Luminescence of silicon films on sapphire irradiated with high-energy particles

Using low-temperature (4.2–78 K) photoluminescence, we study the processes of defect formation in silicon films on sapphire irradiated with high-energy particles (electrons, γ-quanta of⁶⁰Co). It is established that carbon atoms, as a residual process impurity, participate in the formation of luminescence centers stable up to annealing temperatures of about 550 K. For carbon-containing centers we reveal a shift in the spectral lines relative to their position in spectra of single-crystal silicon. It is proposed that this spectral shift is associated with the presence of internal stresses of about 5·10⁸ N/m² in the silicon films. Institute of Solid-State Physics and Semiconductors, National Academy of Sciences of Belarus, 17, P. Brovka Str., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskefii, Vol. 66, No. 3, pp. 383–386, May–June, 1999.     

NMR spectra of androstane analogs of brassinosteroids

We have used two-dimensional NMR spectroscopy to make a complete assignment of signals from the nuclei of hydrogen and carbon atoms in the spectra of brassinosteroids in the androstane series. We have confirmed the stereochemistry of the chiral centers and the structure of the molecules. We have studied the effect of the configuration of the 2,3-diol groups in the A ring of the steroids on the chemical shift of adjacent atoms in the ¹³C and ¹H NMR spectra. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 583–590, September–October, 2007.     

Spectroscopic manifestations of isotope substitution in ultrasound jet-cooled complex molecules and their van der waals complexes

It is shown that, upon formation of ultrasound jet-cooled var der Waals complexes of polar molecules of 9-cyanoanthracene, 3-aminophthalimide, and 3-amino-N-methylphthalimide with water molecules, pronounced manifestations of isotope substitution in the ligand molecules take place, which manifest themselves in shifting 0–0-transitions by 5–7 cm⁻¹ and changes in frequencies of intramolecular vibrations. Spectroscopic effects of isotope substitution of atoms of the amino group are established for substituted phthalimides. We propose a new mechanism of the effect of isotope substitution on frequencies of electronic transitions which cannot be reduced to the known one (realized by means of changes in values of the zero vibrational energy) and is based instead on the change in the charge density distribution in the molecule. Belarusian State University, 4, F. Skorina Ave., Minsk 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 2, pp. 148–154, March–April, 1997.     

Kinetics of the Excited States of Helium in an Atmospheric-Pressure Glow Discharge in a Helium-Nitrogen Mixture

Using an atomic-absorption spectral analysis technique, we determined the concentrations of helium atoms in states 2¹S, 2¹P, 2³S, and 2³P in an atmospheric-pressure glow discharge in helium (99.98%) and in a mixture of helium with nitrogen (99.5%He+0.5%N₂). It is shown that the population of the lower excited levels of helium atoms (n = 2) in its mixture with nitrogen is almost an order of magnitude smaller than in the case of a discharge in helium. The maximum of the concentration of excited atoms in a discharge both in helium and in its mixture with nitrogen is in the cathode region at a distance of about 0.1 mm from the cathode. The reaction of quenching of excited helium atoms by nitrogen molecules is responsible for the sharp decrease in the concentration of He(n = 2) on addition of nitrogen into helium. Presented at the 5th Symposium on Physics and Diagnostics of Laboratory and Astrophysical Plasmas, Belarus, Serbia and Montenegro, Minsk, Belarus, September 20–23, 2004; 12th International Congress on Plasma Physics, October 25–29, 2004, Nice, France. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 530–537, July–August, 2005.     

XPS study of the chemical bonding in hydrogenated amorphous germanium–carbon alloys

A systematic study of the chemical bonding in hydrogenated amorphous germanium–carbon (a-Ge_1-xC_x:H)alloys using X-ray photoelectron spectroscopy (XPS) is presented. The films, with carbon content ranging from 0 at. % to 100 at. %, were prepared by the rf co-sputtering technique. Raman spectroscopy was used to investigate the carbon hybridization. Rutherford backscattering spectroscopy (RBS) and XPS were used to determine the film stoichiometry. The Ge 3d and C 1s core levels were used for investigating the bonding properties of germanium and carbon atoms, respectively. The relative concentrations of C–Ge, C–C, and C–H bonds were calculated using the intensities of the chemically shifted C 1s components. It was observed that the carbon atoms enter the germanium network with different hybridization, which depends on the carbon concentration. For concentrations lower than 20 at. %, the carbon atoms are preferentially sp³ hybridized, and approximately randomly distributed. As the carbon content increases the concentration of sp² sites also increases and the films are more graphitic-like. Received: 4 May 1999 / Accepted: 24 November 1999 / Published online: 24 March 2000     

