Multi-bubble sonoluminescence of phosphoric acid

Multi-bubble sonoluminescence spectra of 85% H₃PO₄ and the dependences of sonoluminescence intensity on the acid concentration and temperature are obtained. The spectra contain a weakly structured 300–600-nm band formed by the superposition of radiation from several emitters (presumably, oxygencontaining products of acid sonolysis, viz., PO, HOPO, and PO₂). Weak luminescence at a wavelength exceeding 600 nm can be due to emission from excited O* and Ar* atoms. The shape of the fundamental band changes upon a transition from multi-bubble sonolysis to sonolysis in the setup for one-bubble sonoluminescence, in which several clusters of cavitation bubbles are formed in a spherical flask at ultrasonic frequencies multiple of the first acoustic resonance frequency (multi-cluster sonoluminescence). The form of the temperature dependence of the sonoluminescence intensity depends on the detection regime: for natural heating of 85% acid under the action of ultrasound, a curve with a luminescence peak at 40°C is observed, while in detection with preliminary thermostating “over points,” only an inflection exists on a monotonic curve describing a decrease of intensity upon heating. An analogous curve for acids with a lower viscosity (hydrochloric and nitric acids) has neither a peak nor inflection irrespective of the detection regime. It is concluded that the viscosity of phosphoric acid plays a decisive role in the evolution of cavitation and in obtaining intense sonoluminescence.     

The charge states’ conversion of the activator ions in CaF2:Eu nanophosphors

According to stationary X-ray-excited luminescence spectra and thermally stimulated luminescence spectra of CaF₂:Eu nanophosphors, it was found that Eu³⁺?→?Eu²⁺ conversion can occur during thermal annealing of fine-grained (d?=?25?nm) nanoparticles in the 200–800°C range, which is accompanied by an increase in their size within 40–189?nm. An important role of the exciton mechanism of Eu²⁺ luminescence excitation was revealed according to the temperature dependence of X-ray-excited luminescence spectra of CaF₂:Eu nanoparticles of 114?nm size. The maximum of the X-ray-excited luminescence light output of CaF₂:Eu nanophosphors in the Eu²⁺ ions’ emission band was traced out at 400–500°C annealing temperature and at the size of nanoparticles of 114–180?nm. The subsequent growth of the annealing temperatures, particularly in the 800–1000°C range, causes the reduction of X-ray-excited luminescence light output because of the increment of lattice defects’ concentration due to a sharp increase in the size of nanoparticles and their agglomeration.     

Anomalous isotopic effect in multibubble sonoluminescence of aqueous solutions of terbium chloride

An anomalously low isotope effect has been discovered in 20-kHz sonoluminescence of terbium chloride solutions in H₂O-D₂O mixtures. The intensity of luminescence in the characteristic 488-and 545-nm lines of the Tb³⁺ ion, which are observed against the solvent continuum (230–700 nm), increases with the content of D₂O to a maximum value of 4.0 ± 0.4, whereas the isotope effect in photoluminescence of the same solutions reaches 10 ± 1.0. The result is explained using the model of nonexponential decay of sonoluminescence of Tb³⁺ ions. These ions, which are formed in an excited state in cavitation bubbles, first undergo radiative and radiationless deactivation in the gas phase. However, some excited ions enter the solution bulk, because the excitation lifetime is longer than the average bubble lifetime. At the first stage, the isotope effect is small, because the density of the gas phase is low and quenching by solvent molecules is weak. At the second stage, the isotope effect coincides with the effect in usual photoluminescence in the solution. The total decrease in the effect in sonoluminescence depends on the weight of the “gas” stage of deactivation of excited Tb³⁺ ions.     

Luminescence of Tb3+ and Gd3+ ions in sonolysis under the conditions of a single bubble moving in aqueous solutions of TbCl3 and GdCl3

Luminescence bands of Tb³⁺ and Gd³⁺ ions are detected during sonolysis in the regime of a moving single bubble in aqueous solutions of TbCl₃ and GdCl₃ salts with concentration 1–2 mol/L. Saturation with argon, low temperatures of solutions (?5°C), and a high concentration of salts are the factors facilitating sonoluminescence of the metal. Comparison with the characteristics of sonoluminescence of lanthanide ions studied earlier in the regimes of multibubble and single-bubble sonolysis with a stationary bubble shows that the electron excitation of metal ions in the given case is associated with translational displacements of the bubble. Our results confirm the validity of the sonochemical model of microdroplet injection, which explains the penetration of nonvolatile salts into cavitation bubbles as a result of their deformation during intense movements.     

