COLORATION EFFECT OF PULSED LASER ON WO3

When laser pulses irradiate the surface of the sample WO₃, an interesting coloration effect is obtained. Only by one pulse of XeCl laser irradiation (wavelength: 308 nm, pulse duration: 36 ns, output power: 100 mJ/pulse), a significant color change appears. X-ray photoelectron spectroscopy (XPS) shows that a partial reduction process of WO₃ occurs and conduction band electrons appears. X-ray diffraction pattern indicates that the lattice parameters of the colored samples are increased. A molten layer can be seen in scanning electron microscopy (SEM) image. It may be concluded that the coloration effect of pulsed laser undergoes a process different from that of electro- or photo- chromism, and may be attributed to thermochromism and substoichiometric WO₃ is formed. The coloration process is characterized by its high speed and stability.     

Pd2+ reduction and gasochromic properties of colloidal tungsten oxide nanoparticles synthesized by pulsed laser ablation

Tungsten oxide nanoparticles were fabricated by a pulsed laser ablation method in deionized water using the first harmonic of a Nd:YAG laser (λ=1064 nm) at three different laser pulse energies (E1 =160, E2 =370 and E3 =500 mJ/pulse), respectively. The aim is to investigate the effect of laser pulse energy on the size distribution and gasochromic property of colloidal nanoparticles. The products were characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy. The results indicated that WO₃ nanoparticles were formed. After ablation, a 0.2 g/l PdCl₂ solution was added to activate the solution against hydrogen gas. In this process Pd²⁺ ions were reduced to deposit fine metallic Pd particles on the surface of tungsten oxide nanoparticles. The gasochromic response was measured by H₂ and O₂ gases bubbling into the produced colloidal Pd–WO₃. The results indicate that the number of unreduced ions (Pd²⁺) decreases with increasing laser pulse energy; therefore, for colloidal nanoparticles synthesized at the highest laser pulse energy approximately all Pd²⁺ ions have been reduced. Hence, the gasochromic response for this sample is nearly reversible in all cycles, whereas those due to other samples are not reversible in the first cycle.     

Laser–diode-pumped passively Q-switched Nd:NaY(WO4)2 laser with GaAs saturable absorber

A laser–diode-pumped passively Q-switched new type crystal Nd³⁺:NaY(WO₄)₂ (known as Nd:NYW) laser with GaAs semiconductor saturable absorber has been realized. The dependence of pulse repetition rate, pulse energy, pulse width, and peak power on pump power for different output coupler reflectivities are measured. The coupled rate equations are used to simulate the Q-switched process of laser, and the numerical solutions agree with the experimental results.     

Passive Q-switching of a laser-diode-pumped intracavity-frequency-doubling Nd:Nd<Superscript>3+</Superscript>:NaY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>/KTP laser with Cr<Superscript>4+</Superscript>:YAG saturable absorber

Nd³⁺:NaY(WO₄)₂, known as Nd:NYW, is a new type crystal. By using laser-diode as pump source, a passive Q-switching of intracavity-frequency-doubling Nd:NYW/KTP laser has been realized with Cr⁴⁺:YAG saturable absorber. The dependence of pulse repetition rate, pulse energy, pulse width, and peak power on incident pump power for different small-signal transmissions of Cr⁴⁺:YAG are measured. The coupled rate equations are used to simulate the Q-switched process of laser, and the numerical solutions agree with the experimental results.     

Effect of molybdenum doping on the electrochromic properties of tungsten oxide thin films by RF magnetron sputtering

Thin films of pure and molybdenum (Mo)-doped tungsten trioxide (WO₃) were deposited on indium tin oxide (ITO)-coated glass and Corning glass substrates by RF magnetron sputtering technique. The effect of Mo doping on the structural, morphological, optical and electrochromic properties of WO₃ films was studied systematically. The energy dispersive X-ray analysis (EDAX) revealed that the films consist of molybdenum concentrations from 0 to 2 at.%. X-ray diffraction (XRD) studies indicated that with the increase of Mo concentration the structural phase transformation takes place from polycrystalline to amorphous phase. The crystallite size of the films decreased from 24 to 12 nm with increase of doping concentration of Mo in WO₃. Scanning electron microscope (SEM) analysis revealed that Mo dopant led to significant changes in the surface morphology of the films. The electrochemical and electrochromic performance of the pure and Mo-doped WO₃ were studied. The WO₃ films formed with 1.3 at.% Mo dopant concentration exhibited high optical modulation of 44.3 % and coloration efficiency of 42.5 cm²/C.     

