Study of defect evolution by TEM with in situ ion irradiation and coordinated modeling

The paper describes a novel transmission electron microscopy (TEM) experiment with in situ ion irradiation designed to improve and validate a computer model. TEM thin foils of molybdenum were irradiated in situ by 1?MeV Kr ions up to ～0.045 displacements per atom (dpa) at 80°C at three dose rates ?5?×?10^?6, 5?×?10^?5, and 5?×?10^?4?dpa/s – at the Argonne IVEM-Tandem Facility. The low-dose experiments produced visible defect structure in dislocation loops, allowing accurate, quantitative measurements of defect number density and size distribution. Weak beam dark-field plane-view images were used to obtain defect density and size distribution as functions of foil thickness, dose, and dose rate. Diffraction contrast electron tomography was performed to image defect clusters through the foil thickness and measure their depth distribution. A spatially dependent cluster dynamic model was developed explicitly to model the damage by 1?MeV Kr ion irradiation in an Mo thin foil with temporal and spatial dependence of defect distribution. The set of quantitative data of visible defects was used to improve and validate the computer model. It was shown that the thin foil thickness is an important variable in determining the defect distribution. This additional spatial dimension allowed direct comparison between the model and experiments of defect structures. The defect loss to the surfaces in an irradiated thin foil was modeled successfully. TEM with in situ ion irradiation of Mo thin foils was also explicitly designed to compare with neutron irradiation data of the identical material that will be used to validate the model developed for thin foils.     

Effects of damage rate on Cu precipitation in Fe–Cu model alloys under neutron irradiation

The formation of Cu precipitates and point defect clusters was investigated in two Fe–Cu binary model alloys, Fe–0.3Cu and Fe–0.6Cu, irradiated at 573?K at three different damage rates, namely 3.8?×?10^?10, 1.5?×?10^?8 and 5?×?10^?8?dpa (displacements per atom)/s, up to about 1.6?×?10^?2?dpa. Results of positron annihilation experiments indicated that Cu precipitates were formed in these irradiations with different damage rates. The growth of Cu precipitates does not increase monotonously with increasing irradiation dose, but it rather depends on the nucleation and growth of microvoids. It is also clear that the nucleation and growth of microvoids are influenced by the irradiation dose rate.     

High density excitation effects on fluorescence from the crystals of aromatic hydrocarbons and charge-transfer complexes

High density excitation effects on fluorescence were studied for the crystals of fluoranthene, chrysene, benzo[g, h, i]perylene, pyrene and pyrene-d₁₀ and also for the crystal of 1,2,4,5-tetracyanobenzene (TCNB)-hexamethylbenzene (HMB) complex. Relative fluorescence intensity in the shorter wavelength region decreased with increasing excitation density (for chrysene, fluoranthene, and benzo[g, h, i]perylene), and the vibrational structure became diffuse at high density excitation (for fluoranthene and chrysene). The rate constants of the bimolecular quenching and exciton migration were obtained by analysis of the fluorescence decay curves at high density excitation for chrysene, pyrene, pyrene-d₁₀, and TCNB-HMB. The exciton hopping rates at 295 K were 2.4 × 10¹⁰ s^?1 in chrysene and 7.9 × 10⁸s^?1 in TCNB-HMB. The differences in the rate between chrysene and fluoranthene (2.2 × 10⁹s^?1) and between TCNB-HMB and TCNB-durene (4.2 × 10⁹s^?1) are discussed in terms of the coupling intensity between two neighboring oscillators accompanying the transition between ground and the lowest excited singlet state. The difference in the rate and activation energy of exciton migration between pyrene and pyrene-d₁₀ corresponded to a quasilocalized exciton model.     

