Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

Structural and electrical properties of pure and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> doped (PVA)<Subscript>0.7</Subscript>(NaI)<Subscript>0.3</Subscript> solid polymer electrolyte

Solid polymer electrolytes (SPE) based on poly-(vinyl alcohol) (PVA)_0.7 and sodium iodide (NaI)_0.3 complexed with sulfuric acid (SA) at different concentrations were prepared using solution casting technique. The structural properties of these electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD data revealed that sulfuric acid disrupt the semi-crystalline nature of (PVA)_0.7(NaI)_0.3 and convert it into an amorphous phase. The proton conductivity and impedance of the electrolyte were studied with changing sulfuric acid concentration from 0 to 5.1 mol/liter (M). The highest conductivity of (PVA)_0.7(NaI)_0.3 matrix at room temperature was 10⁻⁵ S cm⁻¹ and this increased to 10⁻³ S cm⁻¹ with doping by 5.1 M sulfuric acid. The electrical conductivity (σ) and dielectric permittivity (ε′) of the solid polymer electrolyte in frequency range (500 Hz–1 MHz) and temperature range (300–400) K were carried out. The electrolyte with the highest electrical conductivity was used in the fabrication of a sodium battery with the configuration Na/SPE/MnO₂. The fabricated cells give open circuit voltage of 3.34 V and have an internal resistance of 4.5 kΩ.     

Investigation on optical properties of Bi<Subscript>2.85</Subscript>La<Subscript>0.15</Subscript>TiNbO<Subscript>9</Subscript> thin films by prism coupling technique

Layered-perovskite ferroelectric Bi_2.85La_0.15TiNbO₉ (LBTN) optical waveguiding thin films were grown on fused silica substrates by pulsed laser deposition (PLD). X-ray diffraction (XRD) revealed that the film is highly (00l) textured. We observed sharp and distinct transverse electric (TE) and transverse magnetic (TM) multimodes and measured the refractive indices of LBTN thin films at 632.8 nm. The ordinary and extraordinary refractive indices were calculated to be n _TE=2.358 and n _TM=2.464, respectively. The film homogeneity and the film-substrate interface were analyzed using an improved version of the inverse Wentzel–Kramer–Brillouin (iWKB) method. The refractive index of the film remains constant at n ₀ within the waveguiding layer. The average transmittance of the film is 70% in the wavelength range of 400–1400 nm and the optical waveguiding properties were evaluated by the optical prism coupling method. Our results showed that the LBTN films are very good electro-optical active material.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

Structure,transport and field-emission properties of compound nanotubes: CN<Subscript>x</Subscript> vs. BNC<Subscript>x</Subscript> (<Emphasis Type="Italic">x</Emphasis><0.1)

Transport and field-emission properties of as-synthesized CN_x and BNC_x (x<0.1) multi-walled nanotubes were compared in detail. Individual ropes made of these nanotubes and macrofilms of those were tested. Before measurements, the nanotubes were thoroughly characterized using high-resolution and energy-filtered electron microscopy, electron diffraction and electron-energy-loss spectroscopy. Individual ropes composed of dozens of CN_x nanotubes displayed well-defined metallic behavior and low resistivities of ∼10–100 kΩ or less at room temperature, whereas those made of BNC_x nanotubes exhibited semiconducting properties and high resistivities of ∼50–300 MΩ. Both types of ropes revealed good field-emission properties with emitting currents per rope reaching ∼4 μA(CN_x) and ∼2 μA (BNC_x), albeit the latter ropes se- verely deteriorated during the field emission. Macrofilms made of randomly oriented CN_x or BNC_x nanotubes displayed low and similar turn-on fields of ∼2–3 V/μm. 3 mA/cm² (BNC_x) and 5.5 mA/cm² (CN_x) current densities were reached at 5.5 V/μm macroscopic fields. At a current density of 0.2–0.4 mA/cm² both types of compound nanotubes exhibited equally good emission stability over tens of minutes; by contrast, on increasing the current density to 0.2–0.4 A/cm², only CN_x films continued to emit steadily, while the field emission from BNC_x nanotube films was prone to fast degradation within several tens of seconds, likely due to arcing and/or resistive heating. Received: 29 October 2002 / Accepted: 1 November 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Magnetotransport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> with different grain sizes

