Synthesis of LaB6 micro/nano structures using picosecond (Nd:YAG) laser and its field emission investigations

Micro/nano structures have been obtained by laser surface treatment on sintered LaB₆ pellets employing a picosecond pulsed Nd:YAG laser at a pressure of ∼1×10⁻³ mbar. The X-ray diffraction pattern of the laser treated pellet shows a set of well defined diffraction peaks, indexed to the cubic phase of LaB₆ only. The scanning electron microscope studies reveal formation of micro and nano structures upon laser treatment and the resultant surface morphology is found to be strongly influenced by the laser fluence. Field electron emission studies made on the LaB₆ pellet, treated with optimized laser fluence, have been performed in a planar diode configuration under ultra high vacuum conditions. The threshold field required to draw an emission current density of ∼10 μA/cm² has been found to be ∼2.3 V/μm and a current density of ∼530 μA/cm² has been drawn at an applied field of 5.2 V/μm. The Fowler-Nordheim plot is found to be linear in accordance with the quantum mechanical tunneling phenomenon, confirming the metallic nature of the emitter. The emission current at the pre-set value ∼10 μA shows very good stability over a period of more than 3 hours. The present results emphasize the effectiveness of a picosecond laser treatment towards fabrication of a nano metric LaB₆ emitter for high current density applications.     

Low-macroscopic field emission from nanocrystalline Al doped SnO<Subscript>2</Subscript> thin films synthesized by sol–gel technique

We have observed low-macroscopic field electron emission from wide bandgap nanocrystalline Al doped SnO₂ thin films deposited on glass substrates. The emission properties have been studied for different anode-sample spacings and for different Al concentrations in the films. The turn-on field and approximate work function were calculated and we have tried to explain the emission mechanism from this. The turn-on field was found to vary in the range 5.6–7.5 V/μm for a variation of anode sample spacing from 80–120 μm. The turn-on field was also found to vary from 4.6–5.68 V/μm for a fixed anode-sample separation of 80 μm with a variation of Al concentration in the films 8.16–2.31%. The Al concentrations in the films have been measured by energy dispersive X-ray analysis. Optical transmittance measurement of the films showed a high transparency with a direct bandgap ∼3.98 eV. Due to the wide bandgap, the electron affinity of the film decreased. This, along with the nanocrystalline nature of the films, enhanced the field emission properties. PACS 81.20.Fw; 61.10.-i; 79.70.+q     

Low threshold field electron emission from solvothermally synthesized WO2.72 nanowires

Field emission studies of WO_2.72 nanowires synthesized by a solvothermal method have been performed in the planar diode configuration under ultra high vacuum conditions. Fowler–Nordheim plots obtained from the current-voltage characteristics follow the quantum mechanical tunneling process and a current density of ∼8.3×10⁶ μA/cm² can be drawn at an applied electric field of 2 V/μm. The field enhancement factor is 33025, while the turn-on field is only 1.4 V/μm. The emission current-time plot recorded at the pre-set value of emission current of 1 μA over a period of more than 3 h exhibits an initial increase and a subsequent stabilization of the emission current. The results reveal that the WO_2.72 nanowire emitters synthesized by the solvothermal method are promising cathode materials for practical applications.     

Chemical solution-process method to synthesize ZnO nanorods with ultra-thin pinheads and ultra-thin nanobelts

ZnO nanorods with 30 nm-diameter ultra-thin pinheads and ultra-thin nanobelts were successfully synthesized using a thiourea solution to etch nanorods and nancombs, which were obtained by a conventional thermal evaporation method. The materials obtained were investigated by field emission scanning electron microscopy and energy-dispersive X-ray fluorescence. The data shows that hydrogen ions play an important role in synthesizing ZnO nanorods with ultra-thin pinheads and ultra-thin nanobelts. Field emission plots indicated that the turn-on field was reduced from 2.10 V/μm to 1.55 V/μm after thiourea solution treatment at a current density of 0.1 μA/cm². Room-temperature photoluminescence spectra from ZnO nanostructures showed the PL spectrum peaks shifted towards short wavelengths with a large enhancement of UV bands compared with those of ZnO nanorods and nanocombs. PACS 75.55.Gs; 61.46.-w; 81.40.Wx; 78.55.-m; 78.60.Fi     

Sensitive detection of temperature behind reflected shock waves using wavelength modulation spectroscopy of CO2 near 2.7?μm

