Mechanisms of femtosecond laser-induced damage in magnesium fluoride

We studied the single-shot damage in magnesium fluoride irradiated by 800 nm femtosecond (fs) laser. The dependence of damage thresholds on the laser pulse durations from 60 to 750 fs was measured. The pump-probe measurements were carried out to investigate the time-resolved electronic excitation processes. A coupled dynamic model was applied to study the microprocesses in the interaction between fs laser and magnesium fluoride. The results indicate that both multiphoton ionization and avalanche ionization play important roles in the femtosecond laser-induced damage in MgF₂.     

Ultrafast motion of liquids C2H4Cl2 and C2H4Br2 studied with a femtosecond laser

Transient optical Kerr effect of liquids C₂H₄Cl₂ and C₂H₄Br₂ is investigated, for the first time to our knowledge, with a femtosecond (fs) probe laser delayed with respect to a coherent fs pump laser. Coherent coupling and electronic Kerr signals are observed around zero delay when pump and probe overlap. Persisting after the pump-probe overlap are Kerr signals arising from the torsional and other intramolecular vibrations of the trans and gauche conformations; Kerr signals arising from the intermolecular motion are also observed. Vibrational quantum interference is only observed in liquid C₂H₄Br₂ and the related beats data are fitted with the torsional vibrations, 91 cm⁻¹ (gauche) and 132 cm⁻¹ (trans), and the CCBr angle-bending vibrations, 231 cm⁻¹ (gauche) and 190 cm⁻¹ (trans), with dephasing times, 0.45 ps, 0.45 ps, 2 ps, and 1.5 ps, respectively. These vibrational frequencies agree with those obtained in the frequency-domain. That no vibrational mode is observed for C₂H₄Cl₂ might be attributed to ineffective Raman-pumping. Kerr signals observed after the pump-probe overlap are Fourier transformed to give the spectra of the intermolecular motion and the vibrational spectrum, which agrees with the one observed in the infrared absorption and/or Raman scattering heretofore.     

Characteristics of nodular defect in HfO2/SiO2 multilayer optical coatings

Laser-induced damage is associated with nodular defects in HfO₂/SiO₂ multilayer films. In order to investigate the damage characteristics of HfO₂/SiO₂ multilayer mirrors and find the information of improving laser-induced damage threshold, nodular defects are characterized by multiple analytical techniques; the damage morphologies induced by nodular-ejections are presented; the depths of nodular-ejection pits are investigated; the laser-induced damage threshold of zero probability and the stabilities of nodular-ejection pits exposed to repetitive illuminations are studied. Results show that domes in the film surface are nodular defects. Reliable depth information of nodular-ejection pits is obtained by counting layers from the damage edge. The depth statistical result implies nodular defects in these samples are usually originated from deep seeds. Some process optimizations suggestions are given based on the depth information. A simple tractable method is proposed to determine the functional damage threshold of these HfO₂/SiO₂ multilayer films basing on the damage experiments.     

Fabrication of nanostructured CuInS2 thin films by ion layer gas reaction method

CuInS₂ thin films were prepared by a two-stage ion layer gas reaction (ILGAR) process in which the Cu and In precursors were deposited on glass substrate by using a simple and low-cost dip coating technique and annealed in H₂S atmosphere at different temperatures. The influence of the annealing temperature (250-450 °C) on the particle size, crystal structure and optical properties of the CuInS₂ thin films was studied. Transmission electron microscopy revealed that the particle radii varied in the range 6-21 nm with annealing. XRD and SAED patterns indicated polycrystalline nature of the nanoparticles. The optical band gap (E_g) varied from 1.48 to 1.56 eV with variation of particle size. The variation of Urbach tail with temperature indicated higher density of the defects for the films annealed at lower temperature. From the Raman study, it was observed that the FWHM of the A₁ mode at ∼292 cm⁻¹ corresponding to the chalcopyrite phase of CuInS₂ decreased with increasing annealing temperature.     