Charge states of the activator and size effects in BaF2: Eu nanophosphors

ABSTRACT

According to the spectra of stationary X-ray excited luminescence (XEL) of BaF₂: Eu nanophosphors at 80 and 294 K, it was revealed that the thermal annealing of fine-grained nanoparticles (d?=?35?nm) in the range of 400–1000°C, which is accompanied by an increase of their sizes in the range of 58–120?nm, does not result in effective changes of the charge state of Eu^{3 +} → Eu^{2 +} activator, in contrast to CaF₂: Eu nanoparticles. The maximum light output of X-ray excited luminescence of BaF₂: Eu nanophosphors in the 590?nm emission band of Eu³⁺ ion was observed at an annealing temperature of 600°C with the average size of nanoparticles 67?nm. The subsequent growth of annealing temperatures, especially in the range of 800–1000°C, causes decrease in the light output of X-ray excited luminescence due to the increase of defect concentration in the lattice as a result of sharp increase of nanoparticle sizes and their agglomeration. In BaF₂: Eu nanoparticles of 58?nm size, according to the thermostimulated luminescence (TSL) spectrum, transformation of Eu³⁺ → Eu²⁺ under the influence of long-time X-ray irradiation was revealed for the peak of 151?K. Thus, X-ray excited luminescence spectra of BaF₂: Eu nanophosphors are formed predominantly due to the emission of Eu³⁺ ions, while emission of Eu²⁺ ions is observed in the TSL spectra.     

Zum Lumineszenzmodell manganaktivierter Titanate

The emission spectra and the temperature dependence of the relative intensity of luminescence of three manganese activated titanate phosphors [Zn₂TiO₄, (Mg, Zn)₂TiO₄, Mg₂TiO₄] after optical excitation with radiation from 300–500 nm were measured for various temperatures above 4,2 °K. The luminescence of the Mn⁴⁺-centre is influenced by the cations (Mg²⁺ or Zn²⁺) of the lattice. The temperature dependence of the relative intensity of the luminescence depends on the excitation wavelength. The results are discussed and found to be in good agreement with those of aC-C-model which assumes two energy parabolas for the excited state.     

Porous SiO2 nanoparticles containing ruthenium or sulfur compounds: Sonochemical producing and sonoluminescence in aqueous suspensions

Aqueous suspensions of silicon dioxide porous nanoparticles (average size 10–30 nm, average pore size 5.8 nm) were obtained via ultrasonic dispersing. As was shown through recording SiO molecular lines in a moving single-bubble sonoluminescence spectrum, these nanoparticles penetrate into the bubble and then undergo decay. Similarly, suspensions of SiO₂ nanoparticles, the pores of which were saturated with ruthenium dodecacarbonyl or elemental sulfur, were obtained by impregnation of the initial powder with solutions of these reagents in chloroform followed by evaporation of the solvent. Single-bubble sonoluminescence spectra of these suspensions contain more intense lines of Ru or S and Sⁿ⁺ as compared with the SiO lines. This also proves the involvement of water insoluble ruthenium and sulfur compounds into bubble sonoluminescent reactions in the heterogenic aqueous medium. Using the method of comparing the experimentally obtained and computer simulated luminescent spectra, we determined the effective electronic temperature T_e^Ru, which was 9000 ± 500 K, in non-equilibrium plasma of a bubble levitating in the ultrasonic field.     

The kinetics of donor-acceptor pair transitions with strong phonon coupling in GaP

