Electrogenerated chemiluminescence sensor for formaldehyde based on Ru(bpy)32+-doped silica nanoparticles modified Au electrode

A novel and sensitive electrogenerated chemiluminescence (ECL) sensor for formaldehyde was developed with the amine-functionalized Ru(bpy)₃²⁺-doped silica nanoparticles (Ru-DSNPs) as ECL emitter. Ru(bpy)₃²⁺ doped on the silica nanoparticle can maintain its electrochemical activities, which made silica nano-beads a excellent carrier of Ru(bpy)₃²⁺ species. The uniform Ru-DSNPs (about 75 nm) were conjugated with Au electrode using mercaptoacetic acid as the intermediate to fabricate an ECL sensor for formaldehyde. The ECL analytical performances of this ECL sensor for formaldehyde based on its enhancement ECL emission of Ru(bpy)₃²⁺ were investigated in details. Under the optimum condition, the ECL intensity was linear with the formaldehyde concentration in the range of 1.0 × 10^? 8 mol/L to 1.0 × 10^? 6 mol/L. The detection limit was 6.0 × 10^? 9 mol/L (S/N = 3). This approach offered obvious advantages of being simpler, faster, and more stable compared with other sensors, and possessed great potential for formaldehyde detection which could be applied to determine directly the formaldehyde in real samples without pre-separation.     

Thermoluminescence properties of Ce-doped LiSr4(BO3)3 phosphor

Borates LiSr₄(BO₃)₃ were synthesized by high-temperature solid-state reaction. The thermoluminescence (TL) and some of the dosimetric characteristics of Ce³⁺-activated LiSr₄(BO₃)₃ were reported. The TL glow curve is composed of only one peak located at about 209 °C between room temperature and 500 °C. The optimum Ce³⁺ concentration is 1 mol% to obtain the highest TL intensity. The TL kinetic parameters of LiSr₄(BO₃)₃:0.01Ce³⁺ were studied by the peak shape method. The TL dose response is linear in the protection dose ranging from 1 mGy to 1 Gy. The three-dimensional thermoluminescence emission spectra were also studied, peaking at 441 and 474 nm due to the characteristic transition of Ce³⁺.     

Growth and spectral properties of Cr:KAl(MoO4)2 crystal

The Cr³⁺:KAl(MoO₄)₂ single crystal was grown by top seeding solution growth method (TSSG). Based on the absorption and emission spectra, the crystal field strength Dq, the Racah parameters B and C, the effective phonon energy ?ω and the Huang-Rhys factor S were calculated: Dq = 1494.8 cm^− 1, B = 585.5 cm^− 1 and C = 3049 cm^− 1, ?ω = 373.8 cm^− 1 and the Huang-Rhys factor S = 3.74, respectively. The value Dq/B = 2.55 indicates that Cr³⁺ ion occupies the strong crystal field site in KAl(MoO₄)₂ crystal. A comparison of crystal field parameters for Cr³⁺:KAl(MoO₄)₂ with other Cr³⁺-doped crystals was presented. The results of spectral measurement show that Cr³⁺:KAl(MoO₄)₂ may be a potential candidate for broadband laser applications.     

Photoluminescence and radioluminescence of pure and Ce activated Na3Gd(PO4)2

The spectroscopic properties of Na₃Gd(PO₄)₂ and Na₃Gd(PO₄)₂:Ce³⁺ phosphors in the VUV-UV spectral range were investigated. Five excitation bands of Ce³⁺ ions at Gd³⁺ sites are observed at wavelengths of 205, 246, 260, 292, and 321 nm. Doublet Ce³⁺ 5d → 4f emission bands are observed at 341 and 365 nm with a decay constant τ_1/e around 26 ns. The X-ray excited luminescence of Na₃Gd_0.99Ce_0.01(PO₄)₂ at room temperature shows a photon yield of ∼17,000 photons/MeV of absorbed X-ray energy.     

Scintillation and optical properties of Pb-doped YCa4O(BO3)3 crystals

This communication reports optical properties and radiation responses of Pb²⁺ 0.5 and 1.0 mol%-doped YCa₄O(BO₃)₃ (YCOB) single crystals grown by the micro-pulling-down (μ-PD) method for neutron scintillator applications. The crystals had no impurity phases according to the results of X-ray powder diffraction. These Pb²⁺-doped crystals demonstrated blue-light luminescence at 330 nm because of Pb²⁺¹S₀-³P_0,1 transition in the photoluminescence spectra. The main emission decay component was determined to be about 250-260 ns under 260 nm excitation wavelength. When irradiated by a ²⁵²Cf source, the relative light yield of 0.5% Pb²⁺-doped crystal was about 300 ph/n that was determined using the light yield of a reference Li-glass scintillator.     

