Preparation and optical properties of sol–gel neodymium-doped germania/γ-glycidoxypropyltrimethoxysilane organic–inorganic hybrid thin films

Germania/γ-glycidoxypropyltrimethoxysilane organic–inorganic hybrid spin-coating thin films doped with neodymium ions are prepared by a sol–gel technique and a spin-coating process. Acid-catalyzed solutions of γ-glycidoxypropyltrimethoxysilane mixed with germanium isopropoxide are used as matrix precursors. Thermal gravimetric analysis, UV–visible spectroscopy, and Fourier transform infrared spectroscopy are used to study the structural and optical properties of the hybrid thin films. The results indicate that films that are crack-free and have a high transparency in the visible and near-infrared range can be obtained; a strong UV absorption region at short wavelength ∼200 nm, accompanied with a shoulder peaked at ∼240 nm, due to the neutral oxygen monovacancy defects, is also identified. Upconversion emission properties of the transparent dried gel and the thin films heated at different heat treatment temperatures and doped with different neodymium ion concentrations are studied; a relatively strong room-temperature yellow to violet upconversion emission at 397 nm (⁴ D _3/2→⁴ I _13/2) is observed under a xenon lamp excitation with yellow light at the wavelength of 580 nm (⁴ I _9/2→⁴ G _5/2). The effect of Nd³⁺ doping concentration and heat treatment temperature on upconversion emission of the thin films is also studied. The mechanism of the upconversion is proposed. PACS 81.05.Kf; 81.20.Fw; 78.55.Hx     

Tunable ultraviolet optical parametric oscillator for differential absorption lidar measurements of tropospheric ozone

A pulsed optical parametric oscillator (OPO) with intracavity sum frequency mixing was developed generating energies of up to 16 mJ in the 281–293 nm wavelength range. Both OPO process and sum frequency mixing are pumped by the harmonics of a single, medium-sized Nd:YAG laser. The system is characterized by a high overall efficiency (∼4% conversion from 1064 nm to the UV), a very compact set-up and stable and reliable operation. This system was successfully employed to measure tropospheric ozone using the differential absorption lidar (DIAL) technique and shows much promise as a lidar transmitter in airborne case studies as well as in unattended lidar systems for long-term monitoring. An unattended ozone profiling system could already be successfully realized. Received: 1 April 2002 / Revised version: 30 May 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +49-8153/28-1271, E-mail: Andreas.Fix@dlr.de     

Low-threshold field electron emission of Si micro-tip arrays produced by laser ablation

Low-threshold field electron emission (FEE) is reported for periodic arrays of micro-tips produced by laser ablation of Si wafers. The best samples show emission at threshold fields as low as 4–5 V/μm for n-type Si substrates and of 1–2 V/μm for p-doped Si substrates, as measured with a flat-screen technique. Auger electron spectroscopy and X-ray electron spectroscopy reveal island-like deviation of the SiO₂ stoichiometry on the tip surfaces, with lateral dimensions of less than 100 nm. Microscopic studies using a special field-emission STM show that the emission originates from well-conducting regions of sub-micron size. The experimental data suggest FEE from the tip arrays by a geometric field enhancement of both the individual micro-tip and the narrow conducting channels in the tip body. Received: 3 May 2002 / Accepted: 1 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +7-095/135-82-34, E-mail: shafeev@kapella.gpi.ru     

A simple wet-chemical synthesis and characterization of CuO nanorods

Using a simple wet-chemical route, we synthesized CuO nanorods with diameters of ca. 5–15 nm and lengths of up to 400 nm. The purity, crystallinity, morphology, structure features, and chemical composition of the as-prepared CuO nanorods were investigated by powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Received: 22 March 2002 / Accepted: 12 June 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: wangqun@nju.edu.cn     

GaN nanotweezers

A new form of GaN nanomaterial (nanotweezers) has been obtained by chemical vapor deposition on an etched cubic MgO (100) plane. The nanotweezers consist of a bottom rod and two arms. The bottom rods have diameters of about 100–150 nm and lengths of about 200–500 nm, on which two arms grow out. The bottoms of the arms are about 40–70 nm and the tops are about 15–30 nm in diameter, and 0.8–1.5 μm in length. X-ray and electron diffractions indicate the nanotweezers are zinc blende gallium nitride. We infer that the fabrication of the GaN nanotweezers is associated with small convex hillocks on the surface of the etched cubic MgO (100) single-crystal substrates and that the nanotweezers grow by a growth mechanism that is similar to vapor-phase heteroepitaxy. Received: 23 April 2002 / Accepted: 25 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-10/8264-9531, E-mail: xlchen@aphy.iphy.ac.cn     