Donor-acceptor pair luminescence in GaP was studied by time-resolved spectroscopy, by measuring and analysing the integral band decay over many decades of intensity and time and by measuring and analysing the temperature dependence of the luminescence intensity. We report here the results obtained with some or all of these techniques for pairs involving deep as well as shallow centres. Those with a deep centre are: S_P-Si_P and Si_Ga-Si_P, in which the acceptor is the deep centre, and O_P-C_P and O_P-Zn_Ga, in which the donor is the deep centre. These pairs all have a broad, phonon-dominated luminescence band. The pairs involving shallow centres include Si_Ga-C_P, S_P-C_P and Te_P-C_P. Due to the different way of momentum conservation in these pairs, those involving a donor on a Ga-site have strong phonon co-operation and weak zero-phonon (ZP) transitions, whereas those with a donor on a P-site have strong ZP transitions.With time-resolved spectroscopy, well-resolved structure, due to a ZP pair band and its phonon replicas, is obtained for nearly all pairs. A comparison is made with the structure obtained by measuring in the stationary state at very low excitation densities. Some trends in the strength of phonon co-operation are noted. In the case of Si_Ga-C_P pairs, sharp replicas of ZP pair lines with a momentum-conserving phonon are also resolved.Using the integral band decay technique and results from time-resolved spectroscopy we have determined the transition probabilities for the total luminescence band as well as for the ZP band for nearly all pairs mentioned. The influence of incomplete saturation of the pairs during excitation with a focussed beam of an argon-ion laser is discussed and approximately corrected for. Extrapolated to zero pair separation, the total transition probability ranges from ∽ 10⁵s^-1 for Si_Ga-C_P pairs to ∽ 15 × 10⁵s^-1 for O_P-C_P and O_P-Zn_Ga pairs. The ZP probability ranges from ∽ 4 × 10³s^-1 for Si_Ga-C_P and Si_Ga-Si_P pairs to ∽ 4 × 10⁵s^-1 for S_P-C_P pairs. The transition probability for pairs in GaP is discussed in relation to the site occupied by the donor and the depth of the centres involved. The relatively high dope concentrations used in some cases, ∽ 1 to 2 × 10¹⁸cm^-3, are discussed briefly in relation to “concentration quenching”.The temperature dependence of the luminescence intensity of S_P-Si_P pairs is satisfactorily analysed with a simple linear model. The same model is applied to similar literature data on the S_P-C_P pair luminescence. Using in addition data on the average pair transition probability, trapping rate constants for hole capture by the Si_P and C_P acceptors were calculated to be ∽ 10^-9 cm³s^-1. Evidence is presented that the trapping rate constant for holes by the Zn_Ga-O_P complex is about 2 × 10^-9 cm³s^-1.     

Intensity and half-width measurements in the 1·525 μm band of acetylene

Line intensities at 150°K and 295°K, self-broadened half-widths at 171°K, 200°K, 250°K and 295°K, and hydrogen-broadened half-widths at 171°K, 200°K and 295°K have been measured in the ν₁+v₃ band of C₂H₂ at 1·525 μm. The absolute intensity of the band has been determined independently by employing the Wilson-Wells-Penner-Weber technique. Our best estimate for the absolute intensity of the band is S_v=7·82 ± 0·07 cm^?2 atm^?1 at 295°K. Line intensities calculated using this value of S_v are in good agreement with the measured intensities at the two extreme temperatures of 150°K and 295°K considered in the present study, thereby not suggesting any significant intensity anomalies. Line positions have been measured for the first time for this band for R(29)?P(25).     

Measurement of intensities of multiplets in the 2ν3-band of methane at low temperatures

The integrated intensities of the multiplets P(1)–P(10), R(0)–R(9), and of the Q-branch in the 2ν₃-band of ¹²CH₄ have been measured at 102°K, 152°K, 202°K, 251°K, and 300°K. Comparison of our data with theoretical line strengths confirms, at all of the temperatures mentioned, the intensity anomalies observed by Margolis⁽⁵⁾ for lines in this band. The integrated intensity of the 2ν₃-band is found to be S_v = (1·76±-0·04)(300/T (°K)) cm^?2 atm^?1.     

有机溶液中圆锥泡声致发光

在U形管声致发光装置的基础上建立了一套新型的声致发光装置——直管圆锥泡声致发光装置. 利用此装置以有机溶液为液体介质得到了超强的发光脉冲并测量得到了其发光光谱. 结果表明发光光谱为一从紫外光至可见光波长范围的连续谱,上面叠加有C₂的d³Π_g→d³Π_u跃迁形成的五个序列谱带,分别对应于Δv=-2,Δv=-1,Δv=0,Δv< 关键词： 声致发光 光谱 斯旺带 振动温度     

Etude par correlation angulaire γ-γ perturbee des aspects statiques et dynamiques de la structure du heptafluorohafniate de sodium

