Ultrafast relaxation dynamics of electronic excitations in noble-metal clusters

We investigate non-equilibrium relaxation processes in optically excited large gold and silver clusters. Time-resolved pump-probe experiments and model calculations show that optical excitation of the clusters by femtosecond laser pulses results in a heating of the electron system, which is followed by electron cooling via phonon emission. The electron heating leads to an enhanced damping of the surface-plasmon resonance in the clusters. This enhanced damping is caused by an enhancement of the Landau damping and electron scattering rates at high electron temperatures. Furthermore, we find that the rate of electron cooling in the clusters changes with electron temperature; this is a consequence of the temperature-dependent specific heat of the conduction electrons. Finally, pump-probe experiments on ellipsoidal silver clusters show that the thermal expansion of the heated clusters triggers mechanical vibrations at the acoustic eigenfrequencies of the clusters. Received: 6 December 1999 / Published online: 7 August 2000     

SHG studies of plasmon dephasing in nanoparticles

2 . The necessary high SHG efficiency is obtained by nanoparticles produced by an electron beam lithographic method, which enables us to fabricate a two-dimensional array of nearly identical, parallel oriented particles of designed shape without centrosymmetry, essential for high SHG efficiency and the tuning of the plasmon resonance to the driving laser wavelength of 780 nm. Received: 14 October 1998 / Revised version: 4 January 1999     

Theory of spectral hole burning for the study of ultrafast electron dynamics in metal nanoparticles

In order to study the ultrafast relaxation dynamics of surface plasmon excitation in metal nanoparticles in the presence of inhomogeneous line broadening and investigate the influence of the reduced dimensions on the dephasing time T₂ in the size regime below about 10 nm, we have recently demonstrated a novel technique based on persistent spectral hole burning [1]. Here, we describe a theoretical model that has been developed for evaluation of the experimental data and precise determination of T₂ for particles of different size and shape. Comparison of the model to experimental data for Ag nanoparticles on sapphire shows that the theoretical treatment does not only reproduce the shape of the generated holes but also the dependence of their widths on the applied laser fluence. As a result, we have a reliable and versatile tool at hand making possible systematic studies of the ultrafast electron dynamics in small metal particles, and the dependence of the femtosecond dephasing time on their size, shape and surrounding dielectric. Received: 12 September 2001 / Published online: 15 October 2001     

Femtosecond dynamics of chemical reactions at surfaces

One of the major goals in physical chemistry is to obtain a microscopic understanding of chemical reactions. Recent developments in femtosecond laser techniques provide the opportunity to resolve the timescale of elementary steps of chemical reactions at surfaces. This is exemplified for the femtosecond laser-induced oxidation of CO on Ru(001). Among other adsorbate-specific probes vibrational sum-frequency generation spectroscopy offers the possibility to monitor adsorbates or reaction intermediates directly at the surface. Recently, we have employed this technique to investigate the dynamics of the CO-stretch vibration of CO adsorbed on Ru(001) after optical excitation leading to CO desorption. Received: 4 August 2000 / Accepted: 2 September 2000 / Published online: 12 October 2000     

Evidence for the existence of an unusual structure in the nanorods of InSb

Motivated by the recent prediction that InSb nanometer-diameter filaments can exhibit exotic physical properties, we have synthesized this material and have characterized the filaments. In this report, we describe the finding of an unusual phase of InSb. This new phase occurs when an InSb filament has a diameter of less than 100 nm. High-resolution X-ray-diffraction studies of InSb filaments, having radii ≅33.0 nm, indicate the InSb crystal lattice to be tetragonal, S.G. I4/mmm, with a unit-cell volume 12 times larger than that of the β-tin phase observed in bulk InSb above 2.0 GPa. The density of an InSb nanorod, as calculated from X-ray-diffraction data, is ∼22% more than that of the zinc-blende phase of InSb at ambient conditions, implying that the nanorod experiences a pressure of ∼2 GPa. In contrast, InSb nanorods with radii ≥50.0 nm are observed to show zinc-blende structure and densities nearly the same as that of the bulk. Received: 6 February 2002 / Accepted: 26 March 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/767-5301; E-mail: yousuf@seas.gwu.edu     

Energy balance of optical breakdown in water at nanosecond to femtosecond time scales

Received: 3 August 1998/Revised version: 20 October 1998     

Quasi-simultaneous detection of CH2O and CH by cavity ring-down absorption and laser-induced fluorescence in a methane/air low-pressure flame