Formation of chemical compounds in a laser plasma

Using the methods of laser-induced fluorescence and emissive spectroscopy, we carried out investigations of the formation of TiO molecules in a laser plasma produced by focusing the radiation of an AYG:Nd³⁺ laser on the surface of a titanium target in air. The radiation flux density varied within the range 10⁸–10¹⁰ W/cm². We investigated the distribution of molecules over internal states and the space-time distributions of Ti atoms in the ground, metastable, and excited states, as well as of TiO molecules in the ground and excited states. We found that gas-phase reactions with participation of Ti atoms in the ground state provide the most probable channel for the formation of TiO molecules; the role of reagents in ionized, excited, and metastable states is of secondary importance. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 109–115, January–February, 1999.     

Effect of ethylene carbonate plasticizer and TiO<Subscript>2</Subscript> nanoparticles on 49% poly(methyl methacrylate) grafted natural rubber-based polymer electrolyte

The effect of plasticizer and TiO₂ nanoparticles on the conductivity, chemical interaction and surface morphology of polymer electrolyte of MG49–EC–LiClO₄–TiO₂ has been investigated. The electrolyte films were successfully prepared by solution casting technique. The ceramic filler, TiO₂, was synthesized in situ by sol-gel process and was added into the MG49–EC–LiClO₄ electrolyte system. Alternating current electrochemical impedance spectroscopy was employed to investigate the ionic conductivity of the electrolyte films at 25 °C, and the analysis showed that the addition of TiO₂ filler and ethylene carbonate (EC) plasticizer has increased the ionic conductivity of the electrolyte up to its optimum level. The highest conductivity of 1.1 × 10⁻³ Scm⁻¹ was obtained at 30 wt.% of EC. Fourier transform infrared spectroscopy measurement was employed to study the interactions between lithium ions and oxygen atoms that occurred at carbonyl (C=O) and ether (C-O-C) groups. The scanning electron microscopy micrograph shows that the electrolyte with 30 wt.% EC posses the smoothest surface for which the highest conductivity was obtained.     

Application of NMR spectroscopy for analysis of the composition of pine needle essential oil

We have used ¹H and ¹³C NMR spectroscopy to analyze the chemical composition of essential oils of pine needles grown in different regions of the Republic of Belarus. We consider the change in the composition of the oils depending on the area where the pines were grown. We suggest using pine essential oil as a biological indicator of environmental conditions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 246–249, March–April, 2006.     

Photophysics ofβ-carotene and related compounds (review)

A review of data on the photophysics of carotenoids is presented. Results of investigations of spectroscopic, temporal, and energy parameters of excited S₁ and S₂ singlet states of β-carotene and related compounds are critically examined. These states give rise to extremely high probabilities (10¹¹–10¹³ sec⁻¹) of radiationless deactivation of the electronic excitation energy in carotenoids. Results of investigations of photophysical properties of triplet states of carotenoids are considered mainly from the standpoint of quenching of singlet oxygen and triplet states of organic molecules by carotenoids. Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 5–19, January–February, 1997.     

Investigation of proton channeling using nuclear-reaction resonances

To investigate orientation effects, an approach based on the measurements of γ-ray yields following the excitation of “narrow" isolated resonances in the reactions occurring on the nuclei of interstitial impurity atoms, that occupy certain positions in a crystal, has been proposed. The carbon atoms were shown to be located in octahedral interstitial sites of the Re-0.4 at. % ¹³C monocrystalline solution. The proton flux distribution in the (0001) channel was investigated via the 1.7476 MeV resonance of the ¹³C(p,γ)¹⁴N reaction. Some particular qualities of the reaction yield were found to be dependent upon the proton energy. The method of measurement of the electronic stopping power of channeled particles has been deduced. The γ-ray yield of the resonance reactions induced by the channeled protons was shown to be dependent on the amplitude of the thermal vibrations of carbon atoms.     

Isotope effect of the phonons mean free path in graphene by micro-Raman measurement

The isotope labeled graphene was synthesized in the concentration of ¹³C carbon atom in 1%, 25%, 50%, 75% and 99%. The isotope effect on the phonon behavior in graphene was investigated based on the micro-Raman analysis of ¹³C isotope labeled graphene samples. We found that the phonon scattering is affected by the isotopic carbon atom as a point defect. Based on the experiment results, the Klemens-Callaway model and uncertainty principle were used to obtain the mean free path of the G and D phonons. The results agree with the thermal conductivity measurement by non-contact optical method and with other theoretical calculations.     

