Reaction mechanism of the Me3AuPMe3-H2 plasma-enhanced ALD process.

The reaction mechanism of the recently reported Me3AuPMe3-H2 plasma gold ALD process was investigated using in situ characterization techniques in a pump-type ALD system. In situ RAIRS and in vacuo XPS measurements confirm that the CH3 and PMe3 ligands remain on the gold surface after chemisorption of the precursor, causing self-limiting adsorption. Remaining surface groups are removed by the H2 plasma in the form of CH4 and likely as PHxMey groups, allowing chemisorption of new precursor molecules during the next exposure. The decomposition behaviour of the Me3AuPMe3 precursor on a Au surface is also presented and linked to the stability of the precursor ligands that govern the self-limiting growth during ALD. Desorption of the CH3 ligands occurs at all substrate temperatures during evacuation to high vacuum, occurring faster at higher temperatures. The PMe3 ligand is found to be less stable on a gold surface at higher substrate temperatures and is accompanied by an increase in precusor decomposition on a gold surface, indicating that the temperature dependent stability of the precursor ligands is an important factor to ensure self-limiting precursor adsorption during ALD. Remarkably, precursor decomposition does not occur on a SiO2 surface, in situ transmission absorption infrared experiments indicate that nucleation on a SiO2 surface occurs on Si-OH groups. Finally, we comment on the use of different co-reactants during PE-ALD of Au and we report on different PE-ALD growth with the reported O2 plasma and H2O process in pump-type versus flow-type ALD systems.

Thermal atomic layer deposition of gold nanoparticles: controlled growth and size selection for photocatalysis.

Gold nanoparticles have been extensively studied for their applications in catalysis. For Au nanoparticles to be catalytically active, controlling the particle size is crucial. Here we present a low temperature (105 °C) thermal atomic layer deposition approach for depositing gold nanoparticles on TiO2 with controlled size and loading using trimethylphosphino-trimethylgold(iii) and two co-reactants (ozone and water) in a fluidized bed reactor. We show that the exposure time of the precursors is a variable that can be used to decouple the Au particle size from the loading. Longer exposures of ozone narrow the particle size distribution, while longer exposures of water broaden it. By studying the photocatalytic activity of Au/TiO2 nanocomposites, we show how the ability to control particle size and loading independently can be used not only to enhance performance but also to investigate structure-property relationships. This study provides insights into the mechanism underlying the formation and evolution of Au nanoparticles prepared for the first time via vapor phase atomic layer deposition. Employing a vapor deposition technique for the synthesis of Au/TiO2 nanocomposites eliminates the shortcomings of conventional liquid-based processes opening up the possibility of highly controlled synthesis of materials at large scale.

Plasma-Enhanced Atomic Layer Deposition of Nanostructured Gold Near Room Temperature.

A plasma-enhanced atomic layer deposition (PE-ALD) process to deposit metallic gold is reported, using the previously reported Me3Au(PMe3) precursor with H2 plasma as the reactant. The process has a deposition window from 50 to 120 °C with a growth rate of 0.030 ± 0.002 nm per cycle on gold seed layers, and it shows saturating behavior for both the precursor and reactant exposure. X-ray photoelectron spectroscopy measurements show that the gold films deposited at 120 °C are of higher purity than the previously reported ones (<1 at. % carbon and oxygen impurities and <0.1 at. % phosphorous). A low resistivity value was obtained (5.9 ± 0.3 µΩ cm), and X-ray diffraction measurements confirm that films deposited at 50 and 120 °C are polycrystalline. The process forms gold nanoparticles on oxide surfaces, which coalesce into wormlike nanostructures during deposition. Nanostructures grown at 120 °C are evaluated as substrates for free-space surface-enhanced Raman spectroscopy (SERS) and exhibit an excellent enhancement factor that is without optimization, only one order of magnitude weaker than state-of-the-art gold nanodome substrates. The reported gold PE-ALD process therefore offers a deposition method to create SERS substrates that are template-free and does not require lithography. Using this process, it is possible to deposit nanostructured gold layers at low temperatures on complex three-dimensional (3D) substrates, opening up opportunities for the application of gold ALD in flexible electronics, heterogeneous catalysis, or the preparation of 3D SERS substrates.

Polarization-dependent properties of the cladding modes of a single mode fiber covered with gold nanoparticles.

The properties of the high order cladding modes of standard optical fibers are measured in real-time during the deposition of gold nanoparticle layers by chemical vapor deposition (CVD). Using a tilted fiber Bragg grating (TFBG), the resonance wavelength and peak-to-peak amplitude of a radially polarized cladding mode resonance located 51 nm away from the core mode reflection resonance shift by 0.17 nm and 13.54 dB respectively during the formation of a ~200 nm thick layer. For the spectrally adjacent azimuthally polarized resonance, the corresponding shifts are 0.45 nm and 16.34 dB. In both cases, the amplitudes of the resonance go through a pronounced minimum of about 5 dB for thickness between 80 and 100 nm and at the same time the wavelengths shift discontinuously. These effects are discussed in terms of the evolving metallic boundary conditions perceived by the cladding modes as the nanoparticles grow. Scanning Electron Micrographs and observations of cladding mode light scattering by nanoparticle layers of various thicknesses reveal a strong correlation between the TFBG polarized transmission spectra, the grain size and fill factor of the nanoparticles, and the scattering efficiency. This allows the preparation of gold nanoparticle layers that strongly discriminate between radially and azimuthally polarized cladding mode evanescent fields, with important consequences in the plasmonic properties of these layers.