We have studied the temperature dependence of the perturbation of the differential γ-γ angular correlation of the ¹⁸¹Ta 133–482 keV cascade in sodium heptafluorohafnate. In the 20–300°C temperature region, we observed a drastic variation of the quadrupole interaction parameters when raising the temperature from 100 to 180°C. Such a variation is due to the existence of a phase transition corresponding to an orthorhombic-quadratic transformation of the lattice. In the low temperature phase (T < 120°C) the perturbation is static and the nuclear probe is located at two equally populated sites. In the high temperature phase (T > 180°C) the perturbation arises from the combination of static and dynamic interactions. The dynamic part of the interaction could be analysed within the isotropic perturbation model and was ascribed to jumps of the fluorine atoms onto the vertices of the cubic coordination polyhedra of the hafnium in the HfF₇^3? ion. The activation energy of the process is 0.13 ±0.03 eV. The idea of an order-disorder phenomena occuring in the course of the phase transition is consistently supported by these observations. Our results yield also valuable informations about the nature of the hafnium-fluor bond in this compound.     

Nitrogen implantation in GaAs1−xPx (x=0.4; 0.65)

Nitrogen ions were implanted in GaAs_1−xP_x (x=0.4; 0.65) at room temperature at various doses from 5×10¹² cm⁻² to 5×10¹⁵ cm⁻² and annealed at temperatures from 600°C up to 950°C using a sputtered SiO₂ encapsulation to investigate the possibility of creating isoelectronic traps by ion implantation. Photoluminescence and channeling measurements were performed to characterize implanted layers. The effects of damage induced by optically inactive neon ion implantation on photoluminescence spectrum were also investigated. By channeling measurements it was found that damage induced by nitrogen implantation is removed by annealing at 800°C. A nitrogen induced emission intensity comparable to the intensity of band gap emission for unimplanted material was observed for implanted GaAs_0.6P_0.4 after annealing at 850°C, while an enhancement of the emission intensity by a factor of 180 as compared with an unimplanted material was observed for implanted GaAs_0.35P_0.65 after annealing at 950°C. An anomalous diffusion of nitrogen atoms was found for implanted GaAs_0.6P_0.4 after annealing at and above 900°C.     

Preparation and luminescence properties of Eu2+-doped BaSi2O5 glass-ceramics

We report on the preparation of Eu²⁺-doped BaSi₂O₅ glass-ceramics by crystallizing an Eu³⁺-doped barium-silicate glass at temperatures in the range from 750 to 1100 °C. Single phase BaSi₂O₅ glass ceramics can be obtained by thermal annealing at temperatures of about 950 °C. The luminescence intensity of Eu²⁺ increases dramatically if monoclinic BaSi₂O₅ is formed. Monoclinic Eu²⁺:BaSi₂O₅ shows efficient, broad band luminescence between 450 and 550 nm by excitation in the near UV. Annealing at temperatures >1000 °C leads to orthorhombic BaSi₂O₅ with much smaller Eu²⁺ luminescence. Static and time-resolved luminescence measurements indicate that Eu²⁺ ions are incorporated into the BaSi₂O₅ crystallites while Eu³⁺ ions remain in the amorphous phase.     

Model for the blue photoluminescence of cadmium sulfide

A model for the blue luminescence of polycrystalline cadmium sulfide and cadmium sulfide single crystals is proposed on the basis of a joint study of the absorption, reflection, emission, and excitation spectra of this luminescence at 77 °K. The blue luminescence arises in the transition of an electron from the conduction band to the 5s^{2 1}S₀ ground level of a super-stoichiometric cadmium atom which has trapped a hole from the valence band. The width of the energy gap (2.614 eV) at κ = 0 is estimated on the basis of the oscillatory nature of the excitation spectrum for the blue luminescence, and the effective mass of heavy holes is estimated.     

