Quantitative IBBCEAS measurements of I2 in the presence of aerosols

An instrument implementing Incoherent BroadBand Cavity-Enhanced Absorption Spectroscopy (IBBCEAS) for quantitative measurements of molecular iodine (I₂) at ambient pressure and in the presence of aerosols is presented. The instrument is based on a LED emitting in the green spectral region around 500–550 nm, exciting a multitude of rovibronic transitions in the I₂ B ← X electronic absorption spectrum. I₂ was generated using a permeation device and was mixed with a dilution flow of Ar and another flow containing NaCl aerosols. Retrieval of the mirror reflectivity, necessary for quantitative IBBCEAS measurements, was not pursued in this study. Instead, calibrated I₂ flows were used, and a differential optical absorption spectroscopy type of algorithm was implemented for the data analysis. This approach has several benefits, in particular when light extinction due to aerosols is substantial. Estimated detection limits are roughly 0.04 nmol/l without aerosols and 0.4 nmol/l in the presence of aerosols (10¹⁰ particles/l with 60–70 nm mean diameter, leading to I ₀/I _aerosols ≈ 5.4). A drop in measured I₂ concentration in relation to the expected mixing ratio was observed when using the highest aerosol concentration, likely due to adsorption of I₂ onto aerosols.     

Current-voltage characteristics of voltage-biased Tl2Ba2CaCu2O8 intrinsic Josephson junctions

The voltage-biased current-voltage (I–V) characteristics of intrinsic Josephson junctions (IJJs), which are fabricated with misaligned high temperature superconducting Tl₂Ba₂CaCu₂O₈ (Tl-2212) thin film, are investigated experimentally. Three characteristic regions in the I–V curve are observed at 47 K. In the low voltage part, the current firstly increases and then decreases slowly with increasing the biased voltage, which is shown as a bump. In the next region, the current slightly increases with increasing the biased voltage until a sudden decrease of the current appears. Thereafter, branch structure forms with increasing the voltage on the I–V characteristic. The influence of the self-heating on the I–V characteristics is investigated and the temperature dependence of the I–V characteristics is measured to explore these characteristics in detail.     

Photoluminescence of AgGaS2 and CuGaS2 doped with rare-earth impurities

Photoluminescence (PL) related to rare-earth (RE) impurities (Ho, Er and Eu) in AgGaS₂ and CuGaS₂ crystals has been studied. In Ho-doped AgGaS₂ and CuGaS₂, two series of PL lines are observed in 1.86–1.92 eV region and 2.24 eV region, and they are assigned to ⁵F₃–⁵I₇ and ⁵S₂–⁵I₈ transitions of the Ho³⁺ ion, respectively. Similarly, in Er-doped AgGaS₂ and CuGaS₂, Er³⁺-related two PL series are observed: 1.83–1.88 eV region (⁴F_9/2–⁴I_15/2) and 2.22–2.26 eV region (⁴S_3/2–⁴I_15/2). For both Ho and Er impurities, the profile of the PL spectrum in AgGaS₂ is complex, and PL exhibited large number of lines compared with that in CuGaS₂. The differences in PL spectra between this two compounds are related to the crystal field at the cation site and the local atomic arrangement of the RE impurities. This work also refers to the PL band at 2.28 eV observed for the Eu-doped AgGaS₂ crystal.     

Nonlinear blue upconversion luminescence in Gd2O3: Er3+/Yb3+ nanowires

Gd₂O₃: Er³⁺/Y b³⁺ nanowires were prepared by a hydrothermal method. The upconversion luminescence was studied with 978-nm excitation. Ultraviolet and blue upconversion luminescence in which thermalization processes were involved, green and red upconversion luminescence were observed respectively. We analyzed the mechanism of upconversion luminescence. According to the ratio of ² H_11/2–⁴I_15/2 emission intensity to ⁴ S_3/2–⁴I_15/2 emission intensity, the temperature of the sample exposed to radiation of 978-nm laser was given.     