Effect of Al2O3 on the electrical properties of ZnO-Pr6O11-based varistor ceramics

The effect of Al₂O₃ on the electrical properties of ZnO-Pr₆O₁₁-based ceramics is investigated in this work. The average grain size of ZnO increased as the Al₂O₃ content increased from 10.3 to 13.5 μm. It was found that a sample doped with Al₂O₃ of 0.005 mol% showed the highest nonlinear current-voltage characteristics with a nonlinear exponent of 43.8 and a leakage current of 0.66 μA. When the Al₂O₃ content was increased, the donor concentration was increased from 0.51×10¹⁸/cm³ to 1.59×10¹⁸/cm³, but the barrier height was decreased from 1.01 to 0.87 eV. The best electrical stability against aging stress was obtained by doping Al₂O₃ of 0.001 mol%.     

Gd-doping of HfO2

An increase in the density of states between the oxygen 2p bands and the Fermi level is seen with increasing Gd concentrations. In addition, for the Gd-doped HfO₂ films, the Gd 4f photoexcitation peak at 5.5 eV below the valence band maximum was identified using resonant photoemission. Electrical measurements show pronounced rectification properties for lightly-doped Gd:HfO₂ films on p-Si and for heavily-doped Gd:HfO₂ films on n-Si, suggesting a crossover from n-type to p-type behavior with increasing doping level. In addition, there is an increase in the reverse bias current with neutron irradiation.     

Ultra-Fast Decay Process of Electrons in LiNbO3 Crystal Induced by Femtosecond Pulse

Temporal evolution of absorption induced by single femtosecond pulse （13Ors, 800nm） with high intensity in LiNbO3 is obtained using the probe shadow imaging technique in order to investigate light-induced electron relaxation processes. By saturating the polaron density with a high intensity laser pulse, ultra-fast decay process on picosecond time scale is observed. The decay time constant is about 141 ps and it is attributed to the direct interband electron-hole recombination process.     

Influence of substoichiometer on the laser-induced damage characters of HfO2 thin films

HfO₂ is one of the most important high refractive index materials for depositing high power optical mirrors. In this research, HfO₂ thin films were prepared by dual-ion beam reactive sputtering method, and the laser-induced damage thresholds (LIDT) of the sample were measured in 1-on-1 mode for laser with 1064 nm wavelength. The results indicate that the LIDT of the as-grown sample is only 3.96 J/cm², but it is increased to 8.98 J/cm² after annealing under temperature of 200 °C in atmosphere. By measuring the laser weak absorption and SIMS of the samples, we deduced that substoichiometer is the main reason for the low LIDT of the as-grown sample, and the experiment results were well explained with the theory of electronic-avalanche ionization.     

Photoelectron spectroscopic investigation of transformation of trifluoroacetate precursors into superconducting YBa2Cu3O7−δ films

X-ray photoelectron spectroscopy (XPS) has been used to investigate the evolution of surface chemistry of YBa₂Cu₃O_7−δ (Y123) films prepared by the metalorganic deposition (MOD) process using trifluoroacetate (TFA) precursors. Detailed XPS core-level spectra obtained from the samples quenched from various points during the calcining and firing stages have been reported for the first time and are used to identify surface species. The XPS data show evidence of formation of intermediate phases such as Y-O-F, BaF₂, and CuO during the calcining process, which are the decomposition products of yttrium, barium, and copper trifluoroacetates, respectively. The TFA precursors are completely decomposed at the end of calcination. The change of binding energies for Y 3d_5/2, Ba 3d_5/2, and O 1s during the firing process indicates that Y123 starts to form at 800 °C after 0.5 h firing. Based on the experimental results, an alternative mechanism of the chemical evolution from precursor to final film in the TFA-MOD process is proposed.     

