Structure, thermally and optically induced effects in amorphous As2Se3 films prepared by pulsed laser deposition

Thin amorphous As-Se films were prepared by pulsed laser deposition (PLD) and by classical thermal evaporation techniques. Raman spectra and optical properties (optical gap, E_g^opt, index of refraction, n, third-order non-linear susceptibility, χ⁽³⁾) of prepared films and their photo- and thermally induced changes were studied. The structure of laser deposited films was close to the corresponding bulk glasses contrary to thermal evaporated films. The composition of PLD films was practically unchanged during the process of deposition. The optically and thermally induced changes of n and of E_g^opt in PLD films are different from the changes in thermally deposited films. The differences are discussed.     

Nd3+-doped LiYF4 thin films prepared by pulsed laser deposition

Nd:LiYF₄ (YLF) thin films were prepared on CaF₂ or YLF substrates by pulsed laser deposition, using a KrF laser for ablation of Nd:LiYF₄ single-crystal targets. For 10 J/cm², 450 °C and about 10^-6 mbar pressure, transparent and crystalline, highly textured, YLF films were obtained, without oxyfluoride or YF₃ contamination. High surface roughness is shown by optical microscopy and interface ion diffusion between film and substrate is evidenced by Rutherford backscattering spectroscopy. Fluorescence properties of the films are quite similar to those of bulk Nd:YLF crystal, which confirms the pure YLF composition and shows good conservation of Nd³⁺ ion doping rate. PACS 81.15.Fg; 68.55.Jk; 78.55.Hx     

Optical parameters of In–Se and In–Se–Te thin amorphous films prepared by pulsed laser deposition

The thin films of materials based on In–Se are under study for their applicability in photovoltaic devices, solid-state batteries and phase-change memories.The amorphous thin films of In₂Se_3−xTe_x (x=0–1.5) and InSe were prepared by pulsed laser deposition method (PLD) using a KrF excimer laser beam (λ=248 nm, 0.5 J cm⁻²) from polycrystalline bulk targets. The compositions of films verified by energy-dispersive X-ray analysis (EDX) were close to the compositions of targets. The surfaces of PLD films containing small amount of droplets were viewed by optical and scanning electron microscopy (SEM).The optical properties (transmittance and reflectance spectra, spectral dependence of index of refraction, optical gap, single-oscillator energy, dispersion energy, dielectric constant) of the films were determined.The values of index of refraction increased with increasing substitution of Te for Se in In₂Se₃ films, the values of the optical gap decreased with increasing substitution of Te for Se in In₂Se₃ films.     

Nonlinear optical properties in SrTiO3 thin films by pulsed laser deposition

Well-crystallized 250 nm-thick SrTiO₃ thin films on fused-quartz substrate were prepared by pulsed laser deposition. The band-gap of SrTiO₃ thin film by transmittance spectra is equal to 3.50 eV, larger than 3.22 eV for the bulk crystal. The nonlinear optical properties of the films were examined with picosecond pulses at 1.064 μm excitation. A large two-photon absorption (TPA) with absorption coefficient of 87.7 cm/GW was obtained, larger than 51.7 cm/GW for BaTiO₃ thin films. The nonlinear refractive index n₂ is equal to 5.7×10⁻¹⁰ esu with a negative sign, larger than 0.267×10⁻¹¹ esu for bulk SrTiO₃. The large TPA is attributed to intermediate energy levels introduced by the grain boundaries, and the optical limiting behaviors stemming from both TPA and negative nonlinear refraction were also discussed.     

Effect of laser incident energy on the structural,morphological and optical properties of Cu2ZnSnS4 (CZTS) thin films

The polycrystalline Cu₂ZnSnS₄ (CZTS) thin films have been prepared by pulsed laser deposition (PLD) method at room temperature. The laser incident energy was varied from 1.0 at the interval of 0.5–3.0 J/cm². The effect of laser incident energy on the structural, morphological and optical properties of CZTS thin films was studied by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and optical absorption. The studies reveal that an improvement in the structural, morphological and optical properties of CZTS thin films with increasing laser incident energy up to 2.5 J/cm². However, when the laser incident energy was further increased to 3.0 J/cm², leads to degrade the structural, morphological and optical properties of the CZTS thin films.     