Chemical diffusion coefficient of lithium ion in Li3V2(PO4)3 cathode material

The kinetic properties of monoclinic lithium vanadium phosphate were investigated by potential step chronoamperometry (PSCA) and electrochemical impedance spectroscopy (EIS) method. The PSCA results show that there exists a linear relationship between the current and the square root of the time. The D?_Li values of lithium ion in Li_3-xV₂(PO₄)₃ under various initial potentials of 3.41, 3.67, 3.91 and 4.07 V (vs Li/Li⁺) obtained from PSCA are 1.26 × 10^− 9, 2.38 × 10^− 9, 2.27 × 10^− 9 and 2.22 × 10^− 9 cm²·s^− 1, respectively. Over the measuring temperature range 15-65 °C, the diffusion coefficient increased from 2.67 × 10^− 8 cm²·s^− 1 (at 15 °C) to 1.80 × 10^− 7 cm²·s^− 1 (at 65 °C) as the measuring temperature increased.     

Determination of the chemical diffusion coefficient of lithium in Li3V2(PO4)3

The chemical diffusion of lithium ion in Li₃V₂(PO₄)₃ were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods. The CV results show that there exists a linear relationship between the peak current (i_p) and the square root of the scan rate (ν^1/2). The impedance spectrum exhibits a single semicircle and a straight line in a very low frequency region. A linear behavior was observed for every curve of the real resistance as a function of the inverse square root of the angular frequency in a very low frequency region. The obtained chemical diffusion coefficient from EIS measurements varies within 10^− 9 to 10^− 8 cm²·s^− 1, in good agreement with those from CV results.     

Polarized spectroscopic properties of Ho ions in NaLa(MoO4)2 crystal

A Ho³⁺-doped NaLa(MoO₄)₂ single crystal was grown by the Czochralski method. The polarized absorption spectra, polarized fluorescence spectra, and fluorescence decay curves of the crystal were measured at room temperature. The spontaneous emission probabilities, radiative lifetimes, and fluorescence branching ratios of the typical fluorescence multiplets of Ho³⁺ ions were calculated. The polarized stimulated emission and gain cross-sections of the ⁵I₇ → ⁵I₈ transition were obtained. The results show that the Ho³⁺:NaLa(MoO₄)₂ crystal is a promising gain medium for tunable and ultrashort pulse lasers operating around 2.0 μm.     

Growth and spectral properties of Er:NaGd(WO4)2 crystal

A high optical quality Er³⁺-doped NaGd(WO₄)₂ single crystal with dimensions of ∅18 × 50 mm³ has been grown using the Czochralski method. The structure of the grown crystal was proved by X-ray powder diffraction. The accurate concentration of Er³⁺ ion in the crystal was measured. The absorption spectra, fluorescence spectra and fluorescence lifetime of the crystal were measured at room temperature. Green up-conversion luminescence has been observed when the crystal is excited at 965 nm.     

Electrogenerated chemiluminescence from R(bpy)3(2+) ion-exchanged in carbon nanotube/perfluorosulfonated ionomer composite films

The electrochemistry and electrogenerated chemiluminescence (ECL) of ruthenium(II) tris(bipyridine) (Ru(bpy)(3)(2+)) ion-exchanged in carbon nanotube (CNT)/Nafion composite films were investigated with tripropylamine (TPA) as a coreactant at a glassy carbon (GC) electrode. The major goal of this work was to investigate and develop new materials and immobilization approaches for the fabrication of ECL-based sensors with improved sensitivity, reactivity, and long-term stability. Ru(bpy)(3)(2+) could be strongly incorporated into Nafion film, but the rate of charge transfer was relative slow and its stability was also problematic. The interfusion of CNT in Nafion resulted in a high peak current of Ru(bpy)(3)(2+) and high ECL intensity. The results indicated that the composite film had more open structures and a larger surface area allowing faster diffusion of Ru(bpy)(3)(2+) and that the CNT could adsorb Ru(bpy)(3)(2+) and also acted as conducting pathways to connect Ru(bpy)(3)(2+) sites to the electrode. In the present work, the sensitivity of the ECL system at the CNT/Nafion film-modified electrodes was more than 2 orders of magnitude higher than that observed at a silica/Nafion composite film-modified electrode and 3 orders of magnitude higher than that at pure Nafion films. The CNT/Nafion composite film-modified GC electrodes also exhibited long-term stability.     

