Nanoscale materials are promising for optoelectronic devices because their physical dimensions are on the order of the wavelength of light. This leads to a variety of complex optical phenomena that, for instance, enhance absorption and emission. However, quantifying the performance of these nanoscale devices frequently requires measuring absolute absorption at the nanoscale, and remarkably, there is no general method capable of doing so directly. Here, we present such a method based on an integrating sphere but modified to achieve submicron spatial resolution. We explore the limits of this technique by using it to measure spatial and spectral absorptance profiles on a wide variety of nanoscale systems, including different combinations of weakly and strongly absorbing and scattering nanomaterials (Si and GaAs nanowires, Au nanoparticles). This measurement technique provides quantitative information about local optical properties that are crucial for improving any optoelectronic device with nanoscale dimensions or nanoscale surface texturing.

Ag nanoparticles (NPs) are deposited on BiVO 4 photoanodes to study their effect on the photoelectrochemical (PEC) water splitting performance of the semiconductor. 15 nm light-absorbing NPs and 65 nm light scattering NPs were studied separately to compare their light trapping ability for enhancing the semiconductor's absorption through light concentration and light scattering, respectively. The 15 nm NPs enhanced the BiVO 4 external quantum efficiency throughout the semiconductor's absorption range (e.g., % 2.5 fold at l = 400 nm). However, when a hole scavenger was added to the electrolyte, no enhancement was observed upon NP deposition, indicating that the NPs only facilitate the injection of holes from the semiconductor surface to the electrolyte but do not enhance its absorption. On the other hand, the 65 nm scattering NPs not only facilitated hole injection to the electrolyte, but also enhanced the absorption of the semiconductor (by % 6 %) through light scattering. Such a dual effect, i.e., of enhancing both the surface properties and the absorption of the semiconductor, makes light scattering Ag NPs an ideal decoration for PEC water splitting photoelectrodes.The collective oscillation of valence electrons in metal nanoparticles (NPs) resulting from their electromagnetic interaction with light is known as surface plasmon resonance (SPR). As a result of this phenomenon, metal NPs can either absorb or scatter the irradiating light.[1] The photon frequencies in which the SPR takes place (i.e., the resonant frequencies) depend on the material, shape and size of the NPs.[1] Noble metal NPs (e.g., Ag and Au) exhibit resonance frequencies within the visible spectrum and are great candidate materials in solar energy conversion devices (e.g., photovoltaic and photocatalytic). [2][3][4][5][6] It has been shown that the incident energy absorbed by plasmonic NPs can be transferred to a nearby semiconducting photoelectrode, thereby enhancing its performance. [3][4][5][7][8][9] As a result, many noble metal NP/semiconductor systems have been studied to date, in particular to improve the rate of solar photoelectrochemical reactions (e.g., water splitting for hydrogen generation and phenol degradation for water purification). [4,8,[10][11][12][13][14][15][16][17] In many of these studies, the improvement of the semiconductor's performance, upon plasmonic NP functionalization, has been explained by a light trapping mechanism called local electromagnetic field enhancement or light concentration. In this mechanism, the SPR significantly enhances the intensity of the incoming electromagnetic field (e.g., solar radiation) in the vicinity of the NP, which locally increases the absorption in a nearby semiconductor. [3][4][5]7] Increasing the absorption in the vicinity of the NPs is advantageous when the NPs are placed at the semiconductor-electrolyte interface since, in this case, the absorption increase takes place in the semiconductor space-charge layer where the electron-hole pairs are more efficiently separated. In...

Photogenerated hot electrons from plasmonic nanostructures are very promising for photocatalysis, mostly due to their potential for enhanced chemical selectivity. Here, we present a self-optimized fabrication method of plasmonic photocathodes using hot-electron chemistry, for enhanced photocatalytic efficiencies. Plasmonic Au/TiO2 nanoislands are excited at their surface plasmon resonance to generate hot electrons in an aqueous bath containing a platinum (cocatalyst) precursor. Hot electrons drive the deposition of Pt cocatalyst nanoparticles, without any nanoparticle functionalization and negligible applied bias, close to the hotspots of the plasmonic nanoislands. The presence of TiO2 is crucial for achieving higher chemical reaction rates. The Au/TiO2/Pt photocathodes synthesized using hot-electron chemistry show a photocatalytic activity of up to 2 times higher than that of a control made with random electrodeposited Pt nanoparticles. This light-driven positioning of the cocatalyst close to the same positions where hot electrons are most efficiently generated and transferred represents a novel and simple method for synthesizing complex, self-optimized photocatalytic nanostructures with improved efficiency and selectivity.

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/cm 2 , 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/cm 2 by incorporating a back-reflector and improved antireflection, for which we estimate a photovoltaic efficiency above 21% for 1 μm thick Si cells.

Hot electrons generated in metal nanoparticles can drive chemical reactions and selectively deposit cocatalyst materials on the plasmonic hotspots, the areas where the decay of plasmons takes place and the hot electrons are created. While hot electrons have been extensively used for nanomaterial formation, the utilization of hot holes for simultaneous cocatalyst deposition has not yet been explored. Herein, we demonstrate that hot holes can drive an oxidation reaction for the deposition of the manganese oxide (MnO x ) cocatalyst on different plasmonic gold (Au) nanostructures on a thin titanium dioxide (TiO 2 ) layer, excited at their surface plasmon resonance. An 80% correlation between the hot-hole deposition sites and the simulated plasmonic hotspot location is showed when considering the typical hot-hole diffusion length. Simultaneous deposition of more than one cocatalyst is also achieved on one of the investigated plasmonic systems (Au plasmonic nanoislands) through the hot-hole oxidation of a manganese salt and the hot-electron reduction of a platinum precursor in the same solution. These results add more flexibility to the use of hot carriers and open up the way for the design of complex photocatalytic nanostructures.

Thin, flexible and invisible solar cells will be an ubiquitous technology in the near future. Ultrathin crystalline silicon (c-Si) cells capitalise on the success of bulk silicon cells while being light-weight 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. 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, the enhanced light trapping translates to a record efficiency above 15%. The light absorption can potentially be increased up to 33.8 mA/cm2 by incorporating a back-reflector and improved anti-reflection, for which we estimate a photovoltaic efficiency above 21% for 1 µm thick Si cells.

Nanostructured semiconductors feature resonant optical modes that confine light absorption in specific areas called “hot spots”. These areas can be used for localized extraction of the photogenerated charges, which in turn could drive chemical reactions for synthesis of catalytic materials. In this work, we use these nanophotonic hot spots in vertical silicon nanowires to locally deposit platinum nanoparticles in a photo-electrochemical system. The tapering angle of the silicon nanowires as well as the excitation wavelength are used to control the location of the hot spots together with the deposition sites of the platinum catalyst. A combination of finite difference time domain (FDTD) simulations with scanning electron microscopy image analysis showed a reasonable correlation between the simulated hot spots and the actual experimental localization and quantity of platinum atoms. This nanophotonic approach of driving chemical reactions at the nanoscale using the optical properties of the photo-electrode, can be very promising for the design of lithography-free and efficient hierarchical nanostructures for the generation of solar fuels.

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