Influence of nitrogen implantation on thermoluminescence of synthetic quartz

Thermoluminescence (TL) of synthetic quartz exposed to beta irradiation following implantation with 60?keV N⁺ ions at fluences ranging between 1?×?10¹⁴ and 5?×?10¹⁵?ions/cm² is reported. The glow curve measured at 5°C/s typically consists of a prominent peak near 110°C, studied in this work, and minor glow peaks at around 130°C and 190°C. The TL intensity of the main peak increased both with implantation and with fluence of implantation. The dependence of the intensity on heating rate and fluence suggests that the implantation introduces new defects that may possibly act as recombination centres. The increase in TL intensity with the heating rate exhibited by implanted samples has been observed in other luminescence materials. This anti-quenching phenomenon has been described as a competition effect between multiple luminescence pathways in luminescence materials. Kinetic analysis of the main glow peak using the initial rise, various heating rate and glow curve deconvolution methods shows that the activation energy of the main peak is about 0.7?eV with no systematic change due to ion fluence.     

Calculation of absorption coefficient for the ν1 band of sulfur dioxide

The absorption coefficients S/d of sulfur dioxide have been calculated for the ν₁ band for temperatures from 300 ～ 1500°K, taking the major isotopic species S³⁴O₂ into consideration. The total number of the vibrational transitions considered were 4, 10, 23, 41 and 70 for the temperatures of 300, 600, 900, 1200 and 1500°K, respectively. The vibrational energy was calculated to the second order, and the rotational energy and matrix element were calculated exactly with consideration for the asymmetry of the sulfur dioxide molecule. The line intensities greater than 1·0 × 10^-8 cm^-2 atm^-1 STP were included in the calculations. The wavenumber regions of 1000 ～ 1300 cm^-1 were divided into small intervals of Δω = 10 cm^-1 and the S/d averaged over the Δω were obtained. The S/d and some of the line intensities and positions at 300°K were compared with the experimental results of other workers and good agreement was obtained.     

Luminescence enhancement by the reduction–oxidation synthesis in monoclinic RE2O3 (RE=Eu,Gd) phosphors containing Eu3+ activator

A novel synthesis was developed for enhanced luminescence in sesquioxide phosphors containing Eu³⁺ activator. It consisted of two annealing steps: reduction under vacuum with gaseous H₂ at 10 Torr and 1300 °C and re-oxidation at 300–1500 °C in air. The integrated luminescence intensity of the monoclinic Eu₂O₃ phosphor was enhanced ca. 21 times by this method compared with conventional processing. The photoluminescence (PL) intensity was maximized at re-oxidation temperatures of 500–1100 °C. The PL characteristics of monoclinic Eu₂O₃ and Gd₂O₃:0.06Eu samples were compared with a commercial cubic Y₂O₃:Eu phosphor. The evolution of physical characteristics during the two-step annealing was studied by Raman spectroscopy, XPS, XRD, PL decay analysis, and SEM. PL decay lifetime increased proportionally to the PL intensity over the range 0.5–100 μs. Additional vibrational modes appeared at 490, 497, and 512 cm^?1 after the two-step annealing. The increase in PL intensity was ascribed to the formation of excess oxygen vacancies and their redistribution during annealing. Resonance crossovers between the charge transfer state and the emitting ⁵D_J states are discussed in relation to reported luminescence saturation mechanisms for oxysulfides Ln₂O₂S:Eu³⁺ (Ln=Y, La).     

Photoluminescence of sodium-implanted zinc selenide

Luminescence measurements indicate that Na acceptors implanted into ZnSe become optically active after annealing at 500°C. The spectra show a strong Na dependence for both the R series band and the I^Y₁ exciton line. In this work Ne-implanted and unimplanted samples were annealed and measured with the Na-implanted material to isolate defect-induced spectral features. Several new bands resulting from radiation damage are reported, along with annealing properties of the defect bands and Na-related luminescence.     

Investigation of the temperature dependence for the spectra of supercooled water in the middle infrared

The temperature dependence of the bending ν₂, combination ν₂ + ν _L , and stretching (ν₁, ν₃, 2ν₂) absorption bands in the infrared spectra of supercooled water with a temperature-change step Δt from 2 to 2.5°C was studied using an advanced infrared Fourier spectrometer. It was found that the frequency of the maximum of the stretching absorption band (2700–3700 cm^?1) decreases with the reduction of the water temperature from ?0.5 to ?5.0°C. The frequency of the maximum of the combination absorption band (2130 cm^?1) increases with the reduction of the water temperature in a range from ?3.0 to ?5.0°C. The frequency of the maximum of the absorption band of bending oscillation (1640 cm^?1) is invariable with a reduction of the water temperature from ?0.5 to ?5.0°C.