The nonlinear optical property and photoinduced anisotropy of?a?novel azobenzene-containing fluorinated polyimide

A novel azobenzene-containing fluorinated polyimide was synthesized. The nonlinear optical property and photoinduced birefringence of a polyimide thin film were investigated. Large third-order nonlinear refraction (n ₂=−4.49×10⁻¹¹ cm²/W) was observed in the polyimide thin film by carrying out Z-scan measurement. The polyimide thin film exhibited larger nonlinear refraction than that of a mono-azo dye doped PMMA thin film (n ₂=−1.63×10⁻¹² cm²/W). The photoinduced birefringence of the polyimide thin film (▵ n∼10⁻²) under different pump intensities was investigated; it was much larger than that of the mono-azo dye doped PMMA thin film (▵ n∼10⁻³). Moreover, the time constants for birefringence growth and relaxation processes were determined.     

Preparation and characterization of Li2CoMn3O8 thin film cathodes for high energy lithium batteries

An ion layer gas reaction (ILGAR) dip-coating process for the deposition of homogeneous spinel structured Li₂CoMn₃O₈ thin layers has been developed. Thin film cathodes for use in high-energy density lithium batteries with thicknesses of about 200 nm have been prepared. The films were found to be X-ray amorphous after preparation. After annealing at 700°C in air for 2 h, the spinel structure of Li₂CoMn₃O₈ was observed by X-ray diffraction analysis. The composition of the surface was studied by XPS, which indicated enhanced Li and Mn concentrations as a result of the rinsing process and different solubilities of the precursor salts. The electrochemical behavior was investigated by separating the annealed electrode sample from a conventional organic lithium ion-conducting electrolyte by a layer of LiPON solid electrolyte and using elemental lithium as counter electrode. A capacity of 110.8 mAh/g was observed which is related to the valence changes of Mn and Co in the spinel structure.     

Infrared spectra of BeSO4.4H2O and its deuterated analogue in 4000–1200 cm−1 region

IR spectra of BeSO₄.4H₂O and its deuterated analogue at ∼300 K and ∼110 K are reported in the region 4000–1200 cm⁻¹ using thin film and nujol mull techniques. The observed bands have been assigned as the internal modes of the water and the overtones and combinations of various modes using the recently revised assignments of SO₄ ²⁻ and Be(aq)₄ fundamentals in the region 1200–250 cm⁻¹ (Srivastavaet al 1976). The splitting of the internal modes of water has been discussed in the light of the effects of deuteration and cooling and it is shown that all the water molecules in a unit cell are asymmetric but crystallographically equivalent.     

Critical current densities of high pressure oxygen sputtered thin films of YBa2Cu3O7−x by non-resonant rf absorption method

The critical current densities (J _c) have been measured at 77K in high pressure oxygen sputtered thin films of YBa₂Cu₃O_7−x superconductor using the non-resonant rf absorption technique. High values ofJ _c (∼ 10⁵ A/cm²) are observed in these relatively large area (∼ 1·2 cm²) films.     

Effect of V5+ in the complex Li3xLa2/3−xTiO3-LaPO4 system

Lithium fast ion conductors of the composition Li_0.3La_2/3Ti_0.7P_0.3−xV_xO_3.3 (LTV) based on mixtures of Li_3xLa_2/3−xTiO₃ and LaPO₄ were prepared by solid state reaction at high temperature (≈ 1300 °C). AC impedance measurements indicate total conductivities of about 1 × 10⁻⁴ Scm⁻¹ for compositions of x=0∼0.3 at room temperature with an activation energy of ≈18 kJ·mol⁻¹ in the temperature range from 30 to 400 °C. X-ray powder diffraction patterns showed that the LTV system is composed of Li_3xLa_2/3−xTiO₃ perovskite solid solution and LaP_1−xV_xO₄ solid solution.     