The magnetotransport and magnetoresistive (MR) properties of manganese-based La_0.67Ca_0.33MnO₃ perovskite with different grain sizes are reported. The electrical resistivity was measured as a function of temperature in magnetic fields of 0.5 and 1 T. The insulator–metal transition temperature, T _IM, shifted to a higher temperature with the application of the magnetic field. In zero field, T _IM is almost constant (∼271 K) for all samples except for the sample with the largest grain size, where T _IM=265 K. The temperature dependence of resistivity was fitted with several equations in the metallic (ferromagnetic) region and the insulating (paramagnetic) region. The density of states at the Fermi level, N(E _F), and the activation energy of electron hopping were estimated by fitting the resistivity versus temperature curves. The ρ–T ² curves are nearly linear in the metallic regime, but the ρ–T ^2.5 curves exhibit a deviation from linearity. The variable range hopping model and small polaron hopping model fit the data well in the high-temperature region, indicating the existence of the Jahn–Teller distortion that localizes the charge carriers. MR was found to increase with an increase in the magnetic field, an effect which is attributed to the intergrain spin tunneling effect.     

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.     

Galvanomagnetic transport properties of nitrogenated (La,Sr)MnO<Subscript>3-δ</Subscript> and LaMnO<Subscript>3-δ</Subscript>

Epitaxial thin films of nitrogenated La_0.65Sr_0.30MnO₃ were grown on MgO(100) substrates by pulsed laser deposition (PLD). The nitrogenation was achieved by a continuous nitrogen flow in the PLD chamber with pressures of up to 0.12 mbar. The chemical analysis of the samples regarding the exchange of oxygen by nitrogen was achieved by time of flight secondary ion mass spectrometry, sputtered neutral mass spectrometry (SNMS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) and yielded a content of incorporated nitrogen ranging from 0.6% to 3.8%. Without nitrogenation the electrical resistivity of La_0.65Sr_0.30MnO₃ exhibited a metal–insulator (MI) transition at about 180 K. The magnetoresistance (MR) effect (ΔR/R(0)) was about -50% at the transition temperature. Our nitrogen contents affected the MI transition so as to completely disappear and resulted in a resistivity increase of more than three orders of magnitude as well. By carefully reoxidizing the samples with subsequent heat treatments in air the MI transition reappeared at lower temperatures and we found a continuously enhanced MR ratio for decreasing temperatures. MR ratios of more than -99% were observed for a magnetic field of 10 T. The results are interpreted as a percolation phenomenon of ferromagnetic–metallic domains within an antiferromagnetic–semiconducting matrix. PACS 75.47.Gk; 75.47.Lx; 74.62.Dh; 81.15.Fg     

Electro-optic properties of epitaxial Sr<Subscript>0.6</Subscript>Ba<Subscript>0.4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films grown on MgO substrates using Li<Subscript>x</Subscript>Ni<Subscript>2-x</Subscript>O buffer layer

Textured Li_xNi_2-xO (LNO) thin films have been fabricated on (001)MgO substrates by pulsed laser deposition technique. The as-deposited LNO films shows a conductivity of 2.5×10^-3 Ω m and possess a transmittance of about 35% in the visible region. Subsequent deposition of Sr_0.6Ba_0.4Nb₂O₆ (SBN60) thin film on these LNO-coated MgO substrates resulted in a textured SBN layer with a 〈001〉 orientation perpendicular to the substrate plane. Phi scans on the (221) plane of the SBN layer indicated that the films have two in-plane orientations with respect to the substrate. The SBN unit cells were rotated in the plane of the film by ± 8.2° as well as ± 45° with respect to the LNO/MgO substrate. Besides the highly (00l)-orientation, the SBN films also exhibited a dense microstructure as shown by scanning electron microscopy. The electro-optic coefficient (r₃₃) of the SBN film was measured to be 186 pm/V. On the basis of our results, we have demonstrated that the LNO film can be used as a buffer layer as well as a transparent bottom electrode for waveguide applications. The SBN/LNO heterostructure is also a suitable candidate for integrated electro-optics devices. PACS  42.79.Gn; 42.82.Et; 78.20.Ci     