The lowest metal-to-bipyridine charge-transfer excited state of [Cr(2,2′-bipyridine)(CO)4]

The DV-Xα molecular-orbital calculations have been carried out on [Crbpy(CO)₄](bpy,2,2′-bipyridine) and its electron attachment and detachment products. The one-electron attachment of [Crbpy(CO)₄] yields a complex of bipyridine anion radical, while the one-electron detachment results in ionization of the central metal atom. The lowest excited state of [Crbpy(CO)₄] is the metal-to-ligand charge-transfer (MLCT) excited state which consists of the bipyridine anion radical and the central metal ionized. The transition-state calculation predicts the lowest MLCT excited states at around 23～30×10³ cm^?1 and the lowest bipyridine (π,π^*) excitations at 36×10³ cm^?1 and 42～45×10³ cm^?1. The calculation also concludes that the MLCT excitation induces a counter migration of the other electrons not directly involved in the charge-transfer excitation. The configuration-interaction calculations predict the lowest MLCT excited singlet states at around 21～35×10³ cm^?1 and the lowest bipyridine (π, π^*) excited singlet states at 42～62×10³ cm^?1, while the emissive lowest MLCT triplet state is at 17×10³ cm^?1. The transition moments evaluated with the transition-state wavefunctions can reproduce qualitatively the observed absorption spectral profile. The intensity of the MLCT transitions is obtained from the allowed (π, π^*) transitions of coordinated bipyridine but is not due to the intrinsic transition moments of MLCT excitations.     

Electron impact ionisation cross sections of cis- and trans-diamminedichloridoplatinum(II) and its hydrolysis products

ABSTRACT

We report total electron-impact ionisation cross sections (EICSs) of cisplatin, its hydrolysis products and transplatin in the energy range from threshold to 10?keV using the binary-encounter-Bethe (BEB) and its relativistic variant (RBEB), and the Deutsch-Märk (DM) methods. We find reasonable agreement between all three methods, and we also note that the RBEB and the BEB methods yield very similar (almost identical) results in the considered energy range. For cisplatin, the resulting EICSs yield cross section maxima of 22.09?×?10^?20?m² at 55.4?eV for the DM method and 18.67?×?10^?20?m² at 79.2?eV for the (R)BEB method(s). The EICSs of monoaquated cisplatin yield maxima of 12.54?×?10^?20?m² at 82.8?eV for the DM method and of 9.74?×?10^?20?m² at 106?eV for the (R)BEB method(s), diaquated cisplatin yields maxima of 7.56?×?10^?20?m² at 118.5?eV for the DM method and of 5.77?×?10^?20?m² at 136?eV for the (R)BEB method(s). Molecular geometry does not affect the resulting EICS significantly, which is also reflected in very similar EICSs of the cis- and trans-isomer. Limitations of the work as well as desirable future directions in the research area are discussed.     

Table-top kHz hard X-ray source with ultrashort pulse duration for time-resolved X-ray diffraction

The interaction of ultrashort laser pulses with solid state targets is studied concerning the production of short X-ray pulses with photon energies up to about 10 keV. The influence of various parameters such as pulse energy, repetition rate of the laser system, focusing conditions, the application of prepulses, and the chirp of the laser pulses on the efficiency of this highly nonlinear process is examined. In order to increase the X-ray flux, the laser pulse energy is increased by a 2nd multipass amplifier from 750 μJ to 5 mJ. By applying up to 4 mJ of the pulse energy a X-ray flux of 4×10¹⁰ Fe K _α photons/s or 2.75×10¹⁰ Cu K _α photons/s are generated. The energy conversion efficiency is therefore calculated to η _Fe≈1.4×10⁻⁵ and η _Cu≈1.0×10⁻⁵. The X-ray source size is determined to 15×25 μm². By focusing the produced X-rays using a toroidally bent crystal a quasi-monochromatic X-ray point source with a diameter of 56 μm×70μm is produced containing ≈10⁴ Fe K _α1 photons/s which permits the investigation of lattice dynamics on a picosecond or even sub-picosecond time scale. The lattice movement of a GaAs(111) crystal is shown as a typical application.     