The synthesis of highly oriented GaN nanowire arrays

Highly oriented GaN nanowire arrays have been achieved by the catalytic reaction of gallium with ammonium. The resulting materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). SEM images show that the resulting materials are nanowire arrays with a uniform length of about 10 μm. XRD, EDS, TEM and SAED indicate that the nanowire arrays are single-crystal hexagonal GaN with a wurtzite structure. They have diameters of 10 to 20 nm. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. E-mail: wwwangjc@sina.com     

Large-scale synthesis of crystalline β-SiC nanowires

Large quantities of high-purity crystalline β-SiC nanowires have been synthesized at relatively low temperature via a new simple method, the chemical-vapor-reaction approach, in a home-made graphite reaction cell. A mixture of milled Si and SiC powders and C₃H₆ were employed as the starting materials. The results show that the nanowires with diameters of about 10–35 nm are single crystalline β-SiCwithout any wrapping of amorphous material, and the nanowire axes lie along the 〈111〉 direction. Some unique properties are found in the Raman scattering from the β-SiC nanowires, which are different from previous observations of β-SiC materials. A possible growth mechanism for the β-SiC nanowires is proposed. Received: 27 August 2002 / Accepted: 28 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-29/8491-000, E-mail: zjli-sohu@sohu.com     

Preparation and characterizations of SiO2/TiO2/γ-glycidoxypropyltrimethoxysilane composite materials for optical waveguides

SiO₂/TiO₂/γ-glycidoxypropyltrimethoxysilane composite materials processed by the sol-gel technique were studied for optical waveguide applications. Waveguide films with thickness more than 1.7 μm were prepared on a silicon substrate by a single-coating process and low-temperature heat treatment from these high-titanium-content composite materials. Scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal gravimetric analysis (TGA), UV-visible spectroscopy (UV-VIS), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) have been used to characterize the waveguide films. TGA curves showed that organic compounds in the composite materials would decompose in the temperature range from 200 °C to 480 °C. SEM, AFM and UV-VIS results showed that a dense, porous-free, and high transparency in the visible range waveguide film could be obtained at a low heat-treatment temperature. It was also noted that the carbon content in the film with higher titanium content heated at high temperature was evidenced by XPS. The waveguide propagation loss properties of the composite material films were also investigated and showed a dependence on the titanium molar fraction. Received: 13 June 2000 / Accepted: 21 June 2000 / Published online: 20 September 2000     

Properties of an ultrashort-pumped near-IR high gain dye amplifier

An ultra-short-pumped optical dye amplifier operating in the near-IR (720 nm) has been developed. We present an experimental study of the input–output characteristics of this simple device in a traveling wave collinear configuration. In essence, the combined effects of the ultrafast nature of the anisotropy induced by the exciting laser pulse along with the short transit time across the length of the cell allow for optimal output conditions given the number of molecules in the active volume. Two distinct amplifying regimes have been observed depending on photon density. Typical gain values of 10⁴ of the narrow bandwidth (∼9 nm) subpicosecond output signal were measured. The 8-mm² beam cross section enables this photon amplifier to be utilized in time-gated imaging applications. Received: 12 December 2001 / Revised version: 13 May 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-819/564-5442, E-mail: Daniel.Houde@Usherbrooke.ca     

Filling boron nitride nanotubes with metals

The authors’ endeavors over the last few years with respect to boron nitride (BN) nanotube metal filling are reviewed. Mo clusters of 1–2 nm in size and FeNi Invar alloy (Fe ∼60 at. %; Ni ∼40 at. %) or Co nanorods of 20–70 nm in diameter were embedded into BN nanotube channels via a newly developed two-stage process, in which multi-walled C nanotubes served as templates for the BN multi-walled nanotube synthesis. During cluster filling, low-surface-tension and melting-point Mo oxide first filled a C nanotube through the open tube ends, followed by fragmentation of this filling into discrete clusters via O₂ outflow and C→BN conversion within tubular shells at high temperature. During nanorod filling, C nanotubes containing FeNi or Co nanoparticles at the tube tips were first synthesized by plasma-assisted chemical vapor deposition on FeNi Invar alloy or Co substrates, respectively, and, then, the nanomaterial was heated to the melting points of the corresponding metals in a flow of B₂O₃ and N₂ gases. During this second stage, simultaneous filling of nanotubes with a FeNi or Co melt through capillarity and chemical modification of C tubular shells to form BN nanotubes occurred. The synthesized nanocomposites were analyzed by scanning and high-resolution transmission electron microscopy, electron diffraction, electron-energy-loss spectroscopy and energy-dispersive X-ray spectroscopy. The nanostructures are presumed to function as ‘nanocables’ having conducting metallic cores (FeNi, Co, Mo) and insulating nanotubular shields (BN) with the additional benefit of excellent environmental stability. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