Ferroelectric SrxBa1-xNb2O6 optical waveguiding thin films on SiO2-coated Si(100) substrates

x Ba_1-xNb₂O₆ (x=0.5) films (abbreviated as SBN:0.5) on SiO₂-coated Si substrates are potential components for the application of integrated electro-optics devices. SBN:0.5 optical waveguiding thin films on SiO₂-coated Si substrates with a very thin MgO diffusion buffer have been successfully prepared by pulsed laser deposition. The as-grown films have a refractive index of 2.28, which is close to that of bulk SBN. X-ray analysis showed that the as-grown films have a single-phase tetragonal tungsten bronze structure. The SBN:0.5 thin films prepared by PLD exhibit favorable ferroelectric and optical waveguiding properties. The composition and the morphology of the films were also examined by XPS and by SEM, respectively. Ferroelectric SBN:0.5 optical waveguiding thin films on SiO₂-coated Si substrates are expected to be used in integrated electro-optic devices. Received: 27 February 1997/Accepted: 17 October 1997     

The comparison of Ag–As33S67 films prepared by thermal evaporation (TE), spin-coating (SC) and a pulsed laser deposition (PLD)

Chalcogenide thin films could be prepared by many experimental methods resulting in some differences in structure and physicochemical properties of prepared films. In this work, the As₃₃S₆₇ amorphous films were prepared by three different preparation techniques: vacuum thermal evaporation (TE), pulsed laser deposition (PLD) and spin-coating (SC). A silver film was deposited on the top of the As₃₃S₆₇ films and photodoped.The X-ray diffraction analysis showed significant differences in arrangement between bulk glass and thin films and also among films themselves. The Raman spectroscopy showed that the Raman spectra of PLD film and bulk glass are almost similar. On the other hand, TE films contain higher amount of homopolar bonds As–As and S–S. The value of refractive index of As₃₃S₆₇ bulk glass was 2.31. All prepared films have lower index of refraction contrary to bulk glass, i.e. TE∼2.27, PLD∼2.20 and SC∼1.90. The increase of refractive index with silver concentration is shown either. The optical bandgap of undoped As–S prepared films was different: TE∼2.42 eV, PLD∼2.45 eV and SC∼2.54 eV.     

AgAsS2 amorphous chalcogenide films prepared by pulsed laser deposition

A pulsed laser deposition technique has been applied to prepare amorphous ternary Ag–As–S films without an annealing process after the deposition. The films were prepared from AgAsS₂ bulk glass using a KrF excimer laser. Energy-dispersive X-ray analysis and Rutherford backscattering were used to obtain the composition of the studied films. VASE ellipsometry has been used to determine optical properties and homogeneity of the index of refraction. Comparison of two models is presented. PACS 78.66.Jg; 81.15.Fg; 81.40.Wx     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Thickness distribution of thin amorphous chalcogenide films prepared by pulsed laser deposition

Amorphous chalcogenide thin films were prepared from As₂Se₃, As₃Se₂ and InSe bulk glasses by pulsed laser deposition using a KrF excimer laser. Thickness profiles of the films were determined using variable angle spectroscopic ellipsometry. The influence of the laser beam scanning process during the deposition on the thickness distribution of the prepared thin films was evaluated and the corresponding equations suggested. The results were compared with experimental data.     

Characterization and antibacterial functions of Ag–TiO<Subscript>2</Subscript> and W–TiO<Subscript>2</Subscript> nanostructured thin films prepared by sol-gel/laser-induced technique

A novel sol-gel/laser-induced technique (SGLIT) has been developed to form nanocrystalline titanium dioxide (TiO₂) based thin films with an improved antibacterial performance. TiO₂ precursor films loaded with W⁺⁶ and Ag⁺² ions (W–TiO₂, Ag–TiO₂) were prepared separately by sol-gel method and spin-coated on microscopic glass slides. As-dried films were subjected to KrF excimer laser pulses at optimized parameters to generate mesoporous anatase and rutile phases at room temperature. The anatase phase was obtained after irradiation with 10 laser pulses only at 75–85 mJ/cm² fluence in W–TiO₂ films. However, higher number of laser pulses and higher W⁺⁶ content favored the formation of rutile. Whereas Ag–TiO₂ films exhibited anatase up to 200 laser pulses at the same fluence. The films were characterized by using XRD, FEG-SEM, TEM and UV-Vis spectrophotometer to investigate the crystallographic structure, phase transformation, surface morphology, film thickness and the optical properties. A crystallite size of approximately 20 nm was achieved from the anatase prepared by SGLIT. The films exhibited an enhanced antibacterial function against E-Coli cells under the UV excitation.     