Tunneling induced decomposition of Mo(CO)6 onto TiO2(110) surface

Tunneling induced decomposition of Mo(CO)₆ from the gas phase was studied on TiO₂(110) surface by scanning tunneling microscopy (STM) and spectroscopy (STS). The efficiency of the procedure was followed by measuring the dot volume as a proportional indicator of the amount of the decomposed precursor. It was found that below 1 × 10⁻⁵ Pa background pressure of Mo(CO)₆, there is no measurable effect and above 1 × 10⁻⁴ Pa, the nanodot size is too large compared to the curvature of the tip (20-40 nm). A threshold bias of +3.1(±0.1) V on the sample was measured for the decomposition of Mo(CO)₆ in gas ambient. In the absence of the precursor, dot formation was observed only above +3.7(±0.2) V, in good agreement with the results reported in our earlier work about nanolithography on clean TiO₂(110) substrate (E. Kriván, A. Berkó: J. Vac. Sci. & Tech. B 15(1) (1997)25). By applying voltages in the range of 3.1-3.5 V, a systematic enlargement of the created nanodots was found in the range of 2-20 s of duration and 0.01-1.0 nA of tunneling current. The I-V curves detected on the top of the nanodots have shown that the created features are of insulator character. This observation indicates that the decomposition of Mo(CO)₆ is also accompanied by oxidation of the deposited Mo species.     

Sr3.5Mg0.5Si3O8Cl4: Eu bluish-green-emitting phosphor for NUV-based LED

Sr₄Si₃O₈Cl₄:Eu²⁺ and Sr_3.5Mg_0.5Si₃O₈Cl₄:Eu²⁺ phosphors were prepared by a conventional solid state reaction (SS). Excited by 370 nm near-ultraviolet light, the phosphors show an efficient bluish-green wide-band emission centering at 484 nm, which originates from the 4f5d¹ → 4f⁷ transition of Eu²⁺ ion. The excitation spectra of the phosphors are a broad band extending from 250 nm to 400 nm. Mg²⁺-codoping greatly enhances the bluish-green emission of the phosphors. An LED was fabricated by coating the Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ phosphor onto an ~ 370 nm-emitting InGaN chip. The LED exhibits bright bluish-green emission under a forward bias of 20 mA. The results indicate that Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ is a candidate as a bluish-green component for fabrication of NUV-based white LEDs.     

Synthesis and luminescent characteristic of Eu-doped (Gd,Lu)2O3 nanopowders

Eu³⁺ doped (Gd,Lu)₂O₃ nanopowders with particle sizes ranging from 20 to 70 nm were synthesized by the co-precipitant method using mixed precipitants, namely the mixture of ammonium hydroxide (NH₃⋅H₂O) and ammonium hydrogen carbonate (NH₄HCO₃). The precipitate precursor prepared by this method was believed to possess a basic carbonate composition and its thermal decomposition of the (Gd,Lu)₂O₃:Eu³⁺ powders were investigated by Thermogravimetric analysis and differential thermal analysis (TG-DTA). This preparation was followed by a calcination process at 800-1100 °C and corresponding phosphor structure were examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Photoluminescence measurement of the (Gd,Lu)₂O₃:Eu³⁺ particles show typical red emission at the 612 nm corresponding to the ⁵D₀ → ⁷F₂ transition. We found that the optimal Eu³⁺ molar doping concentration, calcined temperature and reaction time were 7 mol%, 1000 °C, and 2 h, respectively, which is helpful to obtain the final transparent ceramics with excellent properties.     

Chemical vapor deposition of NiSi using Ni(PF3)4 and Si3H8

NiSi_x films were deposited using chemical vapor deposition (CVD) with a Ni(PF₃)₄ and Si₃H₈/H₂ gas system. The step coverage quality of deposited NiSi_x was investigated using a horizontal type of hot-wall low pressure CVD reactor, which maintained a constant temperature throughout the deposition area. The step coverage quality improved as a function of the position of the gas flow direction, where PF₃ gas from decomposition of Ni(PF₃)₄ increased. By injecting PF₃ gas into the Ni(PF₃)₄ and Si₃H₈/H₂ gas system, the step coverage quality markedly improved. This improvement in step coverage quality naturally occurred when PF₃ gas was present, indicating a strong relationship. The Si/Ni deposit ratio at 250 °C is larger than at 180 °C. It caused a decreasing relative deposition rate of Ni to Si. PF₃ molecules appear to be adsorbed on the surface of the deposited film and interfere with faster deposition of active Ni deposition species.     