Magnetic ground state and the spin-state transitions in YBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript>

The crystal and magnetic structure of the perovskite-like, oxygen deficient cobalt oxide YBaCo₂O_5.5 has been studied by means of neutron and X-ray diffraction in the 10–300 K temperature range. The magnetic ground state is characterized by a coexistence of two distinct antiferromagnetic phases. In the first one, the ionic moments of high-spin Co³⁺ ions in the pyramidal sites are ordered in a spiral arrangement, while octahedral sites are non-magnetic due to presence of low-spin Co³⁺ ions. The arrangement in the second phase is collinear of the G-type, with non-zero moments both in pyramidal (high-spin Co³⁺ ions) and octahedral sites (presumably a mixture of the low- and high-spin states). With increasing temperature, at 260–300 K, the system develops a gradual structural transformation, which is associated with appearance of spontaneous magnetic moment. This process is related to a thermally induced reversion of low- and high-spin states at the octahedral sites to the intermediate-spin Co³⁺ states, resulting in an insulator-metal transition at T_C ≈ T_IM ≈ 295 K.     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.     

Dielectric properties of thin-film ZrO<Subscript>2</Subscript> up to 50 GHz for RF MEMS switches

The dielectric properties of zirconium dioxide (ZrO₂) ceramic thin films were characterized up to 50 GHz using coplanar waveguides (CPWs) and metal–insulator–metal (MIM) capacitors with top circular electrodes. The ZrO₂ films were deposited using a chemical solution onto high-resistivity Si wafers and metal layers. The real part of the dielectric constant of approximately 22 and 26 was extracted at 50 GHz for CPW and MIM structures, respectively, and the loss tangent was approximately 0.09 at 50 GHz. C–V and I–V measurements were carried out to determine low-frequency and DC dielectric properties. The measurement results indicate that ZrO₂ is a promising material to be used as a dielectric layer for radio-frequency (RF) microelectromechanical systems (MEMS) capacitive switches.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

Highly (100) oriented Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> films grown on amorphous substrates by pulsed laser deposition

Pb(Zr_0.52Ti_0.48)O₃ (PZT)/LaNiO₃ (LNO) thin films with highly (100) out of plane orientation were produced on SiO₂/Si(100) and alkaline earth aluminosilicate glass substrates by pulsed laser deposition (PLD). Orientations of both PZT and LNO films were evaluated using X-ray diffraction. The pure (100)-oriented PZT/LNO films were obtained under optimized deposition conditions. Time of flight-secondary ion mass spectrometry analysis showed that LNO could effectively block interdiffusion between the PZT films and the substrates. Fairly smooth surfaces of the PZT films with roughness of about 4 nm were observed using an atomic force microscope. Cross sectional examination revealed that the films grew in columnar grains. The PZT films grown on both SiO₂/Si and glass substrates demonstrated very good ferroelectric characteristic at room temperature with remnant polarization of up to 26 μC/cm². PACS 79.20.DS; 77.84.DY; 78.70.Ck     

Pseudo-capacitive properties of LiCoO<Subscript>2</Subscript>/AC electrochemical capacitor in various aqueous electrolytes