Mechanisms of femtosecond laser-induced breakdown and damage in MgO

Single-shot laser damage threshold of MgO for 40-986 fs, 800 nm laser pulses is reported. The pump-probe measurements with femtosecond pulses were carried out to investigate the time-resolved electronic excitation processes. A theoretical model including conduction band electrons (CBE) production and laser energy deposition was applied to discuss the roles of multiphoton ionization (MPI) and avalanche ionization in femtosecond laser-induced dielectric breakdown. The results indicate that avalanche ionization plays the dominant role in the femtosecond laser-induced breakdown in MgO near the damage threshold.     

Influence of ZrO2 in HfO2 on reflectance of HfO2/SiO2 multilayer at 248 nm prepared by electron-beam evaporation

Influence of ZrO₂ in HfO₂ on the reflectance of HfO₂/SiO₂ multilayer at 248 nm was investigated. Two kinds of HfO₂ with different ZrO₂ content were chosen as high refractive index material and the same kind of SiO₂ as low refractive index material to prepare the mirrors by electron-beam evaporation. The impurities in two kinds of HfO₂ starting coating materials and in their corresponding single layer thin films were determined through glow discharge mass spectrum (GDMS) technology and secondary ion mass spectrometry (SIMS) equipment, respectively. It showed that between the two kinds of HfO₂, either the bulk materials or their corresponding films, the difference of ZrO₂ was much larger than that of the other impurities such as Ti and Fe. It is the Zr element that affects the property of thin films. Both in theoretical and in experimental, the mirror prepared with the HfO₂ starting material containing more Zr content has a lower reflectance. Because the extinction coefficient of zirconia is relatively high in UV region, it can be treated as one kind of absorbing defects to influence the optical property of the mirrors.     

Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell： Correlation between Performance and Carrier Relaxation Kinetics

Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiO2 solar cell （DSSC） when a certain amount of H2 0 is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interracial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D20 is added. The values of open-circuit photovoltage Voc and the short-circuit photocarrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.     

Effects of annealing on laser-induced damage threshold of TiO2/SiO2 high reflectors

The mechanism of improving 1064 nm, 12 ns laser-induced damage threshold (LIDT) of TiO₂/SiO₂ high reflectors (HR) prepared by electronic beam evaporation from 5.1 to 13.1 J/cm² by thermal annealing is discussed. Through optical properties, structure and chemical composition analysis, it is found that the reduced atomic non-stoichiometric defects are the main reason of absorption decrease and LIDT rise after annealing. A remarkable increase of LIDT is found at 300 °C annealing. The refractive index and film inhomogeneity rise, physical thickness decrease, and film stress changes from compress stress to tensile stress due to the structure change during annealing.     

Interfaces analysis of the HfO2/SiO2/Si structure

The physical and chemical properties of the HfO₂/SiO₂/Si stack have been analyzed using cross-section HR TEM, XPS, IR-spectroscopy and ellipsometry. HfO₂ films were deposited by the MO CVD method using as precursors the tetrakis 2,2,6,6 tetramethyl-3,5 heptanedionate hafnium—Hf(dpm)₄ and dicyclopentadienil-hafnium-bis-diethylamide—Сp₂Hf(N(C₂H₅)₂)₂.The amorphous interface layer (IL) between HfO₂ and silicon native oxide has been observed by the HRTEM method. The interface layer comprises hafnium silicate with a smooth varying of chemical composition through the IL thickness. The interface layer formation occurs both during HfO₂ synthesis, and at the annealing of the HfO₂/SiO₂/Si stack. It was concluded from the XPS, and the IR-spectroscopy that the hafnium silicate formation occurs via a solid-state reaction at the HfO₂/SiO₂ interface, and its chemical structure depends on the thickness of the SiO₂ underlayer.     