Up-conversion and population of excited erbium levels in LiY1−x ErxF4 (x=0.003–1) crystals under CW InGaAs laser-diode pumping

Formation of the inverse population of working levels of 3-μm laser transition in LiY_1−x Er_xF₄ (x=0.003–1) crystals under CW InGaAs laser-diode pumping (0.967–0.982 μm) was investigated. Dependences of population of the ⁴ I _11/2 and ⁴ I _13/2 levels on the dopant concentration and pump power were studied theoretically and experimentally. Relative changes in populations of the studied levels were experimentally monitored by measuring the steady-state spectra of IR crystal luminescence in the wavelength range corresponding to ⁴ I _11/2→⁴ I _13/2 (2.7–2.8 μm), ⁴ I _11/2→⁴ I _15/2 (0.96–1.04 μm), and ⁴ I _13/2→⁴ I _15/2 (1.45–1.65 μm) transitions. Theoretical and experimental estimates of the rates of intracenter and intercenter relaxation processes (migration, self-quenching, and up-conversion) with allowance for statistics of coupling of impurity centers in the system were used to determine the energy-transfer mechanisms, elucidate the predominant mechanisms, and obtain microparameters and concentration dependences of the energy-transfer rates and nonlinear coupling. Dependences of the steady-state population of the levels of laser transition ⁴ I _11/2→⁴ I _13/2 on the dopant concentration and pumping power density were calculated within the context of rate balance equations for the scheme with the five lowest excited states of erbium. Good agreement between theory and experiment was obtained. __________ Translated from Optika i Spektroskopiya, Vol. 92, No. 1, 2002, pp. 73–88. Original Russian Text Copyright ? 2002 by Tkachuk, Razumova, Mirzaeva, Malyshev, Gapontsev.     

Usability of tartaric acid in dose measurements: an ESR study

Unirradiated tartaric acid samples do not exhibit any ESR signal. However, the ESR spectra of irradiated samples contain many resonance signals. The dose–responce curves of the resonance signals, denoted as I ₁, I ₂, I ₃ and I ₄ in the present study, were found to increase linearly with the applied radiation dose in the range of 0.04–25 kGy. Adjusting the microvawe power and modulation amplitudes of 1.0 mW and 1.0 mT, respectively, was found to increase the sensitivity of tartaric acid. From the dose–response curves and room temperature decay data, it was concluded that the I ₃ resonance signal of tartaric acid can be used for dose measurements at intermediate (0.04–0.4 kGy) and high dose (0.5–25 kGy) levels.     

Single-electron tunneling in granular Ag–SiO2films

Current transport properties of thin Ag–SiO₂granular films were studied. In spite of very simple device structures (i.e., just sandwiching the granular film with Al electrodes), clear Coulomb blockade and Coulomb staircase structures were observed in the current–voltage (I–V) characteristics. The observedI–Vcharacteristics were qualitatively explained by a double-barrier and a triple-barrier tunnel-junction model.     

Upconversion emission in CaTiO3:Er3+ nanocrystals

CaTiO₃:Er³⁺ (5%) nanocrystals were obtained by sol–gel method under acidic conditions. The sizes of nanocrystals were 40 nm. Strong green anti-Stokes emission was observed after excitation of the ⁴I_9/2 and ⁴I_11/2 level. The emission is due to excited state absorption (ESA) and energy transfer upconversion (ETU).     

Infrared and Raman spectra and vibrational assignments of diiodomethane and its deuterated analogs

The infrared (from 4000 to 100 cm^?1) and Raman spectra of CH₂I₂ and CD₂I₂ have been recorded in the liquid and gaseous phases. Assignments have been made for all observed bands and, in the case of CH₂I₂, compared with those previously reported. Some bands appearing in the CD₂I₂ spectrum have been attributed to the presence of CHDI₂. The wavenumbers of the fundamental bands of CHDI₂ have been calculated from those of CH₂I₂ and CD₂I₂ using Brodersen and Langseth's rule, and compared with those observed in the CD₂I₂ spectrum.     

Spectroscopic and Conductive Properties of Some Charge Transfer Complexes of Iodine

Abstract

The interaction of iodine with donor bases such as neutral red (NR) and 1, 10 -phenanthroline (Ph) have been studied spectrophotometrically in C₂H₅OH. The results indicate the formation of 2:3 charge transfer complexes of the type (base)₂3I₂. Mass, Raman and ¹H NMR spectra have been recorded for each complex. I₃ ^? and I₂ species are observed in these complexes. In addition, the d.c. conductivity is measured in the range (300–400) K°. The energy gap of the ionic conduction has been calculated. The conduction process is thought to involve iodide transfer between polyanions.     