LiCoO₂ particles were synthesized by a sol-gel process. X-ray diffraction analysis reveals that the prepared sample is a single phase with layered structure. A hybrid electrochemical capacitor was fabricated with LiCoO₂ as a positive electrode and activated carbon (AC) as a negative electrode in various aqueous electrolytes. Pseudo-capacitive properties of the LiCoO₂/AC electrochemical capacitor were determined by cyclic voltammetry, charge–discharge test, and electrochemical impedance measurement. The charge storage mechanism of the LiCoO₂-positive electrode in aqueous electrolyte was discussed, too. The results showed that the potential range, scan rate, species of aqueous electrolyte, and current density had great effect on capacitive properties of the hybrid capacitor. In the potential range of 0–1.4 V, it delivered a discharge specific capacitance of 45.9 Fg^–1 (based on the active mass of the two electrodes) at a current density of 100 mAg^–1 in 1 molL^–1 Li₂SO₄ aqueous electrolyte. The specific capacitance remained 41.7 Fg^–1 after 600 cycles.     

Impurity band in SnBi<Subscript>4</Subscript>Se<Subscript>7</Subscript>: thermoelectric power and electrical resistivity measurements

Thermoelectric power and electrical resistivity measurements on polycrystalline samples of Bi₂Se₃ and stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ in the temperature range of 90–420 K are presented and explained assuming the existence of an impurity band. The variation of the electron concentration with temperature above 300 K is explained in terms of the thermal activation of a shallow donor, by using a single conduction band model. The density of states effective mass m ^*=0.15m ₀ of the electrons, the activation energy of the donors, their concentration, and the compensation ratio are estimated. The temperature dependence of the electron mobility in conduction band is analyzed by taking into account the scattering of the charge carriers by acoustic phonon, optical phonon, and polar optical phonon as well as by alloy and ionized impurity modes. On the other hand, by considering the two-band model with electrons in both the conduction and impurity bands, the change in the electrical resistivity with temperature between 420 and 90 K is explained.     

Fabrication of transparent p-n junction composed of heteroepitaxially grown p-Li<Subscript>0.15</Subscript>Ni<Subscript>0.85</Subscript>O and n-ZnO films for UV-detector applications

Thin films of high-quality p-type Li_0.15Ni_0.85O (LNO) and n-type ZnO were heteroepitaxially grown on MgO(111) substrate by pulsed laser deposition technique to form transparent wide bandgap heterojunctions. The epitaxial nature of this p-LNO/n-ZnO/MgO heterojunction was confirmed to be (111)LNO||(0001)ZnO||(111)MgO (out-of-plane) and (002)LNO||(1002)ZnO||(002)MgO (in-plane) by X-ray diffraction. Optical transmittance spectrum and I–V characteristics were obtained at room temperature. The heterojunction exhibits reasonable optical transmittance of 50–60% on average in the whole infrared and visible region, and highly asymmetric electrical rectification with a turn-on voltage of about 1.0 V and a small leakage current. The highest photoresponsivity for a wavelength of 350 nm is 3.4×10³ V/W when the junction is irradiated under 5 μW UV illumination. The spectral response peak is obtained in the UV region and a reasonable large responsivity is shown for this p-LNO/n-ZnO/MgO heterojunction, which suggests the possibility of an inexpensive transparent oxide UV detector in a wide variety of electronics applications. PACS 68.55.Jk; 81.05.Dz; 81.15.Fg     

An Effect of Irradiation with Trivalent Boron Ions on Pinning in Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8</Subscript> Thin Films as Revealed by MWA and Hall-Probe Measurements

Bi₂Sr₂CaCu₂O₈ thin films 200 nm thick were irradiated with 120 keV trivalent boron ions with the dose ranging from 10¹¹ to 10¹⁴ ion/cm². The critical parameters of the samples prior and after irradiation were monitored by non-resonance modulated microwave absorption and Hall-probe techniques. For low doses of 10¹¹–10¹² ion/cm², a slight increase in the critical current density and expansion of the area of the non-dissipative transport current flow were revealed. Such results are explained by the formation of separate areas of displaced atoms, which serve as effective pinning centers. The positive effects of irradiation faded away with dose increase of up to 10¹³–10¹⁴ ion/cm². This is due to overlap of radiation-induced defects and weak pinning on them.     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.