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO₃ (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO₃. These amorphous thin films of about 4 μm in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO₃ microcrystals in the amorphous phase.     

Graphene-based passively Q-switched Nd:KLu(WO4)2 eye-safe laser operating at 1,425 nm

With graphene as saturable absorber, an Nd:KLu(WO₄)₂ eye-safe laser operating at 1,425 nm is demonstrated. To the best of our knowledge, this is the first demonstration that an Nd:KLu(WO₄)₂ laser operates at the eye-safe 1.4-μm region. A maximum total average output power of 170 mW is obtained under the pump power of 9.6 W, corresponding to an optical–optical efficiency of 1.77 %. The minimum pulse width and the highest pulse repetition rate are 153 ns and 97 kHz, respectively. Also the characteristics of the graphene used as saturable absorber for a 1.4-μm laser were studied for the first time.     

Crystal growth,optical spectroscopy,and continuous-wave laser operation of Ho:KLu(WO4)2 crystals

We present the crystal growth, optical spectroscopy, and room temperature continuous-wave (CW) laser operation of monoclinic Ho:KLu(WO₄)₂ crystals. Macro defect-free crystals of several dopant concentrations were grown by top-seeded solution growth slow-cooling method. The evolution of unit cell parameters with holmium doping level and temperature was studied using X-ray powder diffraction. The spectroscopic properties were characterized in terms of room- and low-temperature optical absorption and photoluminescence. From low-temperature optical absorption measurements, the energy of the Stark levels was determined. Calculation of the emission and gain cross sections is presented. CW laser action was realized for 3 and 5 at. % Ho-doped KLu(WO₄)₂ by in-band pumping using a Tm:KLu(WO₄)₂ pump laser. A maximum output power of 507 mW with a slope efficiency of ~38 % with respect to the incident power was achieved at 2,080 nm with the Ho:KLu(WO₄)₂ laser.     

Preparation, characterization and photocatalytic activity of multi-walled carbon nanotube-supported tungsten trioxide composites

Multi-walled carbon nanotube (MWCNT)-supported tungsten trioxide (WO₃) composite catalysts were prepared by liquid-phase process. WO₃ nanoparticles grew on the inner and outer surface of MWCNTs. Their photocatalytic activities in the degradation of the Rhodamine B Dye were studied. The effects of mass ratio of MWCNTs to WO₃ were discussed. X-ray diffraction, field emission transmission electron microscopy, thermogravimetric-differential thermal analysis and ultraviolet-visible light absorption spectra were carried out to characterize the composite catalysts. The results indicated that the optimum mass ratio of MWCNTs to WO₃ is 5:100.     

Spectral properties and 1.5–1.6 μm laser operation of Er:Yb:NaCe(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

An Er:Yb:NaCe(WO₄)₂ crystal was grown by the Czochralski method. Spectral properties of the crystal were investigated and compared with those of the Er:Yb:Ce:NaGd(WO₄)₂ crystal. The green up-conversion was not observed when the Er:Yb:NaCe(WO₄)₂ crystal was excited by a diode laser at 970 nm. The efficiency of energy transfer from Yb³⁺ to Er³⁺ in the Er:Yb:NaCe(WO₄)₂ crystal was calculated to be about 93%. End-pumped by a diode laser at 970 nm in a hemispherical cavity, 0.95 W quasi-CW laser at 1.5–1.6 μm was achieved in a 1.47-mm-thick c-cut Er:Yb:NaCe(WO₄){ia2} crystal, the slope efficiency was 11%, and the threshold was 2.83 W.     

