Spectroscopic investigation on the lattice dynamics of different cut quartz samples irradiated by neutrons

A spectroscopic study of the effect of neutron radiation on the lattice dynamics of different cut crystalline and glassy quartz (SiO₂) has been performed. The IR spectroscopy method is used to determine the mechanisms by which the spectral characteristics of deformation and valence vibrations vary by radiation-induced alteration of the lattices in two types of modified quartz (α-SiO₂ and ν-SiO₂) as a function of the neutron fluence at low and high frequencies. It has been established that nonlinear changes in the dose dependences between the spectral characteristics of the fundamental modes occur in two types of crystals, with different orientations, and in glass, and the features of the spectrum modifications exist near 300–550 and 700–1400 cm⁻¹ and at higher frequencies. The derived dose dependences are compared to those of the degenerate vibration parameters in ν-SiO₂, and the extreme kinetics of the force coefficients is determined. A conclusion is made that the accumulation of radiation damages, changes in the force field around the bridge bonds, and the phase states of SiO₂ affect the observed specific behavior of the radiation-modified spectral and force parameters of the degenerate and deformation modes in quartz samples of different types.     

Spectral characteristics and force constants of irradiated α-SiO<Subscript>2</Subscript> single crystals

The IR-radiation reflectance spectra of α-SiO₂ single crystals exposed, in a reactor, to fast neutrons with fluences changing in a wide range have been investigated. The regularities of the change in spectral characteristics of the antisymmetric and degenerate vibrations of the bridge bonds of the crystals studied and in the dynamic parameters of these crystals in the process of their irradiation have been determined. The critical dynamics of the crystal lattice in the region of antisymmetric stretching and degenerate modes and the extremum radiation kinetics of the ion-polarizability parameters and the force constants of the indicated crystals were detected. The changes in some characteristics of these crystals, arising on their irradiation as a result of the damage of the substance, the rupture and extension of some silicon—oxygen bonds, and the transformation of the structure of α-SiO₂ single crystals by two mechanisms, have been considered. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 773–777, November–December, 2005.     

Luminescence spectra fine structure for uranyl sulfate and oxalate crystals

Quasi-line low-temperature (T = 77 and 4.2 K) luminescence spectra of uranyl sulfates and oxalates have been recorded and analyzed. It has been shown that the spectral structure is determined by the manifestation of the internal and external vibrations of both the uranyl ion and molecular groups (SO₄)^2– and (C₂O₄)^2–bonded to the uranyl ion. The spectral line half-width is of the order of ≈5–7 cm^–1; the line shape, close to Lorentzian. The fluorescence spectra may be complicated by structural defects in the crystals.     

Whole-body distribution of <Superscript>14</Superscript>C-labeled silica nanoparticles and submicron particles after intravenous injection into Mice

We analyzed the whole-body distribution of ¹⁴C–ADP-labeled silica nanoparticles (¹⁴C–ADP–SiO₂ nanoparticles) and submicron particles (¹⁴C–ADP–SiO₂ submicron particles) after intravenous injection into ICR mice. The ¹⁴C–ADP–SiO₂ nanoparticles and submicron particles were synthesized before the injection and the particle size was 19.6 and 130 nm, respectively. Similarly, the shape was spherical and the crystallinity was amorphous. After the synthesis, we injected mice with the ¹⁴C–ADP–SiO₂ nanoparticles or the ¹⁴C–ADP–SiO₂ submicron particles and dissected tissues after 1, 2, 4, 8 and 24 h. The radioactivity in the tissues was measured with a liquid scintillation counter. As a result, the retention percentage in bone, skin, lymph nodes, and the digestive mixture was at least twofold higher in the ¹⁴C–ADP–SiO₂ nanoparticles-exposed mice, whereas the retention percentage in the kidney was statistically higher in the ¹⁴C–ADP–SiO₂ submicron particles-exposed mice. Both types of ¹⁴C–ADP–SiO₂ particles mainly translocated to the muscle, bone, skin, and liver, but hardly translocated to the brain and olfactory bulb. Furthermore, the ¹⁴C–ADP–SiO₂ nanoparticles had a higher retention percentage (62.4 %) in the entire body at 24-h post-injection than did the ¹⁴C–ADP–SiO₂ submicron particles (50.7 %). Therefore, we suggested that the ¹⁴C–ADP–SiO₂ nanoparticles might be more likely than the ¹⁴C–ADP–SiO₂ submicron particles to be retained in the body, and consequently they might be gradually accumulated by chronic exposure.     

