On the porosity of coldly condensed sers active Ag films: II. Comparison of adsorption and Raman scattering of pyridine

The adsorption of pyridine on coldly deposited Ag films annealed at temperatures ranging from 58 to 330 K, the porous surface topography of which has been investigated in part I of this work, has been studied by means of UPS, work function change and thermal desorption measurements. Pyridine induced work function changes have been employed to follow the surface diffusion of pyridine molecles into the pores of these Ag films. The surface diffusion is very slow below 60 K, but readily takes place at 130 K with an estimated activation energy of surface migration of E_m ≈ 4 kcal/mol. Preadsorption of Xe into the pores of the films causes inhibition of pyridine diffusion into the pores. The onset of pyridine desorption from porous films is detected at ≈ 200 K while from flat films the desorption begins already at 150 K. The careful analysis of our data on the structure of the coldly deposited Ag films and the adsorption behavior of pyridine on these films as well as a survey of published SERS data lead us to conclude that the SERS active sites of coldly deposited Ag films are within the pores. This conclusion is in agreement with recent theoretical calculations.     

Optical and electrical properties of thermally evaporated In49Se48Sn3 films

Nearly stoichiometric thin films of In₄₉Se₄₈Sn₃ were deposited at room temperature, by conventional thermal evaporation of the presynthesized materials, onto precleaned glass substrates. The microstructural studies on the as-deposited and annealed films, using transmission electron microscopy and diffraction (TEMD), revealed that the as-deposited films are amorphous in nature, while those annealed at 498 K are crystalline. The optical properties of the investigated films were determined from the transmittance and reflectance data, in the spectral range 650-2500 nm. An analysis of the optical absorption spectra revealed a non-direct energy gap characterizing the amorphous films, while both allowed and forbidden direct energy gaps characterized the crystalline films. The electrical resistance of the deposited films was carried out during heating and cooling cycles in the temperature range 300-600 K. The results show an irreproducible behavior, while after crystallization the results become reproducible. The analysis of the temperature dependence of the resistance (ln(R) vs. 1000/T) for crystalline films shows two straight lines corresponding to both extrinsic and intrinsic conduction. The room temperature I-V characteristics of the as-deposited films sandwiched between similar Ag metal electrodes shows an ohmic behavior, while non-ohmic behavior attributed to space charge limited conduction has been observed when the films are sandwiched between dissimilar Ag/Al metal electrodes.     

Characterization of chemically deposited ZnSe/SnO2/glass films: Influence of annealing in Ar atmosphere on physical properties

The Zinc Selenide (ZnSe) thin films have been deposited on SnO₂/glass substrates by a simple and inexpensive chemical bath deposition (CBD). The structural, optical and electrical properties of ZnSe films have been characterized by X-ray diffraction (XRD), Energy Dispersive X-ray Analysis (EDAX), optical absorption spectroscopy, and four point probe techniques, respectively. The films have been subjected to different annealing temperature in Argon (Ar) atmosphere. An increase in annealing temperature does not cause a complete phase transformation whereas it affects the crystallite size, dislocation density and strain. The optical band gap (E_g) of the as-deposited film is estimated to be 3.08 eV and decreases with increasing annealing temperature down to 2.43 eV at 773 K. The as-deposited and annealed films show typical semiconducting behaviour, dρ/dT > 0. Interestingly, the films annealed at 373 K, 473 K, and 573 K show two distinct temperature dependent regions of electrical resistivity; exponential region at high temperature, linear region at low temperature. The temperature at which the transition takes place from exponential to linear region strongly depends on the annealing temperature.     

Epitaxial LSMO films grown on MgO single crystalline substrates

The manganite La_0.67Sr_0.33MnO₃ (LSMO) layers are deposited on single crystal MgO(0 0 1) substrates using a magnetron dc sputtering. The crystalline perfection of the layers, both the as-prepared and the annealed, are characterized by X-ray diffraction technique, rocking curve measurements, Rutherford backscattering spectroscopy (RBS) and transmission electron microscopy (TEM). TEM analyses give evidence of the epitaxial growth of the annealed LSMO with a nanocrystalline surface layer. The temperature dependence of resistance in the 77-340 K range is measured by a standard four-probe technique. While the as-prepared film does not show any transition from paramagnetic to ferromagnetic state, the film annealed in oxygen shows steep R(T) dependence with a peak at 330 K and maximal slope (dR/dT) at 290 K where the maximal sensitivity is 3% K⁻¹.     