Correlation between lithium storage and diffusion properties and electrochromic characteristics of WO3 thin films

As essential electrochromic(EC) materials are related to energy savings in fenestration technology,tungsten oxide(WO3) films have been intensively studied recently.In order to achieve better understanding of the mechanism of EC properties,and thus facilitate optimization of device performance,clarification of the correlation between cation storage and transfer properties and the coloration performance is needed.In this study,transparent polycrystalline and amorphous WO3 thin films were deposited on SnO2:F-coated glass substrates by the pulsed laser deposition technique.Investigation into optical transmittance in a wavelength range of 400-800 nm measured at a current density of 130 μA·cm-2 with the applied potential ranging from 3.2 to 2.2 V indicates that polycrystalline films have a larger optical modulation of ～ 30% at 600 nm and a larger coloration switch time of 95 s in the whole wavelength range compared with amorphous films(～ 24% and 50 s).Meanwhile,under the same conditions,polycrystalline films show a larger lithium storage capacity corresponding to a Li/W ratio of 0.5,a smaller lithium diffusion coefficient(2×10-12cm2·s-1 for Li/W=0.24) compared with the amorphous ones,which have a Li/W ratio of 0.29 and a coefficient of ～2.5×10-11cm2·s-1 as Li/W=0.24.These results demonstrate that the large optical modulation relates to the large lithium storage capacity,and the fast coloration transition is associated with fast lithium diffusion.     

Soft X-ray spectroscopic study on the electronic structure of WO3 thin films fabricated under various annealing temperature and gas flow conditions

The electrical properties of WO₃ thin films vary significantly depending on the growth conditions. In this work, the influence of O₂ gas on the band gap of WO₃ thin films during growth was investigated via electronic structure characterization using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES). A substantial decrease in the electrical conductivity of the WO₃ films was observed with an increase in the O₂ partial pressure during growth. Spectral differences in the peak energy and intensity were apparent for WO₃ films grown under only Ar and those grown in Ar:O₂. It is difficult to explain the acquired spectrum of WO₃ with oxygen defects through the rigid-band model in terms of the simple addition of electrons to the conduction band of WO₃. Our results show that an oxygen deficiency in WO₃ moves the conduction band to the Fermi edge.     

Electrochromism in tungsten trioxide films obtained by reactive magnetron sputtering of a tungsten target

The results of structural investigations of electrochromic films of WO₃, obtained by reactive magnetron sputtering of a tungsten target, are presented. It is shown that at low temperatures an amorphous film of WO₃ is formed on the substrate. At a substrate temperature greater than 250°C the film that is formed is polycrystalline and has the structure of hydrotungstic bronze H_0.33WO₃. When annealed in air it transfers into the triclinic modification of WO₃. Spectral investigations showed that the electrochromic properties are most pronounced in amorphous films. Films of WO₃, having a polycrystalline structure after annealing in air, practically lose their ability for electrochromic coloration. Institute of High-Current Electronics, Sib. Otd., Russ. Akad. Nauk. Translated from Izvestiya Vysshykh Uchebnykh Zavedenii, Fizika, No. 5, pp. 3–7, May, 1996.     

XPS study of WC formation process

The surface composition and chemical bonding state of WO₃ carburized in CO at 700°C have been investigated with X-ray photoelectron spectroscopy, in order to clarify the mechanism of WC formation. The experimental results show that the carburization process is based on a direct reaction of WO_x (x≦3) with free carbon which accumulates on the WO_x surface by the disproportionation of CO. A model for the WC formation process is also presented.     

Characteristics of a passively Q-switched Nd:NaY(WO4)2 laser with Cr:YAG saturable absorber

By using xenon flash lamp as pump source and Cr⁴⁺:YAG as passive Q-switcher, we have performed the Q-switched laser operation at 1.06 μm with an Nd³⁺:NaY(WO₄)₂ (known as Nd:NYW) crystal. Meanwhile, the pulse width, the single pulse energy and the repetition rate under different small-signal transmissions of Cr⁴⁺:YAG and different reflectivities of output reflector are measured, and the numerical solutions of the coupling wave rate equations agree with the experimental results.     