Near UV-based LED fabricated with Ba5SiO4(F,Cl)6:Eu as blue- and green-emitting phosphor

A series of halosilicate phosphor, Ba₅SiO₄(F,Cl)₆:Eu²⁺, were synthesized by a solid state reaction. Excited by 370-nm light, Ba₅SiO₄Cl₆:Eu²⁺ exhibits a broad emission band peaking at 440 nm. Partial substitution of Cl⁻ with F⁻ in the host lattice leads to red-shift in the emission band with centering wavelength from 440 nm to 503 nm. The possible mechanism for the luminescence change was discussed based on the XRD patterns. Blue and green LEDs were fabricated by combination of a 370 nm-emitting near UV chip and the optimal Ba₅SiO₄Cl₆:Eu²⁺ and Ba₅SiO₄(F₃Cl₃):Eu²⁺, respectively. This series of phosphors is considered as a promising blue and green component used in fabrication of near UV-based white LEDs.     

Study on ZnGa2O4:Cr a.c. powder electroluminescent device

An a.c. powder electroluminescent (EL) device using ZnGa₂O₄:Cr³⁺ phosphor was fabricated by the screen printing method. Optical and electrical properties of the device were investigated. The fabricated device shows a red emission at 695 nm driven by the a.c. voltage. The emission is attributed to the energy transfer from hot electrons to Cr³⁺ centers via self-activated Ga-O groups. Luminance (L) versus voltage (V) matches the well-known equation of L = L₀exp(− bV ^− 1 / 2) and luminance increases proportionally with frequency due to the increase of excitation probability of host lattice or Cr³⁺ centers. The diagram of the charge density (Q) versus applied voltage (V) is based on a conventional Sawyer-Tower circuit. At 280 V and 1000 Hz, the luminance and the luminous efficiency of the fabricated powder EL device are about 1.0 cd/m² and 13 lm/W, respectively. And under the high field, the device fabricated with the oxide-based phosphor of ZnGa₂O₄:Cr³⁺ shows excellent stability in comparison with the conventional sulfide powder EL device.     

Polarized spectral properties of Tm:K5Bi(MoO4)4 crystal

Trivalent thulium-doped K₅Bi(MoO₄)₄ single crystals were grown by the Czochralski method. Its polarized absorption and fluorescence spectra and fluorescence decay curves were recorded at room temperature. On the basis of the Judd-Ofelt theory, the spectral parameters of the Tm³⁺:K₅Bi(MoO₄)₄ crystal were calculated. The cross relaxations between Tm³⁺ ions were analyzed. The emission cross sections of the ³F₄ → ³H₆ transition were obtained by the Fuchtbauer-Ladenburg formula and then the gain cross sections around 1.9 μm were calculated. The peak emission cross section and width of emission band around 1.9 μm are comparable to those for Tm³⁺:YAG and the tunable range is about 280 nm for the potential ∼1.9 μm laser operation via the ³F₄ → ³H₆ transition.     

Er:YAl3(BO3)4 glassy thin films from polymeric precursor and sol-gel methods: Waveguides for integrated optics

This paper presents the characterization of single-mode waveguides for 980 and 1550 nm wavelengths. High quality planar waveguide structure was fabricated from Y_1 − xEr_xAl₃(BO₃)₄ multilayer thin films with x = 0.02, 0.05, 0.1, 0.3, and 0.5, prepared through the polymeric precursor and sol-gel methods using spin-coating. The propagation losses of the planar waveguides varying from 0.63 to 0.88 dB/cm were measured at 632.8 and 1550 nm. The photoluminescence spectra and radiative lifetimes of the Er^{3+ 4}I_13/2 energy level were measured in waveguiding geometry. For most samples the photoluminescence decay was single exponential with lifetimes in between 640 μs and 200 μs, depending on the erbium concentration and synthesis method. These results indicate that Er doped YAl₃(BO₃)₄ compounds are promising for low loss waveguides.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.