Sputtered magnesium diboride thin films: Growth conditions and surface morphology

Magnesium diboride (MgB₂) thin films were deposited on C-plane sapphire substrates by sputtering pure B and Mg targets at different substrate temperatures, and were followed by in situ annealing. A systematic study about the effects of the various growth and annealing parameters on the physical properties of MgB₂ thin films showed that the substrate temperature is the most critical factor that determines the superconducting transition temperature (T_c), while annealing plays a minor role. There was no superconducting transition in the thin films grown at room temperature without post-annealing. The highest T_c of the samples grown at room temperature after the optimized annealing was 22 K. As the temperature of the substrate (T_s) increased, T_c rose. However, the maximum T_s was limited due to the low magnesium sticking coefficient and thus the T_c value was limited as well. The highest T_c, 29 K, was obtained for the sample deposited at 180 °C, annealed at 620 °C, and was subsequently annealed a second time at 800 °C. Three-dimensional (3D) AFM images clearly demonstrated that the thin films with no transition, or very low T_c, did not have the well-developed MgB₂ grains while the films with higher T_c displayed the well-developed grains and smooth surface. Although the T_c of sputtered MgB₂ films in the current work is lower than that for the bulk and ex situ annealed thin films, this work presents an important step towards the fabrication of MgB₂ heterostructures using rather simple physical vapor deposition method such as sputtering.     

The excitonic absorption spectrum of thin Ag2ZnI4 films

The electron absorption spectrum of thin films of the Ag₂ZnI₄ complex compound is studied at photon energies of 3–6 eV. It is established that the interband absorption edge corresponds to an allowed direct transitions across the energy gap E _g=3.7 eV. A strong exciton band is adjacent to the absorption edge at E _ex=3.625 eV (80 K); in the 80–390 K range, the temperature behavior of the half-width Γ of this band is determined by the exciton-phonon interaction typical of quasi-one-dimensional excitons. At T≤390 K, a discontinuity in the slope of the E _ex(T) and Γ(T) dependences is observed. This discontinuity is associated with the generation of Frenkel defects and is accompanied by the transfer of Ag ions to the interstitial sites and vacancies of the crystal lattice of the compound.     

Synthesis and bactericidal ability of Ag/TiO2 composite films deposited on titanium plate

In this study, we develop a bactericidal coating material for micro-implant, TiO₂ films with Ag deposited on were prepared on titanium plates by sol-gel process. Their anti-microbial properties were analyzed as a function of the annealed temperature using Escherichia coli as a benchmark microorganism. Ag nanoparticles deposited on TiO₂ film were of metallic nature and could grow to larger ones when the annealed temperature increased. The results indicated that the smaller size of Ag nanoparticles, the better bactericidal ability. On the other hand, the positive antibacterial effect of TiO₂ enhanced the bactericidal effect of Ag.     

The influence of substrate temperature and annealing on the properties of pulsed laser-deposited YIG films on fused quartz substrate

Yttrium iron garnet (YIG) thin films were deposited on fused quartz substrate at different substrate temperatures (T_s) varying from room temperature (RT) to 850 °C using pulsed laser deposition (PLD) technique. All the films in the as-deposited state were X-ray amorphous and non-magnetic at RT. The film deposited at RT after annealing at temperatures T_a?700 °C showed both X-ray peaks and the magnetic order. The films deposited at higher T_s (500–850 °C) and then annealed at 700 °C resulted in better-quality films with higher 4πM_s value. The highest value of magnetization was for the sample deposited at 850 °C and annealed at 700 °C, which is 68% of the bulk 4πM_s value.     

On the preparation and the characterization of superconducting thin films of YBa2Cu3O7−x

The results of our initial efforts to deposit thin films of YBa₂Cu₃O_7−x system on sapphire substrate are described. The deposited films are shiny black in appearance and are of quite uniform chemical composition. The annealed films exhibit zero resistance superconducting transition temperatureT _c(R=0) ranging between 23 K and 30 K.     

