot carrier devices. Clarifying the fundamental role of plasmon excitation is therefore critical for exploiting their full potential. Here, we measure the internal quantum efficiency in photoexcited gold (Au)-gallium nitride (GaN) Schottky diodes to elucidate and quantify the distinct roles of surface plasmon excitation, hot carrier transport, and carrier injection in device performance. We show that plasmon excitation does not influence the electronic processes occurring within the hot carrier device. Instead, the metal band structure and carrier transport processes dictate the observed hot carrier photocurrent distribution. The excellent agreement with parameter-free calculations indicates that photoexcited electrons generated in ultra-thin Au nanostructures impinge ballistically on the Au-GaN interface, suggesting the possibility for hot carrier collection without substantial energy losses via thermalization.

Hot Hole Collection and Photoelectrochemical CO2 Reduction with Plasmonic Au/p-GaN Photocathodes.

Harvesting nonequilibrium hot carriers from plasmonic-metal nanostructures offers unique opportunities for driving photochemical reactions at the nanoscale. Despite numerous examples of hot electron-driven processes, the realization of plasmonic systems capable of harvesting hot holes from metal nanostructures has eluded the nascent field of plasmonic photocatalysis. Here, we fabricate gold/p-type gallium nitride (Au/p-GaN) Schottky junctions tailored for photoelectrochemical studies of plasmon-induced hot-hole capture and conversion. Despite the presence of an interfacial Schottky barrier to hot-hole injection of more than 1 eV across the Au/p-GaN heterojunction, plasmonic Au/p-GaN photocathodes exhibit photoelectrochemical properties consistent with the injection of hot holes from Au nanoparticles into p-GaN upon plasmon excitation. The photocurrent action spectrum of the plasmonic photocathodes faithfully follows the surface plasmon resonance absorption spectrum of the Au nanoparticles and open-circuit voltage studies demonstrate a sustained photovoltage during plasmon excitation. Comparison with Ohmic Au/p-NiO heterojunctions confirms that the vast majority of hot holes generated via interband transitions in Au are sufficiently hot to inject above the 1.1 eV interfacial Schottky barrier at the Au/p-GaN heterojunction. We further investigated plasmon-driven photoelectrochemical CO2 reduction with the Au/p-GaN photocathodes and observed improved selectivity for CO production over H2 evolution in aqueous electrolytes. Taken together, our results offer experimental validation of photoexcited hot holes more than 1 eV below the Au Fermi level and demonstrate a photoelectrochemical platform for harvesting hot carriers to drive solar-to-fuel energy conversion.

Hot-Carrier-Mediated Photon Upconversion in Metal-Decorated Quantum Wells.

Manipulating the frequency of electromagnetic waves forms the core of many modern technologies, ranging from imaging and spectroscopy to radio and optical communication. The process of converting photons from higher to lower energy is easily accomplished and technologically widespread. However, upconversion, which is the process of converting lower-energy photons into higher-energy photons, is still a growing field of study with nascent applications and burgeoning interest. Here, we experimentally demonstrate a new photon upconversion technique mediated by hot carriers in plasmonic nanostructures. Hot holes and hot electrons generated via plasmon decay in illuminated metal nanoparticles are injected into an adjacent semiconductor quantum well where they radiatively recombine to emit higher-energy photons. Using GaN/InGaN quantum wells decorated with gold and silver nanoparticles, we show photon upconversion from 2.4 to 2.8 eV. The process scales linearly with illumination power and enables both geometry- and polarization-based tunability. The conversion of plasmonic losses into upconverted optical emission has the potential to impact bioimaging, on-chip wavelength conversion, and high-efficiency photovoltaics.

Personal thermal management by metallic nanowire-coated textile.

Heating consumes large amount of energy and is a primary source of greenhouse gas emission. Although energy-efficient buildings are developing quickly based on improving insulation and design, a large portion of energy continues to be wasted on heating empty space and nonhuman objects. Here, we demonstrate a system of personal thermal management using metallic nanowire-embedded cloth that can reduce this waste. The metallic nanowires form a conductive network that not only is highly thermal insulating because it reflects human body infrared radiation but also allows Joule heating to complement the passive insulation. The breathability and durability of the original cloth is not sacrificed because of the nanowires' porous structure. This nanowire cloth can efficiently warm human bodies and save hundreds of watts per person as compared to traditional indoor heaters.

Electrolessly deposited electrospun metal nanowire transparent electrodes.

Metal nanowire (MNW) transparent electrodes have been widely developed for their promising sheet resistance (R(s))-transmittance (T) performance, excellent mechanical flexibility, and facile synthesis. How to lower the junction resistance without compromising optical transmittance has become the key issue in enhancing their performance. Here we combine electrospinning and electroless deposition to synthesize interconnected, ultralong MNW networks. For both silver and copper nanowire networks, the R(s) and T values reach around 10 Ω/sq and 90%, respectively. This process is scalable and takes place at ambient temperature and pressure, which opens new opportunities for flexible electronics and roll-to-roll large-scale manufacturing.