Recombination kinetics in nonlinear defective LiB3O5 crystals

A study of recombination kinetics in LiB₃O₅ (LBO) crystals by time-resolved luminescence and absorption spectroscopy is reported. An investigation of the kinetics of transient optical absorption (TOA) and luminescence under ns-scale electron-beam excitation performed within a broad temperature range of 77–500 K and a 1.2–5-eV spectral interval has established that the specific features in the recombination kinetics observed in LBO involve electronic, B²⁺, and hole, O⁻, trapping centers. The TOA and luminescence kinetics, as well as their temperature dependence, are interpreted by a model of competing hole centers. Relations connecting the kinetics parameters and the temperature dependence to the parameters of the main LBO point defects are presented. Fiz. Tverd. Tela (St. Petersburg) 40, 2008–2014 (November 1998)     

IR spectra of fused silica irradiated by fast neutrons

IR spectroscopy has been used to study the process of structural damage and changes in some characteristics of fused silica irradiated by fast neutrons over a very broad fluence range (10¹⁷–10²¹ cm⁻²). Features of the change in spectral characteristics of the bending and stretching vibrations of the bridge bonds have been identified, and also a comparative analysis has been carried out with radiation-induced changes in a series of optical spectra in the UV and visible regions, and structural parameters and other characteristics of wafers irradiated by different fluences. A correspondence has been established between the features of the radiation-induced changes in the optical, luminescence, and structural properties, and extremal points have been observed on the dose dependences. Based on the results obtained, a mechanism of radiation-induced rearrangement of the silica structure is suggested. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 494–497, July–August, 2006.     

Infrared absorption spectra and structure of TiO2-SiO2 composites

The composites xTiO₂-(1−x)SiO₂ (x = 0.1, 0.5, 0.9) were obtained by coprecipitation from solutions of alkoxides: tetraethoxysilane (TEOS) and titanium tetraisopropoxide (TIPT). Intermolecular interaction of the components of the composite is apparent in the IR absorption spectra in the 928–952 cm⁻¹ region, and is connected with bending vibrations of the Si-O-Ti bond. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 724–728, September–October, 2008.     

Analysis of the Nonselective Spectra of Photostimulated Electron Emission from the Surface of Irradiated Dielectrics

The methodological aspects of PSEE spectroscopy of the surface of irradiated dielectrics have been considered. A generalized method for processing the nonselective photostimulated electron emission (PSEE) spectra taking into account the effects of radiation electrification and structural disordering is proposed and has been substantiated. The procedure of separation of the emission contribution of discrete radiation centers providing, in the stationary approach, estimation of a number of parameters and the concentration of emission-active defects of the surface layer of the material has been described. The potentialities of the method have been demonstrated with the example of Be₂SiO₄ phenacite crystals and crystalline and glassy SiO₂. Diamagnetic oxygen-deficient centers, body and surface E'-centers, as well as hole O ₁ ⁰ -centers on nonbridging oxygen atoms have been registered. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 381–385, May–June, 2005.     

Dielectric relaxation in Bi12SiO20 crystals

Anomalies of the dielectric properties of undoped and aluminum-and gallium-doped crystals of Bi₁₂SiO₂₀ are investigated in the frequency and temperature range ν=10²–10⁸ Hz and T=300–800 K. They are shown to be due to Debye relaxation processes and determined by the relaxor parameters. The mechanism of electron thermal polarization is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1223–1229 (July 1997)     

Picosecond laser ablation of SiO2 layers on silicon substrates

In this work, we report on laser ablation of thermally grown SiO₂ layers from silicon wafer substrates, employing an 8–9 ps laser, at 1064 (IR), 532 (VIS) and 355 nm (UV) wavelengths. High-intensity short-pulse laser radiation allows direct absorption in materials with bandgaps higher than the photon energy. However, our experiments show that in the intensity range of our laser pulses (peak intensities of <2×10¹² W/cm²) the removal of the SiO₂ layer from silicon wafers does not occur by direct absorption in the SiO₂ layer. Instead, we find that the layer is removed by a “lift off” mechanism, actuated by the melting and vaporisation of the absorbing silicon substrate. Furthermore, we find that exceeding the Si melting threshold is not sufficient to remove the SiO₂ layer. A second threshold exists for breaking of the layer caused by sufficient vapour pressure. For SiO₂ layer ablation, we determine layer thickness dependent minimum fluences of 0.7–1.2 J/cm² for IR, 0.1–0.35 J/cm² for VIS and 0.2–0.4 J/cm² for UV wavelength. After correcting the fluences by the reflected laser power, we show that, in contrast to the melting threshold, the threshold for breaking the layer depends on the SiO₂ thickness.     