Effect of the excimer laser irradiation on sol–gel derived tungsten–titanium dioxide thin films

A novel technique based on the excimer laser induced crystallization and modification of TiO₂ thin films is being reported. W⁺⁶ ions loaded TiO₂ (WTO) precursor films were prepared by a modified sol–gel method and spin-coated onto microscopic glass slides. Pulsed KrF (248 nm, 13 ns) excimer laser was used to irradiate the WTO amorphous films at various laser parameters. Mesoporous and nanostructured films consisting of anatase and rutile were obtained after laser irradiation at room temperature. The effect of varying W⁺⁶ ions concentrations on structural and optical properties the WTO films was analyzed by X-ray diffraction, field-emission scanning electron microscope, UV-Vis spectrophotometer and transmission electron microscope before and after laser treatment. Films irradiated for 10 pulses at 65–75 mJ/cm² laser fluence, exhibited anatase whereas higher parameters promoted the formation of rutile. XPS results revealed WO₃ along with minor proportion of WO₂ compounds after laser irradiation. Photo-absorbance of the WTO films was increased with increase in W⁺⁶ ions concentration in the film. TEM results exhibited a crystallite size of 15 nm which was confirmed from SEM results as well.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

Optical properties of SrTiO<Subscript>3</Subscript> thin films by pulsed laser deposition

SrTiO₃ thin films were prepared on a fused-quartz substrate by pulsed laser deposition (PLD). Dense and homogeneous films with a thickness of 260 nm were prepared. Optical constants (refractive index n and extinction coefficient k) were determined from the transmittance spectra using the envelope method. The optical band gap energy of the films was found to be 3.58 eV, higher than the 3.22 eV for bulk SrTiO₃, attributable to the film stress exerted by the substrate. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The refractive index and the packing density for the PLD-prepared SrTiO₃ thin films are higher than those for the SrTiO₃ films prepared by physical vapor deposition, sol–gel and RF sputtering. Received: 18 March 2002 / Accepted: 7 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: mszhang@nju.edu.cn     

Effect of annealing on the optical properties of In2Te3 thin films

2 Te₃ thin films of different thickness were prepared in a vacuum of 10^-5 Torr onto glass and quartz substrates held at about 300 K during the deposition process. X-ray diffraction analysis showed that the prepared samples in bulk or as-deposited thin-film forms were in an amorphous state. On annealing at 573 K, films have a β-phase polycrystalline structure. Transmittance and reflectance measurements in the spectral range of 400–2500 nm for films deposited onto quartz substrates were used to calculate the optical constants (the refractive index n, the absorption index k and the absorption coefficient α) for In₂Te₃ films, either as-deposited or annealed at different temperatures. The refractive index has anomalous behavior in the region of the fundamental absorption edge. The allowed optical transitions were found to be nondirect transitions, with an optical gap of 1.02 eV for the samples under test. The effect of annealing on the optical gap is interpreted in terms of the density of states proposed by Mott and Davis. Received: 22 June 1997/Accepted: 9 July 1997     

Optical CO gas sensing using nanostructured NiO and NiO/SiO2 nanocomposites fabricated by PLD and sol–gel methods

