Plasmon-enhanced water splitting on TiO2-passivated GaP photocatalysts.

Integrating plasmon resonant nanostructures with photocatalytic semiconductors shows great promise for high efficiency photocatalytic water splitting. However, the electrochemical instability of most III-V semiconductors severely limits their applicability in photocatalysis. In this work, we passivate p-type GaP with a thin layer of n-type TiO2 using atomic layer deposition. The TiO2 passivation layer prevents corrosion of the GaP, as evidenced by atomic force microscopy and photoelectrochemical measurements. In addition, the TiO2 passivation layer provides an enhancement in photoconversion efficiency through the formation of a charge separating pn-region. Plasmonic Au nanoparticles deposited on top of the TiO2-passivated GaP further increases the photoconversion efficiency through local field enhancement. These two enhancement mechanisms are separated by systematically varying the thickness of the TiO2 layer. Because of the tradeoff between the quickly decaying plasmonic fields and the formation of the pn-charge separation region, an optimum performance is achieved for a TiO2 thickness of 0.5 nm. Finite difference time domain (FDTD) simulations of the electric field profiles in this photocatalytic heterostructure corroborate these results. The effects of plasmonic enhancement are distinguished from the natural catalytic properties of Au by evaluating similar photocatalytic TiO2/GaP structures with catalytic, non-plasmonic metals (i.e., Pt) instead of Au. This general approach of passivating narrower band gap semiconductors enables a wider range of materials to be considered for plasmon-enhanced photocatalysis for high efficiency water splitting.

Plasmonic hot spots: nanogap enhancement vs. focusing effects from surrounding nanoparticles.

Thin Au films (~5 nm) are known to form island-like structures with small gaps between the islands, which produce intense electric field "hot spots" under visible illumination. In this work, we perform finite difference time domain (FDTD) simulations based on experimentally observed high resolution transmission electron microscope (HRTEM) images of these films in order to study the nature of the "hot spots" in more detail. Specifically, we study the dependence of the electric field intensity in the hot spots on the surrounding film environment and on the size of the nanogaps. From our simulations, we show that the surrounding film contributes significantly to the electric field intensity at the hot spot by focusing energy to it. Widening of the gap size causes a decrease in the intensity at the hot spot. However, these island-like nanoparticle hot spots are far less sensitive to gap size than nanoparticle dimer geometries, studied previously. In fact, the main factor in determining the hot spot intensity is the focusing effect of the surrounding nano-islands. We show that these random Au island films outperform more sophisticated geometries of spherical nanoparticle clusters that have been optimized using an iterative optimization algorithm.

Plasmon resonant enhancement of photocatalytic water splitting under visible illumination.

We demonstrate plasmonic enhancement of photocatalytic water splitting under visible illumination by integrating strongly plasmonic Au nanoparticles with strongly catalytic TiO2. Under visible illumination, we observe enhancements of up to 66× in the photocatalytic splitting of water in TiO2 with the addition of Au nanoparticles. Above the plasmon resonance, under ultraviolet radiation we observe a 4-fold reduction in the photocatalytic activity. Electromagnetic simulations indicate that the improvement of photocatalytic activity in the visible range is caused by the local electric field enhancement near the TiO2 surface, rather than by the direct transfer of charge between the two materials. Here, the near-field optical enhancement increases the electron-hole pair generation rate at the surface of the TiO2, thus increasing the amount of photogenerated charge contributing to catalysis. This mechanism of enhancement is particularly effective because of the relatively short exciton diffusion length (or minority carrier diffusion length), which otherwise limits the photocatalytic performance. Our results suggest that enhancement factors many times larger than this are possible if this mechanism can be optimized.

Plasmonic nanoparticle arrays with nanometer separation for high-performance SERS substrates.

We demonstrate a method for fabricating arrays of plasmonic nanoparticles with separations on the order of 1 nm using an angle evaporation technique. Samples fabricated on thin SiN membranes are imaged with high-resolution transmission electron microscopy (HRTEM) to resolve the small separations achieved between nanoparticles. When irradiated with laser light, these nearly touching metal nanoparticles produce extremely high electric field intensities, which result in surface-enhanced Raman spectroscopy (SERS) signals. We quantify these enhancements by depositing a p-aminothiophenol dye molecule on the nanoparticle arrays and spatially mapping their Raman intensities using confocal micro-Raman spectroscopy. Our results show significant enhancement when the incident laser is polarized parallel to the axis of the nanoparticle pairs, whereas no enhancement is observed for the perpendicular polarization. These results demonstrate proof-of-principle of this fabrication technique. Finite difference time domain simulations based on HRTEM images predict an electric field intensity enhancement of 82400 at the center of the nanoparticle pair and an electromagnetic SERS enhancement factor of 10(9)-10(10).