XRD, conductivity and FTIR studies on LiI-Li2WO4-Li3PO4 prepared by low temperature sintering

Different amounts of Li₃PO₄ were mixed to a fixed ratio of LiI:Li₂WO₄, ground and pelletised before subjected to sintering at 70°C for 7 days. XRD shows that the product formed after sintering process is most likely Li₆P₄W₈O₃₂ due to peaks present at 10.6°, 22.4°, 24.0°, 24.4, 26.2°, 32.4° and 34.0°. Conductivity studies show that the sample with 25 wt.% Li₃PO₄ exhibits the highest room temperature conductivity of 3.42×10⁻³ Scm⁻¹. Conductivity is expected to occur through channel-like structures which could have formed due to corner or edge sharing of polyhedra. FTIR studies have shown the existence of WO₄ tetrahedra and WO₆ octahedral at 850 cm⁻¹ and 952 cm⁻¹, and phosphate tetrahedral at 564 cm⁻¹, 700 cm⁻¹, 890 cm⁻¹ and 1030 cm⁻¹.     

Influence of post-grown Li-rich and Li-poor vapor transport equilibration on composition, OH− absorption and optical-damage threshold of Mg (5 mol%) : LiNbO3 crystals

Li-rich (Li-poor) vapor transport equilibration (VTE) treatments on a number of Z-cut 0.47 mm thick congruent MgO (5 mol% in melt) : LiNbO₃ crystals were carried out at 1100°C over different durations ranging in 1–172 (40–395) h. Neutron activation analysis shows that neither Li-rich nor Li-poor VTE-induced Mg and Nb loss from the crystal occurred. The Li₂O content in the crystal was measured as a function of VTE duration by the gravimetric method. The Li-rich/Li-poor VTE effects on OH⁻ absorption were studied in comparison with the as-grown crystal. The study shows that the Li-rich VTE results in OH⁻ absorption band annihilation. After further oxidation treatment the band reemerges and peaks at the same wavenumber as that of the as-grown crystal (∼3535.6 cm⁻¹), showing that the MgO concentration in the Li-rich VTE crystal is still above the optical-damage threshold. The Li-poor VTE causes OH⁻ band shift to 3486.3–3491.6 cm⁻¹, indicating that the MgO concentration in all Li-poor VTE crystals is all below the optical-damage threshold. Further successive Li-rich VTE and oxidation treatments on the Li-poor VTE-treated crystal lead the band to shift back to 3535.6 cm⁻¹, showing that the post Li-rich VTE brought the Li-poor VTE-treated crystal above the optical-damage threshold again. It is found that the peaking position, band width, peaking absorption and band area of the absorption at ∼3486 cm⁻¹ all increase monotonously with the decrease of the Li₂O content arising from prolonged Li-poor VTE, and quantitative relationships to the Li₂O content are established for the latter two parameters. The VTE effects on the OH⁻ absorption are conducted with the VTE-induced OH⁻ content alteration and charge redistribution.     

Lithiated c-V<Subscript>2</Subscript>O<Subscript>5</Subscript> thin-film as positive electrode for rocking-chair solid-state lithium microbattery

We report for the first time the use of lithiated crystalline V₂O₅ thin films as positive electrode in all-solid-state microbatteries. Crystalline Li_xV₂O₅ films (x ≈ 0.8 and 1.5) are obtained by vacuum evaporation of metallic lithium deposited on sputtered c-V₂O₅. An all-solid-state lithium microbattery of Li_1.5V₂O₅/LiPON/Li exhibited a typical reversible capacity of 50 μAh/cm² in the potential range 3.8/2.15 V which exceeds by far the results known on all-solid-state lithium batteries using amorphous V₂O₅ films and lithiated amorphous Li_xV₂O₅ thin films as positive electrode. Hence, the present work opens the possibility of using high performance crystalline lithiated V₂O₅ thin films in rocking-chair solid-state microbatteries.     