Comparative study of the spectroscopic properties of Yb3+/Er3+ codoped tellurite glasses modified with R2O (R=Li,Na and K)

Spectroscopic characterization of Yb³⁺/Er³⁺ codoped TeO₂–R₂O–ZnO–Ln₂O₃ glasses as a function of network modifiers (R=Li, Na and K) has been investigated. The Judd–Ofelt parameters (Ω_t), quantum efficiency in near infrared (1.55 μm) and visible up-conversion (546 and 660 nm) and quality factor spectroscopy (χ) were calculated. Three up-conversion emission bands centered at 525, 546 and 660 nm were observed as maxima for glasses containing potassium. The measured lifetime of ⁴I_13/2, ⁴F_9/2 and ⁴S_3/2 from Er³⁺ and ⁴F_5/2 from Yb³⁺ levels increased when potassium (K) replaced lithium (Li) and Na. The maximum emission cross-section (ECS) for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ was calculated to be 1.02×10^?20 cm² for TeO₂–Li₂O–ZnO–Ln₂O₃ glasses. The energy transfer efficiency (ET) from Yb³⁺ to Er³⁺, (⁴F_5/2)+(⁴I_15/2)→(⁴F_7/2)+(⁴I_13/2), was calculated using the measured lifetimes of Yb³⁺ with and without the presence of acceptor (Er³⁺). The maximum calculated ET was 58% for 0.25 mol% of Er³⁺ and 3 mol% of Yb³⁺ for TeO₂–K₂O–ZnO–Ln₂O₃ glass composition.     

Enhanced infrared to visible upconversion emission in Er3+ doped phosphate glass: Role of silver nanoparticles

Phosphate glasses with compositions (59.5–x)P₂O₅–MgO–xAgCl–0.5Er₂O₃ (0.0≤x≤1.5 mol%) containing fixed concentration of Er³⁺ ion with and without silver nanoparticles (NPs) are prepared using melt quenching technique. The amorphous nature of the glass is confirmed using the X-ray diffraction method. The homogeneous distribution of spherical Ag NPs (average size ～37 nm) in the glassy matrix is evidenced from the transmission electron microscopy (TEM) analyses. The UV–vis–NIR absorption spectra shows 10 bands corresponding to ⁴I_13/2, ⁴I_11/2, ⁴I_9/2, ⁴F_9/2, ⁴S_3/2, ²H_11/2, ⁴F_7/2, ⁴F_5/2, ²G_9/2, ⁴G_11/2 transitions in which the most intense bands are ²H_11/2 and ⁴G_11/2. The absorption spectrum of Er³⁺ ions free glass sample containing Ag NPs displays a prominent surface Plasmon resonance (SPR) band located at 528 nm. The infrared to visible frequency upconversion (UC) emission under 797 nm excitation shows two emission bands green (⁴S_3/2–⁴I_15/2) and red (⁴F_9/2–⁴I_15/2) centered at 540 nm and 634 nm, respectively, corresponding to Er³⁺ transitions. An enhancement in UC emission intensity of green band (⁴S_3/2–⁴I_15/2) is observed in the presence of silver NPs and the maximum enhancement occurred for 1.5 mol% AgCl. However, the enhancement of emission intensity of the red band (⁴F_9/2–⁴I_15/2) is smaller. The enhancement of UC emission is understood in terms of the intensified local field effect due to silver NPs.     

Raman scattering of Zn doped CuGaS2 layers grown by vapor phase epitaxy

Raman spectra for non-site-selectively and site-selectively Zn-doped CuGaS₂ layers grown by vapor phase epitaxy (VPE) were investigated. Although an appearance of characteristic Raman line(s) related with the doped Zn atom was not seen, an enhancement of the Raman intensity ratio of the highest LO mode to the A₁ mode (I_LO/I_A1) was observed. The site-selectively Zn-doped layers with p-type conductivity exhibited larger I_LO/I_A1 ratio compared to those with n-type conductivity. The observed correlation between the I_LO/I_A1 ratio and the peak energy of the photoluminescence characteristic for Zn-doped p-type samples (L emission) suggests that the enhancement of I_LO/I_A1 is due to the increase of Zn atom substituting Ga site (Zn_Ga) which is acting as an acceptor.     

Current controlled negative differential resistance behavior in Co2FeO2BO3 and Fe3O2BO3 single crystals

I–V curves showing negative differential resistance (NDR) are reported for single crystals of Co₂FeO₂BO₃ at 315 K and 290 K and for Fe₃O₂BO₃ at 300 K, 260 K and 220 K. Resistivity measurements are presented for both systems, parallel and perpendicular to the c axis, in the range 315–120 K. The high hysteretic behavior of the I–V curves in Co₂FeO₂BO₃ around room temperature is discussed and the heat dissipated is estimated, suggesting an increase in the sample temperature of almost 22 K for the I–V curve at 315 K and a dominant contribution of Joule self-heating for the observed NDR. In contrast, insignificant hysteresis is observed on the I–V curves of Fe₃O₂BO₃ around room temperature. The depinning of charge order domains is suggested as the main contribution to the NDR phenomenon for Fe₃O₂BO₃. The high reproducibility of the NDR in the Fe₃O₂BO₃ single crystal allows its use as a low frequency oscillator, as it is demonstrated.     

