Electric field control of structure, dimensionality, and reactivity of gold nanoclusters on metal-supported MgO films

Electric field control of the structure, dimensionality, and reactivity of gold nanoclusters (Au*(20)) deposited on MgO films of various thicknesses supported on Ag(100) are introduced and studied using first-principles electronic structure calculations. Field-controlled interfacial charging and field-induced dimensionality crossover are predicted. For a field E(z)=1 V/nm, an optimal planar Au(20) island on MgO(8 layers)/Ag(100) is determined, while for E(z)=0, the preferred structure of the cluster is a tetrahedron. Field control of the reactivity of the adsorbed nanocluster with O(2) is discussed.     

Exploring the 2D to 3D dimensionality crossover in thin iron films

The temperature dependence of the spontaneous magnetization of epitaxial iron films with a thickness ranging from d=20$d=20$ to 200 nm has been measured. The films are grown on GaAs (1 0 0) substrates which are covered by a 150 nm thick silver (1 0 0) buffer layer. For three-dimensional BCC iron it was observed already in 1929 that saturation of the spontaneous magnetization for T→0$T\to 0$ is perfectly described by a T² power law. On the other hand, for thin two-dimensional (2D) iron films a T^3/2 law has been established in many recent experimental investigations. In our iron films grown on diamagnetic silver, this dimensionality change occurs at a thickness between d=100$d=100$ and 200 nm. Comparison of the here-observed T^3/2 coefficients with those on iron films grown on paramagnetic tungsten (1 1 0) shows that the 2D interactions are ∼20 times larger in the films on tungsten. Recent results on Fe films which are grown directly on GaAs (1 0 0) confirm that the substrate has a very strong effect on the coefficient of the T^3/2 function, i.e. on the strength of the magnetic interactions in the films.     

Binding of single gold atoms on thin MgO(001) films

In the present Letter the first electron paramagnetic resonance spectra of single metal atoms on a single crystalline oxide surface are presented. For Au atoms on a MgO(001) film investigated here an analysis of the angular dependent resonance positions and the hyperfine coupling to (17)O shows that the atoms are bound on top of oxygen ions on the terrace of the film. This result is in perfect agreement with scanning tunneling microscopy measurements at 5 K presented here. The measured hyperfine matrix components allow an experimental verification of the theoretically proposed binding mechanism of Au atoms on MgO. In particular, the large reduction of the isotropic hyperfine coupling constant of supported Au as compared to free atoms is not due to a charge transfer at the interface but a hybridization of orbitals and a resulting polarization of the unpaired electron.     

VUV absorption in thin MgO films

Amorphous films of MgO prepared by laser evaporation of bulk crystals show anomalous absorption in the region between 5.2 and 9.2 eV. An additional broad absorption band attributable to absorption by O^2? ions in states of low coordination has been observed at 217.5nm (5.7 eV). Amorphous MgO films show no evidence of absorption due to the bulk O^2? exciton at 7.62 eV but do exhibit such a feature when annealed to 800C in air.     

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.     

Two-color laser desorption of nanostructured MgO thin films

Neutral magnesium atom emission from nanostructured MgO thin films is induced using two-color nanosecond laser excitation. We find that combined vis/UV excitation, for single-color pulse energies below the desorption threshold, induces neutral Mg-atom emission with hyperthermal kinetic energies in the range of 0.1-0.2 eV. The observed metal atom emission is consistent with a mechanism involving rapid electron transfer to three-coordinated Mg surface sites. The two-color Mg-atom signal is significant only for parallel laser polarizations and temporally overlapped laser pulses indicating that intermediate excited states are short-lived compared to the 5 ns laser pulse duration.     

The resistivity of thin gold films

Results are obtained on the D.C. electrical resistivity of evaporated gold films on KBr substrates as a function of thickness and temperature. These show that the conduction electrons are not specularly reflected at the sample surface but nevertheless the temperature dependent part of the resistivity is independent of sample thickness. Comparison of the results with Fuchs-Sondheimer theory for the effects of sample thickness upon the resistivity yield a maximum specularity of approximately 0.64 for <100> films on KBr.     