Structural, optical and electrical properties of tin oxide thin film deposited by APCVD method

Tin oxide (SnO₂) thin films have been grown on glass substrates using atmospheric pressure chemical vapour deposition (APCVD) method. During the deposition, the substrate temperature was kept at 400°C–500°C. The structural properties, surface morphology and chemical composition of the deposited film were studied by X-ray diffraction (XRD), scanning electron microscope (SEM) and Rutherford back scattering (RBS) spectrum. XRD pattern showed that the preferred orientation was (110) having tetragonal structure. The optical properties of the films were studied by measuring the transmittance, absorbance and reflectance spectra between λ = 254 nm to 1400 nm and the optical constants were calculated. Typical SnO₂ film transmits ∼ 94% of visible light. The electrical properties of the films were studied using four-probe method and Hall-voltage measurement experiment. The films showed room temperature conductivity in the range 1.08 × 10² to 1.69 × 10² Ω⁻¹cm⁻¹.     

Experimental study of optical gas-dynamic processes of polymeric material ablation by ultrashort laser pulses

Optical gas-dynamic processes occurring in polymeric targets ((CH₂O) _n , (C₂F₄) _n ) exposed to ultrashort laser pulses (τ _0.5 ∼ 45 − 70 fs; λ _I,II,III = 266, 400, 800 nm; and E/S ∼ 0.1 − 40 J/cm² at r ₀ ∼ 20 μm) were studied under normal conditions and in vacuum (p ∼ 10⁻² Pa). The dynamics of the mass flow from the target surface (m′ ∼ 10⁻⁵ − 10⁻⁴ g/J) was studied and the spectral-energy thresholds of laser ablation, the electron density distribution (n _e ∼ 10¹⁴ − 10¹⁸ cm⁻³), the mass-averaged velocity of the material flow from the target surface (∼ 10³ m/s), and the chemical composition and average temperature in the near-surface plasma formation (T ∼ 5000 K) were determined using interference microscopy, emission spectroscopy, and shadowgraphy.     

Mass-spectrometric analysis of diffusion and solubility of helium in cerium-gadolinium ceramics with a submicrocrystalline structure

Diffusion and solubility of helium in Ce_0.8Gd_0.2O_{1.9 − δ} ceramics (δ = 0, 0.015) with a submicrocrystal structure are studied by thermodesorption of helium from preliminarily saturated (in the gas phase) crystals at temperatures of 613 and 673 K in the saturated pressure range 0–21 MPa. It is shown that, in this ceramics (δ = 0), the defect-trap diffusion mechanism operates. The main positions for dissolution are neutral anion vacancies formed as a result of thermal dissociation of impurity-vacancy complexes and saturated up to ∼1 × 10¹⁹ cm⁻³ at P = 6 MPa and T = 673 K. The dissociation energy of the complex and the energy of helium dissolution in the neutral anion vacancy are estimated at ∼2 eV and below −0.3 eV, respectively.     

SnO2 thin films grown by pulsed Nd:YAG laser deposition

SnO₂ thin films have been deposited on glass substrates by pulsed Nd:YAG laser at different oxygen pressures, and the effects of oxygen pressure on the physical properties of SnO₂ films have been investigated. The films were deposited at substrate temperature of 500°C in oxygen partial pressure between 5.0 and 125 mTorr. The thin films deposited between 5.0 to 50 mTorr showed evidence of diffraction peaks, but increasing the oxygen pressure up to 100 mTorr, three diffraction peaks (110), (101) and (211) were observed containing the SnO₂ tetragonal structure. The electrical resistivity was very sensitive to the oxygen pressure. At 100 mTorr the films showed electrical resistivity of 4×10⁻² Ω cm, free carrier density of 1.03×10¹⁹ cm⁻³, mobility of 10.26 cm² V⁻¹ s⁻¹ with average visible transmittance of ∼87%, and optical band gap of 3.6 eV.     