ZnO退火条件对硫化法制备的ZnS薄膜特性的影响

采用反应磁控溅射法在玻璃和石英衬底上沉积了ZnO薄膜, 然后经过不同条件退火和在H22S气氛中硫化最终得到ZnS薄膜. 用x射线粉末衍射仪、扫描电子显微镜和UV—VIS分光光度计 对ZnS薄膜样品进行了分析. 结果表明, ZnO薄膜硫化后的晶体结构和光学性质取决于它的退 火条件. 真空和纯O2₂中退火的ZnO薄膜硫化后只是部分形成六角晶系结构的ZnS . 而在空气 和纯N2₂中退火的ZnO薄膜则全部转变为ZnS, 在可见光范围内的光透过率 关键词： ZnS薄膜 磁控溅射 ZnO硫化 太阳电池     

Characterization of AgInS2 thin films prepared by vacuum evaporation

We characterized AgInS₂ thin films prepared by vacuum evaporation. In the case of thin films annealed at 400 °C, diffraction peaks were observed only for the chalcopyrite AgInS₂ phase. The chemical composition of the thin films annealed at 400 °C was 26.5 at% Ag, 23.8 at% In, and 49.7 at% S. PL spectra of the AgInS₂ thin films at 10.7 K showed peaks at 1.70, 1.80, and 1.83 eV. The PL peak at1.80 eV was attributed to sulfur deficiency.     

Annealing effect on CdS/SnO2 films grown by chemical bath deposition

The extensive investigation of the annealing effect in nitrogen atmosphere on the structural optical and electrical properties of chemically deposited CdS films on SnO₂ has been performed. The as-deposited film shows 2.45 eV band gap (E_g) and decreases with increasing annealing temperature. The film annealed at 623 K having pure hexagonal phase (a = 4.14 Å, c = 6.71 Å for [1 0 0] plane) and E_g = 2.36 eV shows 10 times higher conductivity for all temperature range, and shows two different activation energies E_a = 0.114 eV and E_a = 0.033 eV for the temperature range 395 K ≤ T ≤ 515 K and 515 K ≤ T ≤ 585 K, respectively. The structural parameters such as dislocation density, strain and optical parameters such as absorption and extinction coefficient are calculated and compared for all the films.     

Laser-assisted synthesis of semiconductor chromium disilicide films

Different photo-assisted techniques were employed for chromium disilicide (CrSi₂) semiconductor film fabrication. Flash evaporation of CrSi₂ powder on the Si substrate heated to ∼740 K leads to the formation (according to XRD study) of amorphous films. Post-annealing at 920 K leads to the formation of polycrystalline CrSi₂ phase. Crystallization is improved by further annealing with 1500 Q-Switched Nd:YAG laser pulses. Optical properties of the as deposited and annealed CrSi₂ films have been investigated in the 240-1100 nm spectral range by using spectroscopic ellipsometry. The formation of CrSi₂ semiconductor phase was additionally confirmed by the temperature dependence of electrical resistance of the films treated by Q-switched Nd:YAG laser. The band gap for intrinsic conductivity results E_g ≅ 0.2 eV. Backward laser-induced film transfer (LIFT) was also used for CrSi₂ film deposition from bulk material on Si substrates. Pulsed CO₂ laser was employed for this purpose, because of transparency of silicon at the 10.6 μm wavelength. Measurements of the electrical resistance of the deposited films as a function of temperature showed their semiconductor behavior (E_g = 6 × 10⁻⁴ eV). Chromium disilicide films were also deposited by congruent pulsed laser ablation deposition on Si substrates either at room temperature or heated to about 740 K. In this last case the deposit exhibits semiconducting properties with E_g ≅ 0.18 eV.     

RF-plasma assisted pulsed laser deposition of nitrogen-doped SrTiO3 thin films

Perovskite-type nitrogen substituted SrTiO₃ thin films were deposited with a one-step process by RF-plasma assisted pulsed laser deposition from a SrTiO₃ target using a N₂ plasma, while deposition with a NH₃ plasma yields films with almost no incorporated nitrogen. The deposited films exhibit a cubic perovskite-type crystal structure and reveal oriented growth on MgO(100) substrates. The unit cell parameters of the studied N-doped SrTiO₃ films range within 3.905<a<3.918 Å, which is slightly larger than for SrTiO₃ (a=3.905 Å). The nitrogen content in the deposited films varies from 0.2 to 0.7 atom%. The amount of incorporated nitrogen in the films decreases with increasing RF-power, while the N₂ flow rate does not have any pronounced influence on the N content. Nitrogen incorporation results in an increased optical absorption at 400–600 nm, which is associated with N(2p) energy states that have a higher energy level than the valence band in strontium titanate. The optical band gap energies in the studied N-doped SrTiO₃ films are at 3.2–3.3 eV, which is very similar to that of pure strontium titanate (～3.2 eV). Films deposited with NH₃ for the RF-plasma exhibit a lower degree of crystallinity and reveal almost no nitrogen incorporation into the crystal lattice.     