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     

Structural and optical properties of Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films prepared by chemical solution methods

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films have been grown on Pt/Ti/SiO₂/Si substrates by chemical solution methods. X-ray diffraction analysis shows that BLT thin films are polycrystalline with (171)-preferential orientation. Atomic force microscopy investigation shows that they have large grains about 120 nm in size. A Pt/BLT/Pt capacitor has been fabricated and showed excellent ferroelectricity, with a remnant polarization and coercive field of 24 μC/cm² and 116 kV/cm, respectively. The capacitor shows no polarization fatigue up to 10⁹ switching cycles. The optical constants (n,k) of the BLT thin films in the wavelength range 0.35–1.7 μm were obtained by spectroscopic ellipsometry measurements, and the band-gap energy was found to be about 3.25 eV. Received: 16 October 2001 / Accepted: 6 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/65830-734, E-mail: gswang@mail.sitp.ac.cn     

Evidence for the existence of an unusual structure in the nanorods of InSb

Motivated by the recent prediction that InSb nanometer-diameter filaments can exhibit exotic physical properties, we have synthesized this material and have characterized the filaments. In this report, we describe the finding of an unusual phase of InSb. This new phase occurs when an InSb filament has a diameter of less than 100 nm. High-resolution X-ray-diffraction studies of InSb filaments, having radii ≅33.0 nm, indicate the InSb crystal lattice to be tetragonal, S.G. I4/mmm, with a unit-cell volume 12 times larger than that of the β-tin phase observed in bulk InSb above 2.0 GPa. The density of an InSb nanorod, as calculated from X-ray-diffraction data, is ∼22% more than that of the zinc-blende phase of InSb at ambient conditions, implying that the nanorod experiences a pressure of ∼2 GPa. In contrast, InSb nanorods with radii ≥50.0 nm are observed to show zinc-blende structure and densities nearly the same as that of the bulk. Received: 6 February 2002 / Accepted: 26 March 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/767-5301; E-mail: yousuf@seas.gwu.edu     

New organic–inorganic hybrid matrices doped with rhodamine 6G as solid-state dye lasers

We report on the laser action of rhodamine 6G (Rh6G) incorporated into new hybrid organic–inorganic monolithic materials. The synthesis of these materials proceeded via the simultaneous sol-gel process of the inorganic part (tetraethoxysilane or tetramethoxysilane) and the free-radical polymerization of an organic monomer part (2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and a 1:1 v/v copolymer of this monomer with methyl methacrylate). The wt. % proportion of the alkoxide was systematically varied in each organic formulation, and the effect of each organic–inorganic composition on the lasing properties of Rh6G was evaluated. The laser samples were transversely pumped and the influence on the laser action of dye concentration, pump wavelength and pump repetition rate was analyzed. Lasing efficiencies of up 26% and good stabilities, with a 90% drop in the initial laser output of up to 12000 pump pulses at 2.5 Hz, were obtained when the samples were pumped at 355 nm with 5.5 mJ/pulse from the third harmonic of a Q-switched Nd:YAG laser. Received: 31 July 2002 / Revised version: 14 October 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/564-4853, E-mail: ogarcia@ctp.csic.es     

Magnetic properties of Ni:SiO<Subscript>2</Subscript> nanocomposites synthesized by a modified sol–gel method

Ni nanoparticles embedded in an amorphous SiO₂ matrix were produced by a modified sol–gel method. This method resulted in nanocomposites with a controlled size distribution and good dispersion of the metallic particles. The particle-size distributions were found to have an average radius of ∼3 nm, as inferred from transmission electron microscopy, X-ray-diffraction analysis, and magnetic measurements. Magnetic characterizations revealed that samples exhibit superparamagnetic behavior above the blocking temperature T_B, 20 K≤T_B≤40 K, and absence of a shift along the field axis on hysteresis loops measured at T≤T_B, indicating that the metallic nanoparticles are also free from an oxide layer. Received: 7 October 2002 / Accepted: 9 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +55-11/3091-6984, E-mail: rjardim@if.usp.br     

Microstructures and dielectric properties of compositionally graded (Ba1-xSrx) TiO3 thin films prepared by pulsed laser deposition