The combination of two-dimensional, planar laser-induced fluorescence (PLIF) and cavity ring-down (CRD) absorption spectroscopy is applied to map quantitatively the spatial distributions of CH₂O and CH in a methane/air flame at 25 Torr. Both species are detected in the same spectral region using the overlapping CH₂O A ¹ A ₂ -X ¹ A ₁ 4₁ ⁰ and CH B-X(1,0 )bands. The combination of diagnostic techniques exploits the spatial resolution of LIF and the quantitative CRD absorption measure of column density. The spatially resolved PLIF provides the distribution of absorbers and line-of-sight CRD absorption the absolute number density needed for quantitative concentration images. The peak CH₂O concentration is (3.5±1.4 )×10¹⁴ cm^-3, or 1450±550 ppm at 1000 K. The lack of precise absorption cross-section data produces these large error limits. Although a flame model predicts lower amounts, these large uncertainties limit this measurement’susefulness as a test of the flame chemistry. Received: 24 April 2001 / Revised version: 10 July 2001 / Published online: 10 October 2001     

Precursor effects of the Rhombohedral-to-Cubic Phase Transition in Indium Selenide

We report on the observation of precursor effects of the rhombohedral-to-cubic phase transition in Indium Selenide (InSe) with several experimental techniques. The pressure at which these precursor defects are first observed depends on the sensitivity of the experimental technique. In transport measurements, which are very sensitive to low defect concentrations, precursor effects are observed 5 to 6 GPa below the phase transition pressure whereas in X-ray diffraction measurements precursor effects are only observed 2 GPa below the phase transition pressure. We report optical absorption measurements, in which the precursor effects are shown by the growth and propagation of dark linear defects appearing 3 GPa below the phase transition pressure. On the base of a simple model of the stress field around edge dislocations, we attribute the darkening of the InSe samples to local phase transitions to a high-pressure modification along linear dislocations. These results agree with room-pressure and high-pressure Raman spectra of samples compressed up to 7-8 GPa, which show new phonon lines not corresponding to the low-pressure phase.     

Formation of metallic nanophases in silica by ion-beam mixing Part I: Mixing mechanisms

2 matrix is studied by means of the Rutherford backscattering technique. Two different mechanisms are observed: at low temperature (300 K and below) the variance of the mixed profile varies with the square of the ion fluence, whereas at higher temperature (400 K to 620 K) a linear variation is found. The low-temperature kinetics are accounted for by the migration of Ag-defect complexes after introduction of Ag atoms into the silica matrix by a ballistic process. A combination of ballistic and radiation-enhanced diffusion processes explains the results obtained at high temperature. This work emphasizes the role of the presence of metallic clusters on the migration of metal atoms in silica. Received: 10 June 1997/Accepted: 29 September 1997     

On the theory of relaxation of electrons excited by femtosecond laser pulses in thin metallic films

Received: 14 October 1998 / Revised version: 21 December 1998     

Observation of strain relaxation in Si1-xGex layers by optical and electrical characterisation of a Schottky junction

We have studied the effect of the strain relaxation on the band-edge alignments in a Pt/p-Si_1-xGe_x Schottky junction with x=0.14 by internal photoemission spectroscopy and current–voltage measurements. We have shown that the variations in the band-edge alignments can be observed directly by measuring the optical and electrical properties of a simple Schottky junction. The strain in the Si_1-xGe_x layer has been partially relaxed by thermal treatments at two different temperatures. The degree of relaxation and other structural changes have been determined by a high-resolution X-ray diffractometer. Both optical and electrical techniques have shown that the barrier height of the Pt/Si_0.86Ge_0.14 junction increases with the amount of relaxation in the Si_1-xGe_x layer. This shows that the valence-band edge of the Si_1-xGe_x layer moves away from the Fermi level of the Pt/Si_1-xGe_x junction. The band-edge movement results from the increase in the band gap of the Si_1-xGe_x layer after the strain relaxation. This result agrees with the theoretical predictions for the strain-induced effects on the Si_1-xGe_x band structure. Received: 18 October 2000 / Accepted: 19 December 2000 / Published online: 23 March 2001     