Optical Analysis of Er3+:Boro-Fluoro-Phosphate Glasses

This paper deals with the preparation and optical analysis of Er³⁺ (0.2 mol%) boro-fluoro-phosphate glasses in the following glass compositions:

• Series A: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 AlF₃

• Series B: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 LiF

Measured Vis-NIR absorption spectra of Er³⁺:boro-fluoro-phosphate glasses have revealed nine absorption bands at 377 nm, 405 nm, 450 nm, 486 nm, 519 nm, 543 nm, 649 nm, 973 nm and 1529 nm, which correspond with the transitions of ⁴I_15/2 → ⁴G_11/2, (²G_9/2,⁴H_9/2), ⁴F_5/2, ⁴F_7/2, ²H_11/2, ⁴S_3/2, ⁴F_9/2, ⁴I_11/2, and ⁴I_13/2, respectively. With an excitation at λ _exci = 375 nm, a bright green emission (⁴S_3/2 → ⁴I_15/2) at 547 nm has been observed from these erbium glasses. Judd–Ofelt characteristic intensity Ω_λ (λ = 2, 4, 6) parameters are obtained from the absorption spectra, and these results were used to compute the radiative properties of Er³⁺:boro-fluoro-phosphate glasses. The NIR emission (⁴I_13/2 → ⁴I_15/2) at 1547 nm from these glasses was measured with an Ar⁺ laser (514.5 nm) as an excitation source.     

Polarized spectral analysis of Er3+ ions in biaxial Bi2(MoO4)3 crystal

An Er³⁺:Bi₂(MoO₄)₃ single crystal has been grown by the Czochralski technique. The Stark sublevels of the ⁴I_15/2 and ⁴I_13/2 multiplets of Er³⁺ ions in the crystal were determined. The polarized absorption spectra, polarized fluorescence spectra, and fluorescence decay curve of the crystal were measured at room temperature and the relevant spectroscopic parameters, including the Judd–Ofelt intensity parameters, spontaneous emission probability, fluorescence branching ratio, radiative lifetime, and stimulated emission cross section, were estimated. The effect of re-absorption on the spectroscopic parameters was discussed. When the crystal was excited at 977 nm, up-conversion green fluorescence was observed and discussed.     

Photoluminescence of Er-doped Si-SiO2 and Al–Si-SiO2 sputtered thin films

Er-doped Si-SiO₂ and Al–Si-SiO₂ films have been deposited by rf-sputtering being annealed afterwards. Annealing behavior of the Er³⁺: ⁴I_13/2→⁴I_15/2 emission of Er-doped Si-SiO₂ yields a maximum intensity for annealing at 700–800 °C. ⁴I_13/2→⁴I_15/2 peak emission for Er-doped Al–Si-SiO₂ at 1525 nm is shifted from that for Er-doped Si-SiO₂ at 1530 nm and the bandwidth increases from 29 to 42 nm. ⁴I_13/2→⁴I_15/2 emission decays present a fast decaying component related to Er ions coupled to Si nanoparticles, defects, or other ions, and a slow decaying component related to isolated Er ions. Excitation wavelength dependence and excitation power dependence for the ⁴I_13/2→⁴I_15/2 emission correspond with energy transfer from Si nanoparticles. Populating of the ⁴I_11/2 level in Er-doped Si-SiO₂ involves branching and energy transfer upconversion involving two or more Er ions. Addition of Al reduces the populating of this level to an energy transfer upconversion involving two ions.     

Behavior of mixtures of iodine with anthracene,phenazine and thianthrene

The binary systems I₂-phenazine (I₂P), I₂-anthracene and I₂-thianthrene have been investigated over a wide range of concentrations (0.1 < x_I2 < 1) and over temperatures ranging from 0 to 60°C. EMF measurements were performed in the three systems employing galvanic cells with a silver-ion-conducting solid electrolyte in order to determine the possible compounds and their formation Gibbs energies. Only one compound of stoichiometry I₂P is present in the system I₂phenazine and its formation Gibbs energy can be expressed as follows: Δ_FG⁰(I₂P) = ?20830 + 19.7 T(J mol^?1), 273–333 K. Neither the anthracene nor the thianthrene form compounds or solid solutions in the studied ranges of concentrations and temperatures.