Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.
We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO(2), forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.
The development of carbon nanotube-(CNTs-)based gas sensors and sensor arrays has attracted intensive research interest in the last several years because of their potential for the selective and rapid detection of various gaseous species by novel nanostructures integrated in miniature and low-power consuming electronics. Chemiresistors and chemical field effect transistors are probably the most promising types of gas nanosensors. In these sensors, the electrical properties of nanostructures are dramatically changed when exposed to the target gas analytes. In this review, recent progress on the development of different types of CNT-based nanosensors is summarized. The focus was placed on the means used by various researchers to improve the sensing performance (sensitivity, selectivity and response time) through the rational functionalization of CNTs with different methods (covalent and non-covalent) and with different materials (polymers and metals).
Plasmonic metal/semiconductor heterostructures show promise for visible-light-driven photocatalysis. Gold nanorods (AuNRs) semi-coated with TiO2 are expected to be ideally structured systems for hydrogen evolution. Synthesizing such structures by wet-chemistry methods, however, has proved challenging. Here we report the bottom-up synthesis of AuNR/TiO2 nanodumbbells (NDs) with spatially separated Au/TiO2 regions, whose structures are governed by the NRs' diameter, and the higher curvature and lower density of CnTAB surfactant at the NRs' tips than on their lateral surfaces, as well as the morphology's dependence on concentration, and alkyl chain length of CnTAB. The NDs show plasmon-enhanced H2 evolution under visible and near-infrared light.
A fruitful paradigm in the development of low-cost and efficient photovoltaics is to dope or otherwise photosensitize wide band gap semiconductors in order to improve their light harvesting ability for light with sub-band-gap photon energies.(1-8) Here, we report significant photosensitization of TiO2 due to the direct injection by quantum tunneling of hot electrons produced in the decay of localized surface-plasmon polaritons excited in gold nanoparticles (AuNPs) embedded in the semiconductor (TiO2). Surface plasmon decay produces electron-hole pairs in the gold.(9-15) We propose that a significant fraction of these electrons tunnel into the semiconductor's conduction band resulting in a significant electron current in the TiO2 even when the device is illuminated with light with photon energies well below the semiconductor's band gap. Devices fabricated with (nonpercolating) multilayers of AuNPs in a TiO2 film produced over 1000-fold increase in photoconductance when illuminated at 600 nm over what TiO2 films devoid of AuNPs produced. The overall current resulting from illumination with visible light is ∼50% of the device current measured with UV (ℏω>Eg band gap) illumination. The above observations suggest that plasmonic nanostructures (which can be fabricated with absorption properties that cover the full solar spectrum) can function as a viable alternative to organic photosensitizers for photovoltaic and photodetection applications.
That a nanoparticle (NP) (for example of gold) residing above a gold mirror is almost as effective a surface enhanced Raman scattering (SERS) substrate (when illuminated with light of the correct polarization and wavelength) as two closely coupled gold nanoparticles has been known for some time. The NP-overmirror (NPOM) configuration has the valuable advantage that it is amenable to top-down fabrication. We have fabricated a series of Au-NPOM substrates with varying but thin atomic layer-deposited oxide spacer and measured the SERS enhancement as a function of spacer thickness and angle of incidence (AOI). These were compared with high-quality finite-difference time-domain calculations, which reproduce the observed spacer thickness and AOI dependences faithfully. The SERS intensity is expected to be strongly affected by the AOI on account for the fact that the hot spot formed in the space between the NP and the mirror is most efficiently excited with an electromagnetic field component that is normal to the surface of the mirror. Intriguingly we find that the SERS intensity maximizes at ~60° and show that this is due to the coherent superposition of the incident and the reflected field components. The observed SERS intensity is also shown to be very sensitive to the dielectric constant of the oxide spacer layer with the most intense signals obtained when using a low dielectric constant oxide layer (SiO(2)).
We developed a simple and cost-effective fabrication technique to construct a hydrogen nanosensor by decorating single-walled carbon nanotubes with Pd nanoparticles. By varying the sensor's synthesis conditions (e.g., Pd electrodeposition charge, deposition potential, and initial baseline resistance of the SWNT network), the sensing performance was optimized. The optimized sensor showed excellent sensing properties toward hydrogen (ΔR/R of 0.42%/ppm) with a lower detection limit of 100 ppm and a linear response up to 1000 ppm. The response time decreased from tens of minutes to a few minutes with increasing hydrogen concentration at room temperature. The sensor's recovery time improved under humid air conditions compared to dry air conditions.
The conversion of sunlight into electricity by photovoltaics is currently a mature science and the foundation of a lucrative industry. In conventional excitonic solar cells, electron-hole pairs are generated by light absorption in a semiconductor and separated by the "built in" potential resulting from charge transfer accompanying Fermi-level equalization either at a p-n or a Schottky junction, followed by carrier collection at appropriate electrodes. Here we report a stable, wholly plasmonic photovoltaic device in which photon absorption and carrier generation take place exclusively in the plasmonic metal. The field established at a metal-semiconductor Schottky junction separates charges. The negative carriers are high-energy (hot) electrons produced immediately following the plasmon's dephasing. Some of the carriers are energetic enough to clear the Schottky barrier or quantum mechanically tunnel through it, thereby producing the output photocurrent. Short circuit photocurrent densities in the range 70-120 μA cm(-2) were obtained for simulated one-sun AM1.5 illumination with devices based on arrays of parallel gold nanorods, conformally coated with 10 nm TiO2 films and fashioned with a Ti metal collector. For the device with short circuit currents of 120 μA cm(-2), the internal quantum efficiency is ∼2.75%, and its wavelength response tracks the absorption spectrum of the transverse plasmon of the gold nanorods indicating that the absorbed photon-to-electron conversion process resulted exclusively in the Au, with the TiO2 playing a negligible role in charge carrier production. Devices fabricated with 50 nm TiO2 layers had open-circuit voltages as high as 210 mV, short circuit current densities of 26 μA cm(-2), and a fill factor of 0.3. For these devices, the TiO2 contributed a very small but measurable fraction of the charge carriers.
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