Pulsed photo- and cathodoluminescence of LiF crystals doped with tungsten oxide

We have studied the spectral and kinetic characteristics of activated photo- and cathodoluminescence of LiF-O and LiF-WO₃ crystals in the spectral range of 3.6–1.6 eV using methods of pulsed spectrometry with nanosecond time resolution in the temperature range of 15–300 K and in the range of ionizing radiation dose absorbed by crystals of 10²−2 × 10³ Gy.     

Infrared spectra of brassinolide and castasterone steroid phytohormones and their 24-epi derivatives

Absorption bands in IR spectra of brassinolide, castasterone, and their 24-epi derivatives in the frequency range 3800–1000 cm^–1 have been interpreted. A number of spectral features distinguishing brassinolide from castasterone have been found. The conducted analysis shows that the structural differences manifest themselves in IR spectra of the investigated brassinosteroids in the region of stretching vibrations of CO–H, C=O, C–OH, C–O–C, CH₃, CH₂, and CH groups. The main distinctions in IR spectra of brassinolides and castasterones are due to the B ring structure.     

A computer study of the Raman spectra of the (GaN)<Subscript>129</Subscript>, (SiO<Subscript>2</Subscript>)<Subscript>86</Subscript>, and (GaN)<Subscript>54</Subscript>(SiO<Subscript>2</Subscript>)<Subscript>50</Subscript> nanoparticles

The Raman spectra of the (GaN)₁₂₉, (SiO₂)₈₆, and (GaN)₅₄(SiO₂)₅₀ nanoparticles were calculated using the molecular dynamics method. The spectrum of (SiO₂)₈₆ had three broad bands only, whereas the Raman spectrum of (GaN)₁₂₉ contained a large number of overlapping bands. The form of the Raman spectrum of (GaN)₅₄(SiO₂)₅₀ was determined by the arrangement of the GaN and SiO₂ components in it. The nanoparticle with a GaN nucleus had a continuous fairly smooth spectrum over the frequency range 0 ≤ ω ≤ 600 cm⁻¹, whereas the spectrum of the nanoparticle with a SiO₂ nucleus contained well-defined bands caused by vibrations of groups of atoms of different kinds and atoms of the same kind.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Effect of deuteration on the electronic and electron-vibrational properties of the organic conductor k-(D8-BEDT-TTF)2[Hg(SCN)2Br]

We present here for the first time polarized reflection spectra and optical conductivity spectra of single crystals of the newly deuterated organic conductor k-(D₈-BEDT-TTF)₂[Hg(SCN)₂Br] at room temperature. The spectral region investigated is 700–40 000 cm⁻¹. We examined the effect of deuteration on electronic and electron-vibrational transitions observed in the spectra. The observed shift of the electron “dimer” transition in the infrared toward lower frequencies upon deuteration is linked with an increase in the interaction between neighboring, mutually perpendicular dimers in the structure of the deuterated crystal. A lowering of the symmetry of the BEDT-TTF molecule is demonstrated in crystals similar to k-(BEDT-TTF)₂[Hg(SCN)₂Br], relative to the symmetry D _2h of the free molecule. We refine the assignment of the spectral features determined by the interaction of electrons with the fully-symmetric intramolecular vibrations of the C=C, C-S, and C-C-H bonds of the BEDT-TTF molecule. Fiz. Tverd. Tela (St. Petersburg) 40, 1595–1598 (September 1998)     

Energy transfer from the host to Er<Superscript>3+</Superscript> dopants in semiconductor SnO<Subscript>2</Subscript> nanocrystals segregated in sol–gel silica glasses

Undoped and Er³⁺-doped glass–ceramics of composition (100−x)SiO₂–xSnO₂, with x = 5 or 10 and with 0.4 or 0.8 mol% of Er³⁺ ions, were synthesised by thermal treatment of precursor sol–gel glasses. Structural studies were developed by X-Ray Diffraction. Wide band gap SnO₂ semiconductor quantum-dots embedded in the insulator SiO₂ glass are obtained. The mean radius of the SnO₂ nanocrystals, ranging from 2 to 3.2 nm, is comparable to the exciton Bohr radius. The luminescence properties have been analysed as a function of sample composition and thermal treatment. The results show that Er³⁺ ions are partially partitioned into the nanocrystalline phase. An efficient UV excitation of the Er³⁺ ions by energy transfer from the SnO₂ nanocrystal host is observed. The Er³⁺ ions located in the SnO₂ nanocrystals are selectively excited by this energy transfer mechanism. On the other hand, emission from the Er³⁺ ions remaining in the silica glassy phase is obtained by direct excitation of these ions.     