Iron and its complexes in silicon

This article is the first in a series of two reviews on the properties of iron in silicon. It offers a comprehensive summary of the current state of understanding of fundamental physical properties of iron and its complexes in silicon. The first section of this review discusses the position of iron in the silicon lattice and the electrical properties of interstitial iron. Updated expressions for the solubility and the diffusivity of iron in silicon are presented, and possible explanations for conflicting experimental data obtained by different groups are discussed. The second section of the article considers the electrical and the structural properties of complexes of interstitial iron with shallow acceptors (boron, aluminum, indium, gallium, and thallium), shallow donors (phosphorus and arsenic) and other impurities (gold, silver, platinum, palladium, zinc, sulfur, oxygen, carbon, and hydrogen). Special attention is paid to the kinetics of iron pairing with shallow acceptors, the dissociation of these pairs, and the metastability of iron–acceptor pairs. The parameters of iron-related defects in silicon are summarized in tables that include more than 30 complexes of iron as detected by electron paramagnetic resonance (EPR) and almost 20 energy levels in the band gap associated with iron. The data presented in this review illustrate the enormous complexing activity of iron, which is attributed to the partial or complete (depending on the temperature and the conductivity type) ionization of iron as well as the high diffusivity of iron in silicon. It is shown that studies of iron in silicon require exceptional cleanliness of experimental facilities and highly reproducible diffusion and temperature ramping (quenching) procedures. Properties of iron that are not yet completely understood and need further research are outlined. Received: 14 December 1998 / Accepted: 22 February 1999 / Published online: 26 May 1999     

On the phase-transition in anthracene induced by high pressure

The crystallographic structure of anthracene is studied under high pressure up to 27 GPa using diamond anvil cells. Different pressure-transmitting media (helium, a methanol-ethanol mixture, a normal- and iso-pentane mixture and no medium) were used up to specific critical pressures where the hydrostatic conditions are lost. It is clearly observed that the loss of hydrostaticity is associated with a crystallographic phase-transition in anthracene. The phase-transition is observed as reversible, and it is accompanied by a large hysteresis. These observations clarify conflicting reports in the literature on the high-pressure phase-transition of anthracene.     

On the sensitivity limit of positron annihilation: detection of vacancies in as-grown silicon

14 cm^-3 in FZ-Si was obtained. Received: 2 June 1998 / Accepted: 20 November 1998 / Published online: 24 February 1999     

Calculation of the short-time dynamics of the hot-electron distribution in noble and transition metals

Received: 23 October 1998     

Characterization of the Fermi surface of the organic superconductor - by measurements of Shubnikov-de Haas and angle-dependent magnetoresistance oscillations and by electronic band-structure calculations

The electronic structure of the quasi two-dimensional (2D) organic superconductor -(ET)₂SF₅CH₂CF₂SO₃ was examined by measuring Shubnikov-de Haas (SdH) and angle-dependent magnetoresistance (AMRO) oscillations and by comparing with electronic band-structure calculations. The SdH oscillation frequencies follow the angular dependence expected for a 2D Fermi surface (FS), and the observed fundamental frequency shows that the 2D FS is 5% of the first Brillouin zone in size. The AMRO data indicate that the shape of the 2D FS is significantly non-circular. The calculated electronic structure has a 2D FS in general agreement with experiment. From the temperature and angular dependence of the SdH amplitude, the cyclotron and band effective masses were estimated to be and ,where g is the conduction electron g factor and the free electron mass. The band effective mass is estimated to be from the calculated electronic band structure. Received: 3 March 1997 / Revised: 5 May 1997 / Received in final form: 5 November 1997 / Accepted: 10 November 1997     

Reflectivity of cadmium sulphide nanocrystal films grown by the Langmuir–Blodgett technique

0 ) in the reflectivity spectra has been found to be blue-shifted with respect to that for bulk CdS. The appearance of the E₁(A) peak at about 5 eV is evidence for the hexagonal nature of the particles with the c axis normal or nearly normal to the plane of the film. This suggests the epitaxial nature of the grown particulate films. Another reflectivity peak has been observed at about 320 nm. However, its origin is not yet clear. Received: 26 May 1998/Accepted: 28 May 1998     

Luminescence quantum yield and multiplication of electronic excitations in the corundum crystals

The excitation spectra of luminescence in irradiated and nonirradiated corundum crystals are investigated by means of highly polarised synchrotron radiation in 5 to 30 eV region. In the fundamental absorption region the double-exciton peaks are observed in the region 8.5-9.2 eV for irradiated (especially by neutrons) crystals at temperature 90 K. At 9.5 eV sharp drops appeared, in the luminescence spectrum space which were interpreted as nonirradiative near-surface recombination, the probability of which sharply increased at high absorption coefficients. The enhancement of the luminescence efficiency in the high-energy region was connected with the decay effect of electron excitations as well as with the influence of volumetric excitations leading to the enhancement of recombination glow. Received 16 October 1998 and Received in final form 20 January 1999     

Nanotomographic examinations of ion tracks in cellulose nitrate by ion energy loss spectrometry

Received: 13 October 1997/Accepted: 25 August 1998