Thermal diffusivity of MORB-composition rocks to 15 GPa: implications for triggering of deep seismicity

We have measured the thermal diffusivity of eclogite and majorite with a model MORB composition at pressures of 3 and 15 GPa, respectively. Both phase assemblages show inverse dependences of their thermal diffusivities on temperature: D _eclogite=9(10)×10^?10+7(1)×10^?4/T(K) m ²/s and D _majorite=6.2(5)×10^?7+3.0(5)×10^?4/T(K) m ²/s. The values for majorite are in good agreement with previous measurements for other garnets and are considerably lower than thermal diffusivities of wadsleyite and ringwoodite, which are the main components of the mantle transition zone. We discuss the implications of the low thermal conductivity of subducted oceanic crust in the transition zone for the triggering of deep seismicity.     

Experimental investigations of fast-proton production in a picosecond laser plasma

Results of experimental investigations of fast-proton production in a laser plasma are presented for the case where the intensity of laser radiation at the targets is 2 × 10¹⁸ W/cm². Three processes of fast-proton acceleration in laser plasma are investigated: (1) the acceleration of protons from the front surface toward the laser pulse, (ii) the acceleration of protons from the front surface of the target toward its interior, and (iii) the acceleration of protons from the rear foil surface in the outward direction. The activation procedure and CR-39 tracker detectors featuring a set of various-thickness aluminum filters were used to record fast protons. It turned out that the proton-acceleration process is the most efficient in the case of proton acceleration from the rear foil surface in the outward direction. Experimental results revealed that about N _p = 10⁷ protons of energy in the region E _p > 1.9 MeV that are accelerated from the target surface toward a laser ray, N _p = 4× 10⁷ protons of energy in the region E _p > 1.9 MeV that are accelerated fromthe front surface of the target toward its interior, and N _p = 4×10⁸ protons of energy in the region E _p > 1.9 MeV that are accelerated from the rear foil surface in the outward direction are generated at a laser-radiation intensity of 2 × 10¹⁸ W/cm² at the surface of aluminum, copper, and titanium targets. Experimental investigations aimed at optimizing the process of proton acceleration from the rear surface of aluminum foils were performed by varying the foil thickness over the range between 1 and 100 μm. The results of these experiments showed that there is an optimum foil thickness of 10 μm, in which case protons of maximum energy 5 MeV are generated.     

Enhanced Fluorimetric Determination of Samarium with Dibenzoylmethane and Diphenylguanidine by Gadolinium

Abstract

The fluorescence of Sm-dibenzoylmethane (DBM)-diphenylguanidine (DPG) system was enhanced by about two to three orders of magnitude when it was excited in the presence of Gd in ethanol-water solution. The excitation and emission wavelegths were 390 nm and 652 nm, respectively. The fluorescence intensity was a linear function of the concentration of Sm in the range of 1.0 × 10^?9–2.0 × 10^?6 M. The fluorescence mechanism of the system is discussed.     

Performance improvement of a Kα source by a high-resolution thin-layer-graphite spectrometer and a polycapillary lens

A tabletop, short-pulse laser-based hard X-ray (Kα) source equipped with an advanced X-ray optics and dedicated for high-resolution spectroscopy and time-resolved diffraction is described. Operation of the source together with a high-resolution spectrometer containing a large-aperture highly annealed pyrolytic graphite gave a resolution E/ΔE of ~1,800 for the spectral range around Kα line of Cu. The estimated total flux of the 8.05-keV photons was equal to 5.9 × 10¹⁰ ph/s in 4π sr. Performance boost of the source caused by X-ray optics relied on the significant increase in the Cu-Kα photon flux on both, the sample (4.7 × 10⁶ ph/s) and the detector (3.4 × 10³ ph/s). A spectral brightness of 1.4 × 10⁷ ph/s/mm²/mrad² was derived from the source parameters for the Kα line. Better performance due to high collecting power and reflectivity of the spectrometer enabled application of the cross-correlation technique with an Ni foil. An upper bound of emission duration of 323 ± 47 fs was obtained in this measurement. X-ray absorption near-edge spectroscopy on an Ni sample with an acquisition time of only 15 min confirmed the increased capability of the setup also for continuous spectrum (bremsstrahlung).     