Thin TiO2 grown by metal–organic chemical vapor deposition on (NH4)2S x -treated InP

The electrical characteristics of thin TiO₂ films prepared by metal–organic chemical vapor deposition grown on a p-type InP substrate were studied. For a TiO₂ film of 4.7 nm on InP without and with ammonium sulfide treatment, the leakage currents are 8.8×10⁻² and 1.1×10⁻⁴ A/cm² at +2 V bias and 1.6×10⁻¹ and 8.3×10⁻⁴ A/cm² at −2 V bias. The lower leakage currents of TiO₂ with ammonium sulfide treatment arise from the improvement of interface quality. The dielectric constant and effective oxide charge number density are 33 and 2.5×10¹³ cm², respectively. The lowest mid-gap interface state density is around 7.6×10¹¹ cm⁻² eV⁻¹. The equivalent oxide thickness is 0.52 nm. The breakdown electric field increases with decreasing thickness in the range of 2.5 to 7.6 nm and reaches 9.3 MV/cm at 2.5 nm.     

Aerosol deposition of detonation nanodiamonds used as nucleation centers for the growth of nanocrystalline diamond films and isolated particles

The aerosol deposition of detonation nanodiamonds (DNDs) on a silicon substrate is comprehensively studied, and the possibility of subsequent growth of nanocrystalline diamond films and isolated particles on substrates coated with DNDs is demonstrated. It is shown that a change in the deposition time and the weight concentration of DNDs in a suspension in the range 0.001–1% results in a change in the shape of DND agglomerates and their number per unit substrate surface area N _s from 10⁸ to 10¹¹ cm⁻². Submicron isolated diamond particles are grown on a substrate coated with DND agglomerates at N _s ≈ 108 cm⁻² using microwave plasma-enhanced chemical vapor deposition. At N _s ≈ 10¹⁰ cm⁻², thin (∼100 nm) nanodiamond films with a root-mean-square surface roughness less than 15 nm are grown.     

Characteristics of p-type ZnO:As thin films prepared by the ampoule-tube method and ZnO p–n homojunction

A p-type ZnO thin film was prepared using arsenic diffusion via the ampoule-tube method. This was followed by fabrication of a ZnO p–n homojunction using n-type ZnO and characterization of the device properties. The ZnO thin film exhibited p-type characteristics, with a resistivity of 2.19×10⁻³ Ω cm, a carrier concentration of 1.73×10²⁰/cm³, and a mobility of 26.7 cm²/V s. Secondary ion mass spectrometer analysis confirmed that in- and out-diffusion occurred simultaneously from the external As source and the GaAs substrate. The device exhibited the rectification characteristics of a typical p–n junction; the forward voltage at 20 mA was approximately 5.5 V. The reverse-bias leakage current was very low—0.1 mA for −10 V; the breakdown voltage was −11 V. The ampoule-tube method for fabricating p-type ZnO thin films may be useful in producing ultraviolet ZnO LEDs and other ZnO-based devices.     

Vibrational spectra of thin eulytine films

This is a study of IR reflection spectra of systems of a thin Bi₄X₃O₁₂(X=Si, Ge) film and a substrate of fused quartz v-SiO₂ in the range 400–1600 cm⁻¹ at T=295 K. Bands assigned to Bi₄X₃O₁₂ are interpreted. It is found that single-photon processes are exhibited in the range 400–800 cm⁻¹, while biphonon processes, in the range 800–1600 cm⁻¹. I. Franko State University of Lvov, 50 Dragomanov St., 290005, Lvov, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 494–498, July–August, 1997.     

The effect of LaPO4 in the LixLa2/3Ti1−xPxO3+x system

Lithium ion conductors of the overall composition Li_xLa_2/3Ti_1−xP_xO_3+x (hereafter referred to as LTP) based on La_2/3TiO₃ were prepared by solid state reaction at high temperature (1300 °C). AC impedance measurements indicate that the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ when x=0.28 − 0.35 at room temperature and have an activation energy of 18 kJ·mol⁻¹ in the temperature range from room temperature to 400 °C. X-ray powder diffraction patterns showed that the LTP system has a complex composition, which contains the solid solution perovskite Li_3xLa_2/3−xTiO₃ and LaPO₄.     