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (x:0.0∼0.25) thin films were grown on Pt (111)/TiO₂/SiO₂/Si (100) substrates using layer-by-layer pulsed laser deposition in the temperature range 550–650 °C. Both downgraded (Ba/Sr ratio varying from 100/0 at the bottom surface to 75/25 at the top surface) and upgraded (Ba/Sr ratio varying from 75/25 at the bottom surface to 100/0 at the top surface) BST films were prepared. Their microstructures were systematically studied by X-ray diffractometry and scanning electron microscopy. A grain morphology transition from large ‘rosettes’ (>0.30 μm) to small compact grains (70–110 nm) was observed in the downgraded BST films as the deposition temperature was increased from 550 to 650 °C. No such grain morphology transition was detected in the upgraded BST films. Dielectric measurements with metal electrodes revealed an enhanced dielectric behavior in the downgraded films. This enhancement is mainly attributed to the large compressive stress field built up near the interface between the downgraded film and substrate. Furthermore, the BaTiO₃ layer in the downgraded BST films not only serves as a bottom layer but also as an excellent seeding layer for enhancing the crystallization of the subsequent film layers in the downgraded films. Received: 10 December 2001 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: 86-25/359-5535, E-mail: xhzhu@public1.ptt.js.cn     

Table-top KrF amplifier delivering 270 fs output pulses with over 9 W average power at 300 Hz

Applying the combination of a solid-state Ti:Sa laser system and a newly developed wide-aperture, discharge-pumped KrF amplifier, output pulses with over 9 W average power at 300 Hz have been achieved in a single output beam. The frequency-tripled seed pulses of the Ti:Sa system – delivering approximately 10 μJ energy at 248 nm – were amplified to over 30 mJ using a 3-pass off-axis amplification scheme. The optical set-up has been fitted to the amplifier’s parameters, and stored-energy measurements were carried out with different parameters in order to optimize the operational conditions of the device for the highest average power. Received: 10 June 2002 / Published online: 25 September 2002 RID="*" ID="*"Corresponding author. Fax: +49-551/503-599, E-mail: jbekesi@llg.gwdg.de     

Silicon nanowires grown from Au-coated Si substrate

Amorphous Si nanowires were grown on an Au-coated Si substrate by heat treatment at 1000 °C under an H₂ atmosphere. The nanowires have a length of several tens of a micron and a diameter of 10–20 nm. The growth mechanism of the nanowires was investigated and explained with a solid–liquid–solid model. Received: 11 July 2002 / Accepted: 7 July 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86/10-62751615, E-mail: yudp@pku.edu.cn     

Application of mid-infrared cavity-ringdown spectroscopy to trace explosives vapor detection using a broadly tunable (6–8 μm) optical parametric oscillator

A novel instrument, based on cavity-ringdown spectroscopy (CRDS), has been developed for trace gas detection. The new instrument utilizes a widely tunable optical parametric oscillator (OPO), which incorporates a zinc–germanium–phosphide (ZGP) crystal that is pumped at 2.8 μm by a 25-Hz Er,Cr:YSGG laser. The resultant mid-IR beam profile is nearly Gaussian, with energies exceeding 200 μJ/pulse between 6 and 8 μm, corresponding to a quantum conversion efficiency of approximately 35%. Vapor-phase mid-infrared spectra of common explosives (TNT, TATP, RDX, PETN and Tetryl) were acquired using the CRDS technique. Parts-per-billion concentration levels were readily detected with no sample preconcentration. A collection/flash-heating sequence was implemented in order to enhance detection limits for ambient air sampling. Detection limits as low as 75 ppt for TNT are expected, with similar concentration levels for the other explosives. Received: 1 April 2002 / Revised version: 13 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-408/524-0551, E-mail: mtodd@picarro.com     

Growth of a textured quasicrystalline phase in Ti-Ni-Zr films prepared by pulsed laser deposition

The preparation in thin film form of the known icosahedral phase in Ti-Ni-Zr bulk alloys has been investigated as a function of substrate temperature. Films were deposited by pulsed laser deposition on sapphire substrates at temperatures ranging from room temperature to 350 °C. Morphological and structural modifications have been followed by grazing-incidence and θ–2θ X-ray diffraction, transmission electron diffraction and imaging. Chemical composition has been analyzed by electron probe microanalysis. The in-depth variation of composition has been studied by secondary neutral mass spectroscopy. We show that pulsed laser deposition at 275 °C makes the formation of a 1-μm-thick film of Ti-Ni-Zr quasicrystalline textured nanocrystallites possible. Received: 7 June 2001 / Accepted: 18 February 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +33-3/8357-6300, E-mail: brien@mines.u-nancy.fr