Microstructural evolution and changes in mechanical property of irradiated Fe–0.6Cu alloy under uniaxial tension stress in reactor

Structural materials for commercial reactor are usually used under conditions of stress. However, the evaluation of the microstructural evolution and the changes in the mechanical property induced by the neutron irradiation in structural materials does not typically consider the effect of stress since it is difficult to carry out neutron irradiation testing under conditions of stress. In this study, a model alloy (Fe–0.6Cu) of reactor pressure vessels was irradiated by neutrons at 573?K with a dose of about 3.2?×?10²¹?neutrons/m² (E?>?0.1?MeV), corresponding to 5.2?×?10^?4?dpa (displacement per atom), with and without tension stress. The tension stress caused elastic deformation in the specimens. The size of microvoids in the irradiated sample with tension stress was larger than that in the sample without tension stress. However, the effects of stress on the formation of Cu precipitates and the changes in the mechanical property were not clear.     

A New Candidate Laser Dye Based 1,4-Bis[β-(2-Naphthothiazolyle)Vinyl]Benzene. Spectroscopic Behavior,Laser Parameters and Excitation Energy Transfer

A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μ_g) and the excited singlet state dipole moment (μ_e) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Ф_c) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl₃, EtOH and MeOH at room temperature. The values of φ_c were calculated as 2.3?×?10^?4, 3.3?×?10^?3, 9.7?×?10^?5 and 6.2?×?10^?5 in Dioxane, CHCl₃, EtOH and MeOH, respectively. The dye solutions (2?×?10^?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σ_e) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, R_o of 40 and 32 ? and k_ET equals 2.6?×?10¹³ and 1.06?×?10¹³ M^?1 s^?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.     

A highly luminescent complexes of Eu(III) and Tb(III) with norfloxacin and gatifloxacin doped in sol–gel matrix: A comparable approach of using silica doped Tb(III) and Eu(III) as optical sensor

Highly luminescent complexes of Eu and Tb ions with norfloxacin (NFLX) and gatifloxacin (GFLX) were prepared in sol–gel matrix. The red and green emissions of Eu and Tb ions were obtained by the energy transfer from the triplet state of (NFLX) and (GFLX) to the excited emitting states (⁵D₀ and ⁵D₄) of Eu and Tb, respectively. The intensity of the electric field emission bands (⁵D₀→⁷F₂, 617 nm and ⁵D₄→⁷F₅, 545 nm) of Eu and Tb ions were proportional to the concentration of (NFLX at pH 6.0) and (GFLX at pH 3.5) in acetonitrile with excitation wavelengths (λ_ex) (340 and 395) and (370 and 350 nm) for Eu and Tb ions, respectively. The monitored luminescence intensity of the system showed a good linear relationship with the concentration of NFLX within a range of 5×10^?9–5.8×10^?6 and 5×10^?8–1.0×10^?6 mol L^?1 with a correlation coefficient of 0.990, and for GFLX within a range of 2.4×10^?9–3.2×10^?5 and 5×10^?8–8.0×10^?6 mol L^?1 with a correlation coefficient of 0.995. The detection limit (LOD) was determined as 3.0×10^?9 and 1.0×10^?8 mol L^?1 for NFLX and 1.6×10^?10 and 2.0×10^?8mol L^?1 for GFLX. The limit of quantification (LOQ) is 9×10^?9 and 3.0×10^?8 and 4.8×10^?10 and 6.0×10^?8 in case of Eu and Tb, respectively.     