Deposition of superconducting thin films of YBa2Cu3O x on sintered SrTiO3 substrates

Thin films of highT _coxide superconductor were deposited on sintered SrTiO₃ substrates by 50 Hz a.c. sputtering. The superconducting onset temperature occurred at 90 K and the offset temperature at 72 K. The deposition conditions were found to influence the ordering of the annealed films.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Structural and electrical properties of lithium manganese oxide thin films grown by pulsed laser deposition

LiMn₂O₄ thin films were deposited by reactive pulsed laser deposition technique and studied the microstructural and electrical properties of the films. The LiMn₂O₄ thin films deposited in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 573 K from a lithium rich target were found to be nearly stoichiometric. The films exhibited predominantly (111) orientation representing the cubic spinel structure with Fd3m symmetry. The intensity of (111) peak increased and a slight shift in the peak position was observed with the increase of substrate temperature. The lattice parameter increased from 8.117 to 8.2417 Å with the increase of substrate temperature from 573 to 873 K. The electrical conductivity of the films is observed to be a strong function of temperature. The evaluated activation energy for the films deposited at 873 K is 0.64 eV.     

Effect of annealing on the magnetic and magnetooptical properties of Ni films

The magnetic and magnetooptical properties of 50-to 200-nm-thick Ni films, both as-deposited and annealed at T_ann = 300, 400, or 500°C, were studied. Volume and near-surface hysteresis loops were measured with a vibrating-sample magnetometer (VSM) and with the use of the transverse Kerr effect (TKE). The annealing temperature was found to exert a strong effect on the magnetic characteristics of the samples under study. It was established, in particular, that the coercivity H _C of Ni films increases and the remanent magnetization decreases with increasing annealing temperature. The observed dependences of the magnetic properties of the films on film thickness and annealing temperature are explained as being due to microstructural characteristics of the samples. It was found that, while TKE spectra obtained in the incident-photon energy region from 1.5 to 6 eV have the same shape for all the Ni films studied, the magnitude of the TKE decreases with increasing T_ann. This experimental observation is accounted for by the decreased saturation magnetization of the annealed films.     

Surface and interface effects on structural transformation of vapor-deposited ethylbenzene films

We have investigated how the structures of vapor-deposited glassy films change with increasing temperature by using time-of-flight secondary ion mass spectrometry and ion scattering spectroscopy. It is found that intermixing of the topmost layer of an ethylbenzene film occur at temperature (~ 80 K) considerably lower than the glass transition temperature (T_g = 118 K) when the film is deposited at 20 K. This phenomenon can be interpreted as the occurrence of a two-dimensional liquid that diffuses into pores of the film, which is evidenced from comparison with surface diffusivity measurements using a porous silicon layer. For nonporous films deposited at higher temperatures, the molecules intermix gradually prior to the abrupt film morphology change at T_g. This phenomenon can be interpreted as decoupling between translational diffusivity and viscosity in the bulk. The film thickness has no significant effects on the evolution of supercooled liquid at T_g except for the monolayer film, whereas crystallization is quenched for the films thinner than 8 monolayers. The roles of the 2D liquid on the surface and an immobilized layer formed at the interface are discussed in finite-size effects on the glass-liquid transition and crystallization.     

Polycrystalline GaSb films prepared by the coevaporation technique

Gallium antimonide (GaSb) films were deposited onto fused silica and n-Si (100) substrates by coevaporating Ga and Sb from appropriate evaporation sources. The films were polycrystalline in nature. The size and the shape of the grains varied with the change in the substrate temperature during deposition. The average surface roughness of the films was estimated to be 10 nm. Grain boundary trap states varied between 2×10¹² and 2.2×10¹² cm^?2 while barrier height at the grain boundaries varied between 0.09 eV and 0.10 eV for films deposited at higher temperatures. Stress in the films decreased for films deposited at higher temperatures. XPS studies indicated two strong peaks located at ～543 eV and ～1121 eV for Sb 3d_3/2 and Ga 2p_3/2 core-level spectra, respectively. The PL spectra measured at 300 K was dominated by a strong peak located ～0.55 eV followed by two low intensity peaks ～0.63 eV and 0.67 eV. A typical n-Si/GaSb photovoltaic cell fabricated here indicated V _oc～311 mV and J～29.45 mA/cm², the density of donors (N _d)～3.87×10¹⁵ cm^?3, built in potential (V _bi)～0.48 V and carrier life time (τ)～28.5 ms. Impedance spectroscopy measurements indicated a dielectric relaxation time ～100 μs.