Spectral components that form UV absorption spectrum of Ce3+ and Ce(IV) valence states in matrix of photothermorefractive glasses

We have measured the UV absorption spectra of photothermorefractive glasses of the system Na₂O-ZnO-Al₂O₃-NaF-SiO₂ doped by cerium oxide in the range of (2.8–5.0) × 10⁴ cm⁻¹ (360–200 nm). The spectra have been processed by the method of dispersion analysis based on the analytical convolution model for the complex dielectric function of glasses. We show that the absorption band centered at 3.3 × 10⁴ cm⁻¹ (∼303 nm) that is attributed to the transition 2F _5/2 → 5d in the Ce³⁺ ion, is an envelope of three spectral components. The broad absorption range (3.5–4.7) × 10⁴ cm⁻¹ (200–270 nm) that is commonly interpreted as a charge transfer band of the Ce(IV) valence state, is an envelope of at least three spectral components.     

Structure and Ionic Conductivity of Halocomplexes of Main Group Metallic Elements Studied by NMR and NQR

Li₃InBr₆ undergoes phase transition to a lithium superionic conductor at T _tr = 314 K (σ = 5.0 × 10⁻⁴ S cm⁻¹ at 330 K). The Rietveld analysis and the DSC measurement suggested that the positional disorder is introduced at the cationic sites above T _tr. The X-ray powder diffraction pattern at the superionic phase changes gradually with temperature and finally shows a simple powder pattern at 420 K which is quite similar to that of LiBr. This rock salt structure contains intrinsic vacancies because one In³⁺ and two vacancies substitute for three Li⁺. ⁷Li and ¹¹⁵In NMR support the rapid diffusion of the Li⁺ and the introduction of the In³⁺ into the rock salt structure. On the other hand, the ionic conductivity for Na₃InCl₆ was 10⁻⁵ S cm⁻¹ even at 500 K. Conduction path for the sodium ions could be proposed by means of the Rietveld analysis and the NMR experiment using a single crystal.     

Tailoring ceramics for specific applications: A case study of the development of all-solid-state lithium batteries

Metal oxides with the nominal chemical compositions Li₅La₃M₂O₁₂ (M=Nb, Ta), possessing a garnet-like structure, exhibit ionic bulk conductivities of the order of magnitude of ∼10⁻⁶ S/cm at 25 °C. Partial substitution of La by alkaline earth elements (Ca, Sr, Ba) in Li₅La₃M₂O₁₂ yields new members of compounds with garnet-like structure with the composition Li₆ALa₂M₂O₁₂ (A=Ca, Sr, Ba). Among the investigated compounds, so far, the Ba-compound Li₆BaLa₂Ta₂O₁₂ exhibits the highest bulk conductivity of 4.0×10⁻⁵ S/cm at 22 °C with an activation energy of 0.40 eV. All Ta-members were found to be stable against chemical reaction with molten elemental lithium. Li₆ALa₂Ta₂O₁₂ (A=Sr, Ba) exhibit also high electrochemical stability of ∼6 V vs. lithium and chemical stability against reaction with LiCoO₂ cathode material. A novel high voltage thin-film battery was constructed using spinel-type Li₂MMn₃O₈ (M=Co, Fe) as positive electrode, LiPON as electrolyte and Al as negative electrode material. Li₂MMn₃O₈ (M=Fe, Co) electrodes show two reversible plateaus during the charging and discharging cycle at ∼4 and ∼5 V vs. Li. The former plateau is due to the valence change of Mn³⁺ to Mn⁴⁺ and the latter one is due to the oxidation of M³⁺ to M⁴⁺. The chemical diffusion coefficient ( ) was found to be in the range 10⁻¹³–10⁻¹² cm²/sec for any composition x of Li_2−xMMn₃O₈ (M=Fe, Co) in the range from 0.1 to 1.6 by employing the galvanostatic intermittent titration technique (GITT). AC impedance studies revealed an electrolyte-electrode charge transfer resistance of 260–290 Θ and an electrode double layer capacity of ∼45–70 μF for an electrode area of 6.7 cm² at room temperature. The chemical diffusion coefficient of the Al,LiAl negative electrode is about three orders of magnitude higher than that of the positive electrode materials. Accordingly, we believe that the diffusion of Li into and out of the cathode material is the rate determining process. Paper presented at the Patras Conference on Solid State Ionics - Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.