Pulsed laser treatment of gold and black gold thin films fabricated by thermal evaporation

The effect of pulsed laser treatment of metal, and metal blacks, was studied. Gold and black gold thin films were fabricated by thermal evaporation of gold in a vacuum and nitrogen atmosphere respectively. Black gold films were grown in a nitrogen atmosphere at pressures of 200 Pa and 300 Pa. UV pulsed laser radiation (λ = 266 nm, τ = 4 ns), with fluence ranging from 1 mJ·cm⁻² to 250 mJ·cm⁻² was used for the film treatment in a vacuum and nitrogen atmosphere. The nitrogen pressure was varied up to 100 kPa. Surface structure modifications were analyzed by optical microscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Energy dispersive X-ray spectroscopy (EDX) was used for chemical characterization of the samples. A significant dependence of the film optical and structural properties on laser treatment conditions (laser fluence, ambient pressure and number of applied pulses) was found. The threshold for observable damage and initiation of changes of morphology for gold and black gold surfaces was determined. Distinct modifications were observed for fluences greater than 106 mJ·cm⁻² and 3.5 mJ·cm⁻² for the gold and black gold films respectively. Absorbtivity of the black gold film is found to decrease with an increase in the number of laser pulses. Microstructural and nanostructural modifications after laser treatment of the black gold film were observed. EDX analysis revealed that no impurities were introduced into the samples during both the deposition and laser treatment.      

Ultrafast dynamics of bis (<Emphasis Type="Italic">n</Emphasis>-butylimido) perylene thin films excited by two-photon absorption

We report a pump-probe study of the two-photon induced reflectivity changes in bis (n-butylimido) perylene thin films. To enhance the two-photon excitation we deposited bis (n-butylimido) perylene films on top of gold nanoislands. The observed transient response in the reflectivity spectrum of bis (n-butylimido) perylene is due to a depletion of the molecule’s ground state and excited state absorption.     

金、铜、铂、银表面光学二次谐波参数的研究

以1.06μm激光为基频光,测量了金、铜、铂、银膜的反射二次谐波随基频光偏振角的变化,在b=-1的条件下拟合求得了这几种样品面谐波电流的唯象参数“a”值。     

Epitaxial growth of YBa2Cu3O7−δ superconducting thin films by DC magnetron sputtering using a partially melted sintered target

In situ epitaxially grown YBa₂Cu₃O_7– (YBCO) thin films on (100)SrTiO₃ substrates with high critical current J _c=3.4 × 10⁶ A/cm² (at 77 K) and low microwave surface resistance R _s37 m (at 77 K, 50.9 GHz) are fabricated by dc magnetron sputtering using a large partially melted sintered planar target. A comparatively large homogeneous composition region can be obtained. The X-ray diffraction, X-ray double crystal diffraction, and high resolution transmission electron microscopy (HRTEM) analyses show that our deposited YBCO thin films are single crystalline containing mosaic blocks. The influence of substrate quality on the orientation behaviour of the films is also discussed. A method to improve the surface quality of the SrTiO₃ substrate, which improves the properties of the thin film, is presented.     

Low-temperature diffusion of gold in germanium under the influence of atomic hydrogen

An investigation is made of the diffusion of gold in germanium under the influence of the energy released by the recombination of hydrogen atoms to form molecules. Crystals of n-type germanium with gold films (d=1×10⁻⁷ m) are exposed to atomic hydrogen for various times (up to 10⁴ s) at temperatures close to room temperature. The diffusion of gold in the germanium is analyzed by laser mass spectrometry, and also by measuring the surface resistance, the minority carrier lifetime, and the infrared transmission spectra. Mechanisms are proposed for the stimulation of heterodiffusion and accompanying processes. Zh. Tekh. Fiz. 69, 73–76 (July 1999)     

Effect of nanoparticle dispersion on glass transition in thin films of polymer nanocomposites

We present spectroscopic ellipsometry measurements on thin films of polymer nanocomposites consisting of gold nanoparticles embedded in poly(styrene). The temperature dependence of thickness variation is used to estimate the glass transition temperature, T _g . In these thin films we find a significant dependence of T _g on the nature of dispersion of the embedded nanoparticles. Our work thus highlights the crucial role played by the particle polymer interface morphology in determining the glass transition in particular and thermo-mechanical properties of such nanocomposite films.     