Calculation of conformations and vibrational spectra of a fragment of the 2,6-hydroxyethyl cellulose molecule

We have used the molecular mechanics method for conformational analysis of a fragment of the molecule of a water-soluble cellulose ether: 2,6-hydroxyethyl cellulose (2,6-HEC). As a result of rotation about the C-C and C-O bonds within the bulky side substituents on the C5 and C2 backbone atoms in the fragment of the 2,6-HEC molecule, we have obtained 12 of the most stable conformers for this fragment with strain energies differing within the range 0–2.3 kcal/mol. We have shown that the most stable conformers have the following conformations for the groups of atoms on the bonds C5-C6, C6-O6, C13-O6, C10-C13: gt, g⁻, g⁺, g⁺ and gg, t, g⁺, g⁺ respectively; and on the bonds C2-O2, C11-O2, C7-C11: g⁺g⁻, g⁻, g⁺ respectively. For the conformers obtained, using the same method we calculated the frequencies and the potential energy distribution (PED) for their normal vibrations (NV). Comparative analysis showed high sensitivity of both the frequency and the PED of the normal vibrations to conformational changes within the indicated bulky substituents over the entire analyzed spectral region (800–1500 cm⁻¹ for the methylene groups). We introduce the concept of “conformational characteristicity” of both the frequency and the mode of vibration. We show that it is possible to analyze the conformations of the bulky substituents of the fragment of the 2,6-HEC molecule using its vibrational spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 42–53, January–February, 2006.     

A New EPR Data on the MA1 and NIRIM8 (NP1) Phosphorus-Related Centers in Synthetic 1b Diamonds

Microdiamonds grown under high-pressure and high-temperature conditions from a P–C medium at different temperatures have been studied by electron paramagnetic resonance (EPR). Two paramagnetic centers P1 and MA1 were observed in microdiamonds grown at 1,873 K. Analysis of weak lines around these centers suggests that they may be due to ¹³C hyperfine structure (HFS) of the MA1 center. The calculated s/p hybridization parameter for this carbon atom (C₁) was similar to that for the undistorted lattice. At a growth temperature of 1,973 K, in addition to MA1 and P1, a new center, labeled NP1, with HFS from nitrogen and phosphorus atoms and with EPR parameters similar to NIRIM 8 was identified. The NP1 (NIRIM8) centers have an electron spin S = 1/2. We propose that nitrogen–phosphorus defects are created through subsequent migration of nitrogen atoms towards phosphorus atoms upon increasing of the growth.     

Calculation of conformations and vibrational spectra of a monomeric fragment of the 2,6-carboxymethyl cellulose molecule

A theoretical conformational analysis has been carried out for the side substituents of a fragment of the molecule for 2,6-carboxymethyl cellulose (a water-soluble cellulose ether), and the frequencies and the potential energy distribution of the normal vibrations have been calculated for the most stable conformers of the ether groups of this fragment in the approximation of the molecular mechanics method. It has been shown that the most stable conformers are those that have the conformations gg, t, g⁻, g⁻, g⁻-for the groups of atoms on the bonds C5-C6, C6-O6, C13-O6, C10-C13, C10-O9 and the conformations g⁺g⁻, g⁺, g⁻, g⁻; g⁺g⁻, g⁻, g⁻, g⁻; g⁺g⁻, g⁻, g⁺, t for the groups of atoms on the bonds C2-O2, C11-O2, C7-C11, C7-O8. Comparative analysis of the calculated frequencies and the potential energy distribution of the normal vibrations for 13 of the most stable conformers showed, as in the case of the 2,6-hydroxyethyl cellulose molecule, that the frequencies and modes of the normal vibrations are highly sensitive to conformational transitions in the analyzed spectral region (800–1500 cm⁻¹). The characteristic patterns for the change in the frequencies and modes of the normal vibrations have been established in connection with conformational transitions within both side substituents. The observed conformational lability of the bulky substituents in the cellulose ether molecules and its manifestations in the vibrational spectrum provide a basis for hypothesizing that one of the major mechanisms for the process of their thermal gelation in aqueous solutions is conformational transitions within these substituents. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 5–15, January–February, 2007.     