The influence of the activator concentration on electroluminescence properties of thin layers in a system ZnS: Cu,Mn, Cl

The influence of activators, especially copper, on the electric properties of vacuum-evaporated electroluminescent layers excited by dc voltage is investigated. In the course of the “one step” method of preparation, non-uniform incorporation of the activators occurs. The layers are divided into three groups according to the copper concentration. 1 — “low” (1×10^?3 g Cu/g ZnS) with the emission stimulated at Al^? electrode, 2 — “medium” (5–8×10^?3 g Cu/g ZnS) with the emission at both polarities, 3 — “high” (9×10^?3?5×10^?2 g Cu/g ZnS) with the emission at Al⁺ electrode. Layers in these groups differ not only in their electrical properties and in the existence of the forming process but they have also various distribution of the light-emitting regions. The light emission has been found in the intermediate regions between the microcrystalline grains as well as on the interface between the microcrystalline grain and ZnS phosphor phase. According to structural properties the light emission originates from microcrystalline grains too.     

Two photon absorption characteristics of bulk GaTe crystal

We have investigated the structural and optical properties of bulk GaTe crystal grown by vertical Bridgman method. Two photon absorption (TPA) properties of GaTe crystal have been investigated by the open aperture Z-scan technique under 1064 nm wavelength with 4 ns or 65 ps pulse durations. The TPA coefficients are greater in ns regime than that of ps regime. Upon increasing intensity of incident light from 5.02×10⁷ W/cm² to 1.07×10⁸ W/cm², the TPA coefficients increased from 3.47×10^?6 cm/W to 8.53×10^?6 cm/W for nanosecond excitation. Similarly, when intensity of incident light was increased from 6.81×10⁸ W/cm² to 9.94×10⁸ W/cm² the TPA coefficients increased from 3.53×10^?7 cm/W to 6.83×10^?7 cm/W for picosecond excitation. Measured TPA coefficient of GaTe crystal is larger than that of GaSe and GaS layered crystals.     

Measurement of diffusion coefficients of Ag in YBa2Cu3O7 by the EDXRF technique

The diffusion of Ag in superconducting YBa₂Cu₃O₇ ceramic was studied over the temperature range 700–850 °C by the energy‐dispersive X‐ray fluorescence (EDXRF) technique. For the excitation of silver atoms, an annular Am‐241 radioisotope source (50 mCi) emitting 59.543 keV photons was used. The temperature dependences of Ag diffusion coefficients in grains (D₁) and over the grain boundaries (D₂) are described by the equations D₁ = 1.4 × 10^?2exp[?(1.18 ± 0.10)/kT] and D₂ = 3.1 × 10^?4exp[?(0.87 ± 0.10)/kT]. Copyright © 2003 John Wiley & Sons, Ltd.     

Modifications induced by swift heavy ions in rapidly solidified Sn–8.5Sb–5.5Cu alloy

Alloys of composition Sn–8.5Sb–5.5Cu (in atomic percent) were rapidly solidified by a melt-spinning technique. The samples were irradiated at room temperature with GeV uranium ions of fluences between 9×10⁸ and 9×10¹¹ ions cm^?2. X-ray diffraction analysis revealed the formation of a new-phase Cu₁₁Sb₃ as well as a reduction in the axial ratio (c/a) of the matrix (β -Sn) indicating the regular re-arrangement of atoms. Scanning force microscopy showed no surface topographic changes with the ion fluence. The mechanical properties (Young's modulus and hardness) of the irradiated alloys were studied as a function of ion fluence. The radiation-annealing process is discussed in terms of the evolution of both resistivity and hardness as a function of ion fluence.     