The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films

We present a detailed study of free polymer surfaces and their effects on the measured glass transition temperature (T_g) of thin polystyrene (PS) films. Direct measurements of the near-surface properties of PS films are made by monitoring the embedding of 10 and 20 nm diameter gold spheres into the surface of spin-cast PS films. At a temperature T = 378K( > T_g), the embedding of the spheres is driven by geometrical considerations arising from the wetting of the gold spheres by the PS. At temperatures below T_g ( 363K < T < 370K), both sets of spheres embed 3-4 nm into the PS films and stop. These studies suggest that a liquid-like surface layer exists in glassy PS films and also provide an estimate for the lower bound of the thickness of this layer of 3-4 nm. This qualitative idea is supported by a series of calculations based upon a previously developed theoretical model for the indentation of nanoscale spheres into linear viscoelastic materials. Comparing data with simulations shows that this surface layer has properties similar to those of a bulk sample of PS having a temperature of 374 K. Ellipsometric measurements of the T_g are also performed on thin spin-cast PS films with thicknesses in the range 8nm < h < 290nm. Measurements are performed on thin PS films that have been capped by thermally evaporating 5 nm thick metal (Au and Al) capping layers on top of the polymer. The measured T_g values (as well as polymer metal interface structure) in such samples depend on the metal used as the capping layer, and cast doubt on the general validity of using evaporative deposition to cover the free surface. We also prepared films that were capped by a new non-evaporative procedure. These films were shown to have a T_g that is the same as that of bulk PS (370±1 K) for all film thicknesses measured (> 7 nm). The subsequent removal of the metal layer from these films was shown to restore a thickness-dependent T_g in these samples that was essentially the same as that observed for uncapped PS films. An estimate of the thickness of the liquid-like surface layer was also extracted from the ellipsometry measurements and was found to be 5±1 nm. The combined ellipsometry and embedding studies provide strong evidence for the existence of a liquid-like surface layer in thin glassy PS films. They show that the presence of the free surface is an important parameter in determining the existence of T_g reductions in thin PS films.     

Preparation of ultrathin gold films by oxygen-ion sputtering and their optical properties

The optical and electrical properties of gold films of thickness varying from less than 1 to 8 nm are studied. The films are obtained by sputtering with argon ion and oxygen ion beams. It is shown that the properties of the films are independent of the type of ions used for sputtering. The 1-to 5-nm-thick films are continuous and offer a high transparency. Sputtering by oxygen ion beams is used to produce NiO_x/Au ohmic contacts to p-GaN.     

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.     

Inhibition effect of self-assembled films formed by gold nanoparticles on iron surface

The self-assembled (SA) films formed by gold nanoparticles on iron surface had been proved to have inhibition effect for the substrate in 0.5 M H₂SO₄ solutions. The inhibition action was investigated using electrochemical impedance spectroscopy (EIS). The SA films formed by gold nanoparticles protected with sodium oleate had better corrosion protection to the iron substrate than only by sodium oleate. Scanning electron microscopy (SEM) was used to observe the imagines of the SA films. In addition, it was found that the gold nanoparticles could influence the nickel electroless plating films on the iron substrate. The structure and composition of the plating films were test by electron probe microanalyzer (EPMA). The mechanisms of the formation of the SA films and the nickel electroless plating reaction were also discussed.     

Modulation of residual stress in diamond like carbon films with incorporation of nanocrystalline gold

Residual stress modulation in the diamond-like carbon coatings with incorporation of gold nanoparticles was studied critically. The films were deposited on glass and Si (1 0 0) substrates by using capacitatively coupled plasma chemical vapor deposition. Stresses in the films were determined from the broadening of the optical absorption tail and were found to decrease from 2.3 GPa to 0.48 GPa with increasing gold content (2-7 at.% Au) in the DLC matrix. Gold incorporation also made the films harder than the corresponding DLC coatings. Modulation of stress with nanocrystalline gold content in the DLC matrix was related to the relative amount of sp²/sp³ content in the DLC films.     