Several kinds of NiO-based nanostructured films were prepared by pulsed-laser deposition (PLD) and sol–gel method, and CO sensing properties (1%, balanced by N₂) of these films were studied. The sensitivity, defined as a difference of optical transmittance by gas atmospheric change (T=T(CO)-T(air)), increased with increasing NiO content for the sol–gel prepared films, and increased with the film thickness for the laser deposited NiO films. Sol–gel films exhibited shorter response time than NiO films prepared by PLD under low Ar pressure of 6.7×10^-2 Pa indicating a better gas permeability. A shorter response time was also obtained upon raising argon pressure from 6.7×10^-2 Pa to 8.0 Pa during laser ablation due to the morphological change. Covering a NiO film even with a very thin (0.8 nm) layer of SiO₂ by sputtering drastically reduced the CO sensitivity. The multilayered NiO/SiO₂ films were substantially less sensitive to the CO gas than NiO films due to the same reason. Sensing mechanism of the NiO films is due to catalytic CO oxidation that reduces the concentration of adsorbed O₂ species and results in optical transmittance increase upon change in the environment from air to CO. PACS 81.15.Fg; 81.20.Fw; 83.85.Gk     

Study on the properties and charge generation in dye-sensitized n-TiO2|dye|p-CuI solid state photovoltaic solar cells

Transparent semiconducting copper iodide (CuI) films were prepared by XeCl Excimer laser and their characteristics are investigated. These films exhibited optical transmittance over 80% in the wavelength range from 400 to 900 nm and minimum resistivity of about 2 kΩ cm⁻¹. The optical absorption of the these films shows a remarkable blue shift compared to that of polycrystalline of CuI, which can be explained from the viewpoint formation of ultra fine of CuI grains. The titanium dioxide (TiO₂) films have been prepared by sol-gel method. The properties of pulsed laser deposited CuI and TiO₂ films in power output of n-TiO₂|dye|p-CuI cells is studied. An efficient charge generation is observed through the illumination of TiO₂ layer of the fabricated n-TiO₂|dye|p-CuI solid state photovoltaic solar cells. From the current-voltage characteristics, the fill factor and power conversion efficiency were about of 45 and 3%, respectively. The maximum photo-current of about 12.5 mA/cm² and photo-voltage of 475 mV under AM 1.5 conditions were obtained for the n-TiO₂|dye|p-CuI solid states photovoltaic solar cells with good reproducibility. Adsorbed dye molecules to the TiO₂ surface act as a relay, especially under illumination through TiO₂ layer in the wave range region of 300-400 nm.     

Preparation of Tl-Ba-Ca-Cu-O thin films by diffusion of Tl into laser evaporated Ba2Ca2Cu3Ox films

Preparation of superconducting Tl-Ba-Ca-Cu-O thin films by diffusion of Tl into laser evaporated Ba₂Ca₂Cu₃O_x thin films is reported. From a sintered Ba₂Ca₂Cu₃O_x bulk sample we prepared using a pulsed Nd:YAG laser, Ba-Ca-Cu-O thin films on sapphire and SrTiO₃ single-crystal substrates. Subsequently the films were loaded with Tl by simultaneously annealing the films together with a sintered Tl₂Ba₂Ca₂Cu₃O₁₀ sample both enclosed in a small stainless steel box; in our procedure Tl contamination was reduced to a minimum. T_c values near 100 K and critical currents of 5·10³ A/cm² at 77 K were obtained.     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Optical properties of high-density amorphous carbon films grown by nanosecond and femtosecond pulsed laser ablation

High-density tetrahedral amorphous carbon (ta-C) films have been prepared by nanosecond (17 ns) and femtosecond (150 fs) pulsed laser deposition (PLD) using fluences and repetition rates compatible with fast and homogeneous growth over large areas. Their optical properties were measured by spectroscopic ellipsometry from 1.0 to 4.7 eV and analyzed using a multi-layer Tauc-Lorentz model. In spite of very different ablation mechanisms, both PLD techniques produce high density bulk layers as revealed by a refractive index (n at 2 eV) of 2.7±0.1 for both fs-PLD and ns-PLD. Films are covered by a few nm-thick sp²-rich top layer which is denser and thicker in femtosecond PLD as compared to nanosecond PLD. The respective roles of low and high energies in the kinetic energy distribution of the incident carbon species are discussed in terms of densification and sp³↦sp² configurational relaxation predicted by the subplantation growth model. The significantly higher optical gap found in the ns-PLD films is attributed to the larger contribution of energetic species with kinetic energies E_c≥200 eV, as revealed by time-of-flight optical studies. PACS 81.40.Tv; 81.05.Uw; 81.15.Fg