Tunable diode-laser absorption of CO₂ near 2.7 μm incorporating wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) is used to provide a new sensor for sensitive and accurate measurement of the temperature behind reflected shock waves in a shock-tube. The temperature is inferred from the ratio of 2f signals for two selected absorption transitions, at 3633.08 and 3645.56 cm⁻¹, belonging to the ν ₁+ν ₃ combination vibrational band of CO₂ near 2.7 μm. The modulation depths of 0.078 and 0.063 cm⁻¹ are optimized for the target conditions of the shock-heated gases (P∼1–2 atm, T∼800–1600 K). The sensor is designed to achieve a high sensitivity to the temperature and a low sensitivity to cold boundary-layer effects and any changes in gas pressure or composition. The fixed-wavelength WMS-2f sensor is tested for temperature and CO₂ concentration measurements in a heated static cell (600–1200 K) and in non-reactive shock-tube experiments (900–1700 K) using CO₂–Ar mixtures. The relatively large CO₂ absorption strength near 2.7 μm and the use of a WMS-2f strategy minimizes noise and enables measurements with lower concentration, higher accuracy, better sensitivity and improved signal-to-noise ratio (SNR) relative to earlier work, using transitions in the 1.5 and 2.0 μm CO₂ combination bands. The standard deviation of the measured temperature histories behind reflected shock waves is less than 0.5%. The temperature sensor is also demonstrated in reactive shock-tube experiments of n-heptane oxidation. Seeding of relatively inert CO₂ in the initial fuel-oxidizer mixture is utilized to enable measurements of the pre-ignition temperature profiles. To our knowledge, this work represents the first application of wavelength modulation spectroscopy to this new class of diode lasers near 2.7 μm.     

Studies on PEO-based sodium ion conducting composite polymer films

A sodium ion conducting composite polymer electrolyte (CPE) prepared by solution-caste technique by dispersion of an electrochemically inert ceramic filler (SnO₂) in the PEO–salt complex matrix is reported. The effect of filler concentration on morphological, electrical, electrochemical, and mechanical stability of the CPE films has been investigated and analyzed. Composite nature of the films has been confirmed from X-ray diffraction and scanning electron microscopy patterns. Room temperature d.c. conductivity observed as a function of filler concentration indicates an enhancement (maximum) at 1–2 wt% filler concentration followed by another maximum at ∼10 wt% SnO₂. This two-maxima feature of electrical conductivity as a function of filler concentration remains unaltered in the CPE films even at 100 °C (i.e., after crystalline melting), suggesting an active role of the filler particles in governing electrical transport. Substantial enhancement in the voltage stability and mechanical properties of the CPE films has been noticed on filler dispersion. The composite polymer films have been observed to be predominantly ionic in nature with t _ion ∼ 0.99 for 1–2 wt% SnO₂. However, this value gets lowered on increasing addition of SnO₂ with t _ion ∼ 0.90 for 25 wt% SnO₂. A calculation of ionic and electronic conductivity for 25 wt% of SnO₂ film works out to be ∼2.34 × 10⁻⁶ and 2.6 × 10⁻⁷ S/cm, respectively.     

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     

Wavelength modulation and cavity enhanced absorption spectroscopy using ～1.9?μm radiation produced by difference frequency generation with a MgO doped PPLN crystal

We have demonstrated the production of ∼1.9 μm near-infrared radiation by using difference frequency generation within a 5% MgO doped PPLN crystal by coupling ∼735 nm radiation from a tunable external cavity diode laser with relatively high powered 532 nm radiation from both Nd:YVO₃ and Nd:YAG lasers. The radiation produced is of low power, ∼15 μW, and was used in conjunction with the sensitivity enhancing techniques of wavelength modulation spectroscopy (WMS) and cavity enhanced absorption spectroscopy (CEAS). Experiments were carried out on rotationally resolved transitions in the combination bands of NH₃ and CO₂ in the 1.9 μm region. An α _min value of 3.6×10⁻⁶ cm⁻¹ Hz^−1/2 was achieved for WMS measurements on CO₂. A comparable α _min value of 2.2×10⁻⁶ cm⁻¹ Hz^−1/2 was achieved for NH₃ using CEAS. The low NIR power indicates that despite the level of MgO doping quoted for the crystal, under prolonged exposure photorefractive damage has occurred.     