Nanoporous gold thin films synthesised via de-alloying of Au-based nanoglass for highly active SERS substrates

Nanoporous gold thin films have been fabricated through chemical de-alloying of Au-based nanoglass with a nanocolumnar structure, with composition Au₄₀Cu₂₈Ag₇Pd₅Si₂₀ (at.%), that had previously been deposited by magnetron sputtering. By varying the de-alloying conditions, gold ligaments ranging from 20 to 100?nm were obtained. The microstructure and chemical composition of the as-prepared films were characterised by various techniques. Surface-enhanced Raman scattering (SERS) of thin films was investigated using rhodamine 6G. The results indicate that the main microstructural features with interconnected ligaments and defects of nanoporous gold result in significant SERS enhancement.     

Self-assembled monolayers of decanethiol on Au(111)/mica

We report here a preparation for thin gold films on mica substrates. We have investigated the influence of the substrate temperature and the evaporation rate on the morphology of the films. After careful outgasing of the substrate, 100 nm of Au is evaporated onto the mica surface maintained at high temperature. After slow cooling, ex situ characterizations are performed using AFM and STM. For our purposes, the best compromise between roughness and grain size is found to occur for an evaporation rate of 2 ?s^-1 onto a mica substrate maintained at 460 C. We have used these substrates for STM and AFM study of decanethiol self-assembled monolayers (SAMs). We present results for gold samples immersed for a few seconds in decanethiol solutions, revealing an incomplete organization of the films. The organization process is discussed through comparison between AFM and STM data recorded on the SAMs. Then we present molecular resolution STM pictures of ordered SAMs for longer immersion times. Received 25 May 1999     

Nucleation of Polypropylene with Gold Nanoparticles. Part 1: Introduction of Sandwich Method for Evaluation of Very Weak Nucleation Activity

Although gold particles are known to nucleate isotactic polypropylene (PP), the nucleating effect of chemically pure 5 nm Au, prepared in vacuum sputter coater, was found to be hardly observable. In order to detect such a weak effect, we deposited a homogeneous layer of Au nanoparticles between thin PP films and evaluated the nucleation activity by a combination of three independent methods: polarized light microscopy (PLM), differential scanning calorimetry (DSC), and 2D wide-angle X-ray scattering (2D-WAXS). This new technique, which was called sandwich method, allowed us to demonstrate that gold nanoparticles were able to nucleate PP crystallization, although the effect was much weaker than that produced by commercial α-nucleant [1,2,3,4-bis(3,4-dimethylbenzylidene)sorbitol] and β-nucleant (N,N-Dicyclohexyl-2,6-naphthalene dicarboxamide). The sandwich method appeared to be quite universal and applicable for any micro-sized nucleants or nanonucleants.     

Fabrication, structure and luminescence properties of polycrystalline Tb-doped Lu2SiO5 films by Pechini sol–gel method

Tb³⁺-doped lutetium oxyorthosilicate (Tb:Lu₂SiO₅, LSO) films have been successfully fabricated on carefully cleaned silicon (1 1 1) substrates by Pechini sol–gel method combined with the spin-coating technique. X-ray diffraction (XRD), photoluminescence (PL) spectra and atomic force microscopy (AFM) were employed to characterize the resultant films. XRD patterns indicated that the films were crystallized into A-type LSO phase at 1000 °C, followed by a phase transition from A-type LSO to B-type LSO occurred at 1100 °C. The AFM observation revealed that the phosphor films were uniform and crack-free, consisting of closely packed grains with an average size of 200–300 nm. The PL spectra showed the characteristic emission ⁵D₄ → ⁷F_J (J = 3–6) for Tb³⁺, The lifetime of Tb³⁺ in Tb:LSO films was 2.33 ms. The effect of heat-treatment temperature on the luminescent properties was also investigated.     