Photoluminescence properties and energy transfer of Ca3WO6:Sm3+ co-doped Eu3+

A reddish-orange phosphor, Ca₃WO₆:Sm³⁺, was synthesized by the convenient solid-state reaction method and characterized by X-ray diffraction (XRD). Photoluminescence properties and concentration quenching of Ca₃WO₆:Sm³⁺ phosphor have been discussed in the excitation and emission spectra. Ca₃WO₆:Sm³⁺ phosphor is able to generate a strong excitation peak, which matches the emission wavelength from near-UV LEDs. Energy transfer from Sm³⁺ to Eu³⁺ in Ca₃WO₆ host is observed and investigated in detail. The chromaticity coordinates of Ca₃WO₆:Sm³⁺ can be regulated to approach the NTSC standard values of red phosphor by codoping Eu³⁺ ions. The photoluminescence properties suggest that novel Ca₃WO₆:Sm³⁺, Eu³⁺ phosphor might have a potential application for near-UV LEDs.     

Structural, optical and morphological studies on laser ablated nanostructured WO3 thin films

Thin films of tungsten trioxide (WO₃) are prepared by reactive pulsed laser deposition (PLD) technique on glass substrates at three different substrate temperatures (T_s). The structural, morphological and optical properties of the deposited films are systematically studied using X-ray diffraction (XRD), grazing incidence X-ray diffraction (GIXRD), micro-Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-VIS spectrophotometry techniques. X-ray diffraction analysis reveals that crystalline WO₃ films can grow effectively even at 300 K at an oxygen pressure of 0.12 mbar. All the films deposited at various T_s exhibit mixed oxide phase consisting of orthorhombic and triclinic phase of tungsten oxide with a preferred orientation along (0 0 1) lattice plane reflection. Micro-Raman results are consistent with X-ray diffraction findings. The SEM analysis shows that deposited films are porous and crystalline grains are of nano-metric dimension. The effect of T_s on mean surface roughness studied by AFM analysis reveals that mean surface roughness decreases with increase in T_s. The optical response of WO₃ layers measured using UV-VIS spectrophotometry is used to extract the optical constants such as refractive index (n), extinction coefficient (k) and optical band gap (E_g), following the method of Swanepoel.     

插层化合物钨青铜单晶的物理研究

本工作利用X射线衍射分析、电导测量、红外、喇曼散射等手段,对用熔盐电解法生长的K_xWO₃,Na_yWO₃和K_xNa_yWO₃单晶进行了深入的研究,得出K_xNa_yWO₃是钠离子插入到K_xWO₃的结论,提出了K_xNa_{y关键词：}     

CW laser performance of Yb and Er,Yb doped tungstates

 Room temperature cw laser action of Yb³⁺-doped KY(WO₄)₂ and KGd(WO₄)₂ crystals at 1.025 μm and Er, Yb : KY(WO₄)₂ at 1.54 μm has been demonstrated under pumping by both Ti-sapphire laser and InGaAs laser diodes. A slope efficiency of Yb-lasers up to 78% has been obtained. Received: 19 June 1996     

Electrochromic properties of nanocrystalline WO3 thin films grown on flexible substrates by plasma-assisted evaporation technique

Thin films of Tungsten trioxide (WO₃) were deposited on ITO-coated flexible Kapton substrates by plasma-assisted activated reactive evaporation (ARE) technique. The influence of growth and microstructure on optoelectrochromic properties of WO₃ thin films was studied. The nanocrystalline WO₃ films grown at substrate temperature of 250°C were composed of vertically elongated cone-shaped grains of size 65 nm with relative density of 0.71. These WO₃ films demonstrated higher optical transmittance of 85% in the visible region with estimated optical band gap of 3.39 eV and exhibited better optical modulation of 66% and coloration efficiency of 52.8 cm²/C at the wavelength of 550 nm.