Output characteristics and parameters of the plasma from a gas-discharge low-pressure ultraviolet source using helium-iodine and xenon-iodine mixtures

The output characteristics and parameters of the plasma of a powerful gas-discharge source of UV radiation are studied. The UV source uses He-I₂ and Xe-I₂ mixtures and is excited by a longitudinal glow discharge. The pressure of the gas mixtures is varied from 100 to 1500 Pa, and the discharge power falls into the range 15–250 W. The source (lamp) emits in the spectral interval 200–390 nm, which covers the spectral line of the iodine atom at 206.2 nm, the spectral band of XeI(B-X) with a maximum at 253 nm, and the spectral band of with a maximum at 342 nm. For He(Xe)-I₂ mixtures at a pressure of 800–1000 Pa (this pressure range is near-optimal according to our experimental data), the electron energy distribution functions and the electron kinetic coefficients as functions of parameter E/N (E is the electric field strength, and N is the particle concentration in the discharge) are calculated. The calculated plasma parameters are used in the qualitative analysis of key electronic processes in the plasma of an exciplex halogen UV source and will be subsequently employed in numerical simulation of the process kinetics and output characteristics of a UV source based on helium-iodine or xenon-iodine mixtures.     

Infrared spectra of S-and R-isomers of biologically active brassinosteroids

Comparative analysis of IR spectra of S-and R-isomers differing in the configuration of OH groups in the side chain of biologically active 24-epi-and 28-homocastasterones and 24-epi-and 28-homobrassinolides is carried out. Stretching vibration frequencies of H-bonded OH groups of isomers of corresponding brassinosteroids practically coincide. The optical density in maxima of these bands is higher in spectra of the R-isomers. Alteration in the configuration of the OH groups weakly influences also the band intensities of CH3, CH₂, and CH groups. Band intensities of stretching vibrations of associated C=O groups of S-and R-isomers also neglibibly differ from each other. Their frequency characteristics do not experience substantial changes. These features differ considerably in IR spectra of castasterones and brassinolides. For castasterones, the difference in frequencies of band maxima of free and bound C=O groups amounts to ∼15 cm⁻¹; for brassinolides, 23 cm⁻¹. Intensities of both bands are approximately equal in spectra of castasterones. The band intensity of free C=O groups of brassinolides is considerably lower than that of H-bonded ones. The above spectral differences can be used to identify these brassinosteroids. Frequencies of both symmetric and antisymmetric deformation vibrations of CH₃ and CH₂ groups are close in spectra of all brassinosteroids studied. The frequency of CH₂ in a CH₂-OC group belongs only to brassinolides; of deformation vibrations of CH in a CH-C=O group, to castasterones. The frequency of stretching vibrations of C-O-C and C-O groups is observed only in spectra of brassinolides. In the region 1130–900 cm⁻¹ of IR spectra of brassinosteroids, stretching vibrations of CC, CCH, and C-OH groups are predominantly observed. In the frequency range 1130–995 cm⁻¹, the optical density of band maxima of S-isomers is higher than that of R-isomers, which can be used to identify isomers. At the same time frequencies of corresponding bands of isomers practically coincide. Differences in the structure of the side chain of brassinosteroids do not influence essentially the frequency characteristics of the IR spectra. The exception is the band related to stretching vibrations ν(C23-OH) of the side chain which features a considerable frequency ν_max ≈ 983 cm⁻¹ only in spectra of R-isomers of homocastasterone and brassinolide. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 623–630, September–October, 2008.     

Photosensitivity and thermosensitivity of polymers doped with Eu(fod)<Subscript>3</Subscript> molecules

We have studied the photoluminescence (PL) spectra of Eu³⁺ ions and the decay kinetics for the photoluminescence intensity on exposure to temperature and UV radiation in polypropylene and oligo(urethane methacrylate) (OUM) doped with Eu(fod)₃ molecules (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) by soaking in a supercritical CO₂ solution. We have established that the decay kinetics for the photoluminescence intensity on exposure to UV radiation depends on the temperature of the sample and the concentration of the dopant in it. Based on studies of the spectral characteristics of doped OUM samples, we suggest that this material can be used as a two-color luminescent temperature sensor. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 104-111, January-February, 2009.