Revisiting the physical processes of vapodeposited thin gold films on chemically modified glass by atomic force and surface plasmon microscopies

The preparation of very thin (at the scale of a few tens of nanometers) gold films by thermal evaporation and deposition on a solid substrate (glass) remains a key step for the elaboration of transparent and sensitive optical biosensors. We study the influence of the glass surface treatment and its thermal conductivity on the structure and composition of evaporated gold films. Using a combination of atomic force microscopy (AFM), high resolution surface plasmon resonance (SPR) imaging, and X-ray photoelectron spectroscopy (XPS), we demonstrate that the grafting of a layer of long chain mercaptant, using 11-mercaptoundecyltrimethoxysilane (S_ξSi), prior to gold deposition produces a drastic modification of gold inner and surface textures. A thorough investigation of AFM image topography by 2D wavelet-based segmentation method reveals the flat conical shape of the gold surface grains and their shape invariance with the glass surface chemical treatment. However, this treatment leads to a drastic decrease of the mean size and polydispersity of these grains by a factor of 2, thereby lowering the gold surface roughness. The rationale is that the combination of surface forces and thermal transfer drives the formation of homogeneous and flatter gold films.     

Polarization properties of porous gold and silver films

Using the method of polarization modulation of electromagnetic radiation and the Kretschmann geometry, we perform comparative studies of surface plasmon resonance in porous and continuous gold and silver films. The spectral dependences of the polarization difference of the reflection coefficients of nano-composites are obtained for the first time and are supplemented by angular characteristics of this parameter. We show that these dependences characterize particular features of the optical properties related to the structure, morphology, and topology of porous films. We reveal that surface plasmon-polaritons and local plasmons in porous films can be excited both by radiation that is p polarized with respect to the plane of incidence, as is the case with continuous films, and by s polarized radiation. We demonstrate that the measurement results can yield information on the structural properties of films, such as their thickness, roughness height, degree of dispersion of nanoparticles, and so on.     

Fabrication and characterization of Au/SiO2 nanocomposite films grown by radio-frequency cosputtering

Au/SiO₂ nanocomposite films were prepared on Si wafers by cosputtering of SiO₂ and gold wires. Au/Si atomic ratios in Au/SiO₂ nanocomposite films were varied from 0.53 to 0.92 by controlling the length of gold wire to study the evolution of the crystallization of gold, the size of Au/SiO₂ nanocomposite particles, and the optical properties of as-deposited Au/SiO₂ nanocomposite films. An X-ray photoelectron spectroscopy reveals that Au exists as a metallic phase in the bulk of SiO₂ matrix. Dome-shaped Au/SiO₂ nanocomposite particles and both Au (1 1 1) and (2 0 0) planes were observed in a field-emission scanning electron microscopy and X-ray diffraction studies respectively. With an ultraviolet-visible, absorption peaks of Au/SiO₂ nanocomposite films were observed at 525 nm.     

Polarization stokes polarimetry of the amplitude and phase characteristics of surface plasmon polariton resonance

The amplitude and phase characteristics of internal reflection of gold nanofilms have been investigated using polarization modulation of electromagnetic radiation in the Kretschmann geometry. The component Q (the difference between the reflection coefficients R _s ² and R _p ² for the s and p polarizations, respectively) and the component V of the Stokes vector (the difference between the phases of the orthogonal components of linearly polarized radiation) of light reflected from a half-cylinder of the total internal reflection with gold films of different thicknesses on its flat surface have been measured as a function of the angle of incidence of light in the wavelength range 500–1000 nm. It has been demonstrated that, in the range of parameters corresponding to the manifestation of the plasmon polariton resonance (the angle of incidence of light, the wavelength, the metal film thickness), the dispersions of the amplitude and phase characteristics are in quantitative and qualitative agreement with the model concepts of a classical oscillator.     

Plasmonic interactions between a perforated gold film and a thin gold film

Based on the finite difference time domain method,we investigated theoretically the optical properties and the plasmonic interactions between a gold film perforated with periodic sub-wavelength holes and a thin gold film.We showed that the plasmon resonant energies and intensities depend strongly on the thicknesses of the two films and the lattice constant.Based on the distributions of normal electric field component E z,tangential electric field component E y and total energy,we showed that the optical transmission is due to the collaboration of the localized waveguide resonance,the surface plasmon resonance and the coupling of the flat-surface plasmon of the two layers.