Laser modification of silver nanoclusters in SiO2 thin films

Thin films of silica containing silver nanoclusters have been deposited by magnetron co-sputtering followed by thermal annealing. Laser modification of the mean cluster size was performed using the fourth harmonic of a Nd:YAG laser with energies of between 35 and 125 mJ/cm². The mean size of the clusters was estimated from the shape of the plasmon resonance band in the optical absorption spectra with the help of a computer simulation based on the Mie theory in static approximation. It was found that laser treatment with fluences above a certain threshold leads to a reduction of the mean size of the clusters and this reduction is greater for greater fluences. After a long treatment with the same fluence the effect saturates. The final mean size of the clusters after saturation depends only on the laser fluence and not on the initial mean cluster size. When lower laser fluences were used it was possible after laser annealing to return the mean cluster size to its initial value by thermal annealing. In this way by using a combination of laser treatment and thermal annealing a predetermined mean cluster size could be achieved. The mechanism of laser-induced cluster-size modification is discussed. PACS 81.07.-b; 42.62.-b; 36.40.Qv     

Photon mapping of MgO thin films with an STM

The light emission from an STM junction consisting of an MgO thin film on Mo(0 0 1) and an Au tip is analyzed with respect to its spatial distribution for various excitation conditions. The spectral characteristic of the light is compatible with an emission mechanism mediated by tip-induced plasmons that are excited by inelastic electron tunneling involving field-emission resonances in the tip-sample gap. The dependence of field-emission resonances on the MgO work function allows the controlled stimulation of differently thick oxide islands in the photon maps by changing the sample bias.     

Interaction of thin gold films with silicon

The study of thin (~ 10 monolayers) films Au on Si(III) after heating using LEED, ELS, AES, TEM, PES methods has been carried out. We came to the conclusion that gold on the silicon surface forms a chemical bond with the semiconductor forming surface phases with different electron structures, depending on the Si and Au concentrations.     

Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.     

The microstructure of SiO thin films: from nanoclusters to nanocrystals

The microstructure and electronic structure of silicon-rich oxide (SRO) films were investigated using transmission electron microscopy and electron energy loss spectroscopy as the main analytical techniques. The as-deposited SRO film was found to be a single phase SiO_1.0, as suggested by its electronic structure characteristics determined by the valence electron energy loss spectrum. This single phase undergoes a continuous but incomplete phase decomposition to Si and SiO₂ for films annealed between 300 and 1100°C. The resulting Si phase first appears as ～2?nm-diameter amorphous clusters which grow to larger sizes at higher annealing temperatures, but only crystallize at a critical temperature between 800 and 900°C. This cluster/matrix configuration of the SRO films is consistent with the appearance of the interface plasmon and its oscillator strength as a function of the nanoparticle size. Three separate stages were identified in the sequence of annealed films that were characterized by the presence of single-phase SiO, amorphous silicon nanoclusters, and silicon nanocrystals, respectively. The presence of amorphous silicon nanoclusters in the intermediate stage, the mean size of which can be controlled via annealing, may offer an alternative to silicon nanocrystal composites for optical applications.     

Control of the charge state of metal atoms on thin MgO films

The arrangement of single gold and palladium atoms deposited on the surface of a 3 monolayer thin film of MgO was investigated using low-temperature scanning tunneling microscopy. While Pd atoms are arranged in a random fashion, Au forms an ordered array on the surface. The long-range ordering as well as the scanning tunneling microscopy appearance of single Au atoms on a 3 monolayer thin MgO film can be explained by partial charge transfer from the substrate to Au atoms as predicted recently by density functional theory calculations [Phys. Rev. Lett. 94, 226104 (2005)10.1103/PhysRevLett.94.226104]. In contrast with that, Au atoms on a thick film were found to be essentially neutral.     

Ultrafast heat transfer on nanoscale in thin gold films

Heat transfer processes, induced by ultrashort laser pulses in thin gold films, were studied with a time resolution of 50 fs. It is demonstrated that in thin gold films heat is transmitted by means of electron–phonon and phonon–phonon interactions, and dissipated on nanoscale within 800 fs. Measurements show that the electron–phonon relaxation time varies versus the probe wavelength from 1.6 to 0.8 ps for λ=560–630 nm. The applied mathematical model is a result of transforming the two-temperature model to the hyperbolic heat equation, based on assumptions that the electron gas is heated up instantaneously and applying Cattaneo’s law to the phonon subsystem, agrees well with the experimental results. This model allows us to define time of electron–phonon scattering as the ratio of the heat penetration depth to the speed of sound in the bulk material that, in turn, provides an explanation of experimental results that show the dependence of the electron–phonon relaxation time on the wavelength.     