Modeling and analysis of birefringence in magneto-optical thin film made by SiO2/ZrO2 doped with ferrite of cobalt

We report the device characteristics of the metal–dielectric high-reflectivity (HR) coated 1.55 μm laterally coupled distributed feedback (DFB) laser with metal surface gratings by using holographic lithography. The HR coating films are composed of Au/Ti/SiO₂. It provides a variety of advantages compared to the uncoated DFB laser on the same processed wafer while there is no degradation on current–voltage characteristics. For 3 μm wide and 300 μm long HR coated DFB laser, it exhibits a maximum output power of ∼17 mW and a threshold current of 14.2 mA at 20°C under continuous-wave mode. It is clear that the threshold current and slope efficiency are improved by 36% and 96%, respectively, due to the reduction of mirror loss. The metal–dielectric HR coating on one facet of DFB laser is found to have significantly increased characteristic temperature (i.e., T ₀∼88 K). Furthermore, the stable single-mode operation with an increased single-mode suppression ratio was achieved.     

Large-scale synthesis of SnO2 nanobelts

Tin dioxide (SnO₂) nanobelts have been successfully synthesized in bulk quantity by a simple and low-cost process based on the thermal evaporation of tin powders at 800 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations reveal that the nanobelts are uniform, with lengths from several-hundred micrometers to a few millimeters, widths of 60 to 250 nm and thicknesses of 10 to 30 nm. X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and selected-area electron diffraction analysis (SAED) indicate that the nanobelts are tetragonal rutile structure of SnO₂. The SnO₂ nanobelts grow via a vapor–solid (VS) process. Received: 3 June 2002 / Accepted: 10 June 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-551/559-1434, E-mail: gwmeng@mail.issp.ac.cn     

MgB2 thick films deposited on stainless steel substrate with Tc higher than 39K

Thick MgB₂ (magnesium diborate) films, ∼10 μm, with T _c (onset) = 39.4 K and T _c (zero) = 39.2 K have been successfully grown on a stainless steel substrate using a technique called hybrid physical-chemical deposition (HPCVD). The deposition rate is high, ∼6.7 nm/s. The X-ray diffraction (XRD) indicates that it is highly (101) and c-axis oriented. The scanning electron microscope (SEM) images demonstrate that the film grown is in “island-mode”. The uniform superconducting phase in the film is shown by the M-T measurement.     

Electron field emission from magnetic nanomaterial encapsulated multi-walled carbon nanotubes

The present work describes the field emission characteristics of nanoscale magnetic nanomaterial encapsulated multi-walled carbon nanotubes (MWNTs) fabricated over flexible graphitized carbon cloth. Ni/MWNTs, NiFe/MWNTs and NiFeCo/MWNTs have been synthesized by catalytic chemical vapor decomposition of methane over Mischmetal (Mm)-based AB₃ (MmNi₃, MmFe_1.5Ni_1.5 and MmFeCoNi) alloy hydride catalysts. Metal-encapsulated MWNTs exhibited superior field emission performance than pure MWNT-based field emitters over the same substrate. The results indicate that a Ni-filled MWNT field emitter is a promising material for practical field emission application with a lowest turn-on field of 0.6 V/μm and a high emission current density of 0.3 mA/cm² at 0.9 V/μm.     

Structure and NO2 gas sensing properties of SnO2-core/In2O3-shell nanobelts

SnO₂-core/In₂O₃-shell nanobelts were fabricated by a two-step process comprising thermal evaporation of Sn powders and sputter-deposition of In₂O₃. Transmission electron microscopy and X-ray diffraction analyses revealed that the core of a typical core–shell nanobelt comprised a simple tetragonal-structured single crystal SnO₂ and that the shell comprised an amorphous In₂O₃. Multiple networked SnO₂-core/In₂O₃-shell nanobelt sensors showed the response of 5.35% at a NO₂ concentration of 10 ppm at 300 °C. This response value is more than three times larger than that of bare-SnO₂ nanobelt sensors at the same NO₂ concentration. The enhancement in the sensitivity of SnO₂ nanobelts to NO₂ gas by sheathing the nanobelts with In₂O₃ can be accounted for by the modulation of electron transport by the In₂O₃–In₂O₃ homojunction.     

Effects of hydroxyls on the structural and room temperature ferromagnetic properties of Co doped SnO2 nanoparticles

Co doped SnO₂ nanoparticles have been prepared via a wet chemical method with different precipitation processes. The structure and morphology of Co doped SnO₂ nanoparticles demonstrate that the nanoparticles are in a rutile single phase and uniform, respectively. X-ray photoelectron spectroscopy shows that the Co dopants are in 2+ oxidation valence state and doped ∼2 atm% in SnO₂ nanoparticles. Moreover, Raman spectroscopy further confirms that Co doped SnO₂ nanoparticles have single phase crystallinity without forming any extra modes related to secondary phases. The magnetic measurements reveal that all nanoparticles exhibit room temperature ferromagnetism (RTFM) due to the presence of disorders and defects introduced by hydroxyls in the crystal structure. In addition, it has been clearly observed that the saturated magnetic moments are strongly affected by the precipitation processes which control the incorporation of hydroxyls into the lattice.     