Cavity-enhanced optical feedback-assisted photo-acoustic spectroscopy with a 10.4 μm external cavity quantum cascade laser

An ultra-sensitive photo-acoustic spectrometer using a 10.4 μm broadly tunable mid-IR external cavity quantum cascade laser (EC-QCL) coupled with optical feedback to an optical power buildup cavity with high reflectivity mirrors was developed and tested. A laser optical power buildup factor of 181 was achieved, which corresponds to an intra-cavity power of 9.6 W at a wavelength of 10.4 μm. With a photo-acoustic resonance cell placed inside the cavity this resulted in the noise-equivalent absorption coefficient of 1.9 × 10^?10 cm^?1 Hz^?1/2, and a normalized noise-equivalent absorption of 1.1 × 10^?11 cm^?1 W Hz^?1/2. A novel photo-acoustic signal normalization technique makes the photo-acoustic spectrometer’s response immune to changes and drifts in the EC-QCL excitation power, EC-QCL to cavity coupling efficiency and cavity mirrors aging and contamination. An automatic lock of the EC-QCL to the cavity and optical feedback phase optimization permitted long wavelength scans within the entire EC-QCL spectral tuning range.     

Spectroscopic study of thulium-activated double sodium yttrium fluoride Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Tm<Superscript>3+</Superscript> crystals: I. Intensity of spectra and luminescence kinetics

Na_0.4Y_0.6F_2.2:Tm³⁺ crystals with a thulium content from 1 to 100 at % have been grown by the Stockbarger-Bridgman method. The optical spectra of Na_0.4Y_0.6F_2.2:Tm³⁺ crystals were investigated in detail at room and low (10 K) temperatures, and the luminescence kinetics was analyzed using different excitation methods. The structure of the Stark splitting of thulium levels as “quasi-centers,” characterized by inhomogeneous broadening of the Stark components, is determined from analysis of the absorption spectrum at 10 K. The oscillator strengths of the transitions from the ground state to excited multiplets are determined from the absorption cross-section spectra at 300 K for ten transitions in the range 5000–38 500 cm^?1 and seven transitions in the range 5000–28 500 cm^?1. The transition intensity parameters Ω _t , obtained by the Judd-Ofelt method from the spectra due to the transitions to ten and seven excited levels, were found to be, respectively, (i) Ω₂ = 1.89 × 10^?20, Ω₄ = 2.16 × 10^?20, and Ω₆ = 1.40 × 10^?20 cm² and (ii) Ω₂ = 2.04 × 10^?20, Ω₄ = 2.01 × 10^?20, and Ω₆ = 1.44 × 10^?20 cm². These values of the intensity parameters were used to calculate the radiative transition probabilities and branching ratios and to estimate the multiphonon nonradiative transition probabilities for NYF:Tm. The luminescence decay kinetics from thulium radiative levels upon their selective excitation by nanosecond laser pulses has been studied and the lifetimes of thulium radiative levels in NYF crystals have been found.     

First-principles study of structural,elastic, electronic and thermodynamic properties of topological insulator Bi2Se3 under pressure

The structural, elastic, electronic and thermodynamic properties of the rhombohedral topological insulator Bi₂Se₃ are investigated by the generalized gradient approximation (GGA) with the Wu–Cohen (WC) exchange-correlation functional. The calculated lattice constants agree well with the available experimental and other theoretical data. Our GGA calculations indicate that Bi₂Se₃ is a 3D topological insulator with a band gap of 0.287 eV, which are well consistent with the experimental value of 0.3 eV. The pressure dependence of the elastic constants C_ij, bulk modulus B, shear modulus G, Young’s modulus E, and Poisson’s ratio σ of Bi₂Se₃ are also obtained successfully. The bulk modulus obtained from elastic constants is 53.5 GPa, which agrees well with the experimental value of 53 GPa. We also investigate the shear sound velocity V_S, longitudinal sound velocity V_L, and Debye temperature Θ_E from our elastic constants, as well as the thermodynamic properties from quasi-harmonic Debye model. We obtain that the heat capacity C_v and the thermal expansion coefficient α at 0 GPa and 300 K are 120.78 J mol^?1 K^?1 and 4.70 × 10^?5 K^?1, respectively.