Anisotropic magnetoresistance in thin inhomogeneous gold films

We investigate the magnetoresistance (MR) of thininhomogeneous gold films applying the magnetic field perpendicular as well as parallel to the film plane. The MR-data show a strong anisotropy which can be well explained within the theory of weak electron localization (WEL) in 2d for both field orientations. The important results is that fitting the MR-data for both orientations by the corresponding theoretical expressions we obtain nearly identical values for the phase coherence lengthsL and its temperature dependence. This confirms (i) the correctness of the fitting process and (ii) the validity of the theory. From this we conclude that WEL in 2d can also be used to describe the MR ofinhomogeneous films.     

C-axis oriented growth of magnetron sputtered YBaCuO thin films on MgO substrates

Highly textured YBaCuO thin films were sputtered on MgO (100)-oriented single crystal substrates at ambient temperature followed by an anneal in oxygen for 1 h at temperatures up to 920 °C. X-ray diffractograms of the highly textured films indicate an orientation of the c-axis of the YBaCuO lattice perpendicular to the substrate surface. There are strong indications that the oriented c-axis growth is due to a CuO self-flux effect. Auger measurements reveal a copper diffusion profile into the substrate down to a depth of more than 400 nm.     

Nanostructuring of thin gold films by femtosecond lasers

Novel experimental data on microstructuring of thin (60 nm) gold films by femtosecond laser pulses are presented and discussed. Material modifications are induced by different laser field distributions on the sample surface. Images of specially fabricated masks are transferred onto the gold surface with a 50× and 100× demagnifications. It is shown that, in the irradiated region of the gold film, the heated material tends to concentrate in the center. For example, a square-like field distribution on the target surface produces a cross with a jet in the middle. It is shown that this technique allows producing of a variety of microstructures with controllable nanorelief. Possible mechanisms leading to the observed material modifications as well as the resolution limits of this technique are discussed.     

Tunable optical limiting of gold nanorod thin films

Permalloy (Py) films were deposited on Si(111) or Corning 0211 glass substrates. There were two deposition temperatures: T _s=room temperature (RT) and T _s=270°C. The film thickness (t _f) ranges from 10 to 130 nm. The crystal structure properties of the films were studied by X-ray diffraction and transmission electron microscopy. Mechanical properties (including Young’s modulus E _f and hardness H _f) of each film were measured by the nanoindentation (NI) technique. E _f of the Py/Si(111) films was checked again by the laser induced surface acoustic wave (LA-SAW) technique. It was found that the NI technique is best suited for the measurements of E _f and H _f, but only when the sample belongs to the (soft film)/(soft substrate) system, such as the Py/glass film. For the (soft film)/(hard substrate) system, such as the Py/Si(111) film, the NI technique often provides higher values of E _f and H _f than expected. The anomalous phenomenon, associated with the NI technique may be related to the anisotropic crystal structures in the Py films on different kinds of substrates. From this study, we conclude that [E _f of Py/Si(111)]>[E _f of Py/glass] and [H _f of Py/Si(111)]>[H _f of Py/glass]. The good mechanical properties of the Py/Si(111) film make it a better candidate for recording head applications.     

Hydrogen adsorption on thin low temperature deposited unsintered gold films

It has been found that molecular hydrogen does adsorb at 78 K on unsintered thin gold films deposited at low temperature, while sintering of these films at 420 K precludes H₂ chemisorption. The adsorbate is characterized by a single TD peak with a maximum placed at 125 K. The rate of desorption fits neither the first nor the second order kinetic equations exactly.     

On the electroluminescence from evaporated thin gold films

Au films with island structure show a spot-like electroluminescence (EL) under a low dc or ac voltage. I–V characteristics and their relation to the EL, and some EL features were investigated.