Spin splitting of image-potential states on fcc Fe/Cu(100)

Received: 19 October 1998     

Growth and characterization of Y2O3 thin films

Y₂O₃ thin films were grown on silicon (1 0 0) substrates by pulsed-laser deposition at different substrate temperatures and O₂ pressures. The structure and composition of films are studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Y₂O₃ thin films deposited in vacuum strongly oriented their [1 1 1] axis of the cubic structure and the film quality depended on the substrate temperature. The magnitude of O₂ pressure obviously influences the film structure and quality. Due to the silicon diffusion and interface reaction during the deposition, yttrium silicate and SiO₂ were formed. The strong relationship between composition and growth condition was discussed.     

Transient differential reflectivity of ferromagnetic and paramagnetic phases in the bilayered manganite La1.24Sr1.76Mn2O7

Photoinduced effects in a single crystal of bilayered manganites, La_2−2xSr_1+2xMn₂O₇ (x=0.38), were investigated in a wide range of temperatures by pump-probe measurement at a photon energy of 1.6 eV. In a ferromagnetic metallic state, significant enhancement of positive rise in differential reflectivity with a slow relaxing time of 100 ps was observed just below T_C=127 K, indicating that the reflectivity change with the slow relaxation time constant is induced by laser heating. We have also observed an unconventional fast relaxing component that has a time constant of the order of 10 ps. This fast relaxing component, whose absolute value has an asymmetric peak at T_C, is presumably due to short-range correlation of Jahn-Teller distortion.     

SiO2-PbF2-CdF2 glasses and glass ceramics

Lead-Cadmium fluorosilicate stable glasses were prepared and the vitreous domain region determined in the composition diagram. Characteristic temperatures were obtained from thermal analysis and the structural studies performed illustrate clearly the role played by lead atoms in the glasses crystallization behavior and the glass-forming ability of cadmium atoms. The occurrence of either a cubic lead fluoride or a lead-cadmium fluoride solid solution in crystallizing samples was found to be dependent on Er³⁺ doping. The optically active ions were found to concentrate in the crystalline phase and in fact play the role of nucleating agent as suggested from X-ray diffraction and EXAFS measurements.     

Theory for the laser-induced femtosecond phase transition of silicon and GaAS

We analyze he femtosecond instability of the chamond lattice of silicon and GaAs, which is induced by a dense electron-hole plasma after excitation by a very imense laser pulse. We obtain that the electron-hole plasma causes an instability of both transverse acoustic and longitudinal optical phonons. So, within less than 200fs, the atoms are displaced more than 1 Å from their equilibrium position. The gap between the conduction and the valence band then vanishes and the symmetries of the diamond structure are destroyed, which has important effects on the optical reflectivity and second-harmonic generation. After that, the crystal melts very rapidly because of the high kinetic energy of the atoms. Note that mis is in good agreement with recent experiments done on Shand GaAs using a pump laser to excite a dense electron hole plasma and a probe laser to observe the resulting changes in the atomic and electronic structure.Paper presented at the 129th WE-Heraeus-Seminar on Surface Studies by Nonlinear Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994     

Photoelectronic and electrical properties of Tl2InGaS4 layered crystals

Tl₂InGaS₄ layered crystals are studied through the dark electrical conductivity, space charge limited current and illumination- and temperature-dependent photoconductivity measurements in the temperature regions of 220-350 K, 300-400 K and 200-350 K, respectively. The space charge limited current measurements revealed the existence of a single discrete trapping level located at 0.44 eV. The dark electrical conductivity showed the existence of two energy levels of 0.32 eV and 0.60 eV being dominant above and below 300 K, respectively. The photoconductivity measurements reflected the existence of two other energy levels located at 0.28 eV and 0.19 eV at high and low temperatures, respectively. The photocurrent is observed to increase with increasing temperature up to a maximum temperature of 330 K. The illumination dependence of photoconductivity is found to exhibit supralinear recombination in all the studied temperature ranges. The change in recombination mechanism is attributed to exchange in the behavior of sensitizing and recombination centers.