Optical properties of ion-implanted polymer layers

Polyethylene and polyamide-6 films implanted with 100 keV B⁺ ions within the dose range of 1·10¹⁴–1·10¹⁷ cm⁻² are investigated by the methods of optical spectroscopy. It is shown that in the case of ion-implanted polymers, optical absorption is caused by carbon nanoclusters formed in the tracks of bombardment ions. The dynamics of growth of these nanonclusters during ion implantation are studied. The concept of formation of a carbonized ion-implanted layer is suggested, which takes into consideration the formation of lower unsaturated compounds (dienes, trienes) and primitive carbon clusters, cluster growth and formation of saturated and unsaturated intercluster bridge bonds. Moreover, an investigation is made of the side process of compensation of broken carbon bonds due to interaction with atmospheric oxygen. Belarusian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 377–381, May–June, 1998.     

NMR determination of the composition of balsams from scotch pine resin

We have used ¹H and ¹³C NMR spectroscopy to study the composition of pine resin balsams from Scotch pines grown in different regions of the Republic of Belarus. We have established that their chemical composition does not depend very much on the region where they are grown or the level of contamination of the forests by radioactive and industrial emissions. Prolonged storage of the balsams leads to a substantial change in their compositions, due to isomerization of the resin acids. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 411–415, May–June, 2008.     

Optoacoustic gas analyzer based on a13C16O2 laser for multicomponent pollution of air

A computer-aided optoacoustic gas analyzer based on a continuous¹³C¹⁶C₂ laser for multicomponent pollution of atmospheric air is described. The analyzer has the ability to detect absorption of radiation by detected substances at the level of ∼1·10⁻⁹ cm⁻¹ at a time resolution of 30 sec. Results of an experiment on simultaneous detection of H₂O, CO₂, NO₂, NH₃, HNO₃, OCS, and C₂H₄ in the atmospheric air using 40 laser lines are presented. B. I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, 68, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 345–350, May–June, 1999.     

Effect of nickel on the structure and bond type in amorphous diamond-like carbon films

Experimental data are presented from studies of the structure and bond type of carbon atoms in amorphous carbon-nickel films deposited from pulsed vacuum-arc discharge plasma sources. X-ray photoelectron spectroscopy was used. The characteristics of the plasmon loss spectra depend significantly on the deposition parameters. Carbon exists in a mixed sp²+sp³ hybridized state in the carbon–nickel films. The ratio of sp³/sp² carbon bonds increases when the nickel content is reduced (from 5.5 to 1.0 atomic %) and the deposition angle is increased. The structure closest to that of diamond was with a substrate bias voltage of –80 to –100 V and a deposition angle of 90°.     

Light-Induced shifts in the frequency of a multiphoton radiooptical SHF resonance in alkali atoms

A computation is carried out for light-induced shifts in the frequency of a multiphoton radiooptical SHF resonance in alkali atoms on the basis of the quantum formalism of spherical tensors. The components of a light-induced shift in frequency at magneto-independent 0–0– and 1,–1-transitions in⁸⁷Rb atoms under the conditions of isotopic filtration of the resonance light of pumping are calculated. The difference between the temperatures of a filter cell is discovered at which the point of zero shift in the frequency of radiooptical resonance is attained. The components of the light-induced shift of frequency in optically oriented⁸⁷Rb and¹³³Cs atoms are compared in the absence of collisional reorientation in excited state. The prevailing role of the tensor component of light-induced shift in pumping by the D₁-line of a head doublet and the effect of the orientational dependence of the frequency of a multiphoton resonance on change in the sign of the pumping source radiation polarization are noted. St. Petersburg State Polytechnical University, 29 Politekhnicheskaya Str., St. Petersburg, 195251, Russia. Translated from Zburnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 832–838, November–December, 1998.     

Intramolecular photoinduced electron transfer in Pd-porphyrin-quinone in the picosecond time range

Photoinduced electron transfer (PET) was studied in toluene solutions of the Pd-porphyrin-quinone (Pd-PQ) dyad by flash photolysis in the picosecond time range and by a luminescence method. It is found that Pd-PQ has a high rate of intercombination conversion K_isc=(7.7±0.2)·10¹⁰ sec⁻¹. Competing intramolecular PET occurs from the lower excited singlet state of the dyad with the rate constant K _et ^s =(2.7 ±0.3)·10¹⁰ sec⁻¹. Therefore, ∼74% of excited molecules from the dyad make a transition to the triplet T₁ state and 26% take part in intramolecular PET resulting in formation of radical products. The radical products relax to the ground state with the rate constant K=(7.4±0.2)·10⁹ sec⁻¹. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina St., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 11–18, January–February, 1999.