Magnetic behaviour of (Fe<Subscript>0.85</Subscript>Cr<Subscript>0.15</Subscript>)<Subscript>2</Subscript>As

Magnetization and neutron diffraction measurements have been made on the title pseudo-binary of tetragonal anti-ferromagnets Fe₂ As and Cr₂ As. In this system antiferromagnetic (AFM) ordering appears below 310 K. The moments are confined in theab plane but unlike in the end members they are tilted off thea-axis. In addition to the AFM structure a weak ferromagnetic behaviour shows up below∼80 K with a rather low moment of ∼0.07 μB per formula unit at 5 K and under a field of 3 T.     

Porous silicon based β-FeSi2 and photoluminescence

Highly-pure iron powder was covered on porous silicon for fabricating semiconducting β-FeSi₂ structures. X-ray diffraction and Raman scattering results confirm the formation of pure-phase β-FeSi₂ after high-temperature annealing at 1100°C and then long-time persistence at 900°C. Scanning electron microscope observations reveal that large-size (>μm) β-FeSi₂ grains mainly form in the pores of porous silicon and some nanocrystals grow on local surfaces. The temperature-dependent photoluminescence spectra disclose that the observed ∼1.54 μm emission arises from free exciton recombination, which is confirmed via the activation energy (0.25 eV) measurement. Our method provides a way to synthesize single-phase β-FeSi₂ materials.     

Dielectric and phase transition of BaTi<Subscript>0.6</Subscript>Zr<Subscript>0.4</Subscript>O<Subscript>3</Subscript> ceramics prepared by a soft chemical route

BaTi_0.6Zr_0.4O₃ (BTZ) ceramic was synthesized by a soft chemical route. X-ray diffraction at room temperature shows that the sample has cubic perovskite structure with space group Pm-3m. Temperature dependent dielectric study of the sample has been investigated in the frequency range from 50 Hz to 1 MHz. The density of the sample was determined using Archimedes’ principle and found to be ∼ 97% of the X-ray density. The average grain size in the pallet was found to be ∼ 1 μm. The dielectric constant peaks at temperature T_m which is dependent on the frequency. The dielectric relaxation rate follows the Vogel–Fulcher relation with activation energy = 0.0185 eV, and freezing temperature = 186 K. All these measurements confirm that BTZ is a relaxor ferroelectric. PACS 77.22.Jp; 77.84.-s; 77.80.Bh; 77.22.Gm     

Sub-THz radiation room temperature sensitivity of long-channel silicon field effect transistors

Room temperature operating n-MOSFETs (n-type metal-oxide silicon field effect transistors) used for registration of sub-THz (sub-terahertz) radiation in the frequency range ν = 53−145 GHz are considered. n-MOSFETs were manufactured by 1-μm Si CMOS technology applied to epitaxial Si-layers (d ≈15 μm) deposited on thick Si substrates (d = 640 μm). It was shown that for transistors with the channel width to length ratio W/L = 20/3 μm without any special antennas used for radiation input, the noise equivalent power (NEP) for radiation frequency ν ≈76 GHz can reach NEP ∼6×10⁻¹⁰ W/Hz^1/2. With estimated frequency dependent antenna effective area S_est for contact wires considered as antennas, the estimated possible noise equivalent power NEP_pos for n-MOSFET structures themselves can be from ∼15 to ∼10³ times better in the specral range of ν ∼55–78 GHz reaching NEP_pos ≈10⁻¹² W/Hz^1/2.     

Low-temperature synthesis of Cu-doped Li<Subscript>1.2</Subscript>V<Subscript>3</Subscript>O<Subscript>8</Subscript> as cathode for reversible lithium storage

Li_{1 .2}V₃O₈ and Cu-doped Li_1.2V₃O₈ were prepared at a temperature as low as 300 °C by a sol-gel method. The structure, morphology, and electrochemical performance of the as-prepared samples were characterized by means of X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, and the galvanostatic discharge–charge techniques. It is found that the Cu-doped Li_1.2V₃O₈ sample exhibits less capacity loss during repeated cycling than the undoped one. The Cu-doped Li_1.2V₃O₈ sample demonstrates the first discharge capacity of 275.9 mAh/g in the range of 3.8–1.7 V at a current rate of 30 mA/g and remains at a stable discharge capacity of 264 mAh/g within 30 cycles. Furthermore, the possible role that copper plays in enhancing the cycleability of Li_1.2V₃O₈ has also been elucidated.