Si–Ge alloys in C2/c phase with tunable direct band gaps: A comprehensive study

Si–Ge alloys are a new type of semiconductor material that are of great significance for the development of microelectronic technology, especially in the photoelectricity industry and for thermoelectric conversion in high temperature applications (>700 K). In the present work, a novel Ge allotrope in the C2/c phase with band gap of 1.102 eV was firstly proposed, which is suitable for the absorption of sunlight. C2/c-Ge are mechanically, dynamically and thermodynamically stable. A series of Si_24-xGe_x alloys (x = 0, 8, 16, 24) in the C2/c phase with band gaps of 1.10–1.50 eV are predicted by ab initio calculations at ambient conditions. The Si_24-xGe_x alloys (x = 0, 8, 16, 24) in C2/c phase have better absorption ability than that of the Si in diamond, hP12 and oC12 phases. The Si_24-xGe_x alloys in the C2/c phase have the strong absorption in the visible, which have a great impact on the new-generation photovoltaic applications.     

Effect of fullerenes C60and C70 on the absorption spectrum of 2-cyclooctylamino-5-nitropyridine

The influence of fullerenes C₆₀ and C₇₀ on the absorption spectrum of 2-cyclooctylamino-5-nitropyridine (COANP) is studied. A substantial shift of the absorption band edge of COANP-C₇₀ to the IR region was observed. This effect was compared with the data obtained for COANP-C₆₀. The experimental results were explained using the model that takes into account the interaction between electronic subsystems of COANP and fullerene.     

High-resolution Fourier transform infrared spectra of 12C32S, 12C33S, 12C34S,and 13C32S

The v = 1-0 infrared absorption bands of the ¹²C³²S, ¹²C³³S, ¹²C³⁴S, and ¹³C³²S isotopes and the v = 2-1 “hot” band of ¹²C³²S all in the ground electronic state were measured using a high-resolution Fourier transform spectrometer coupled to a long-path absorption cell. P- and R-branch transitions, up to J = 41 for ¹²C³²S, have been measured at 0.004 cm⁻¹ unapodized resolution. Rotational and centrifugal distortion parameters which are improved over those obtained in previous diode laser measurements for the less abundant ¹²C³³S and ¹³C³²S isotopes are reported. Improved v = 1-0 band origins of the various isotopes are also reported. Analysis included published microwave data along with the present IR measurements. The present results are compared with previous infrared diode laser, Fourier transform spectrometer, and microwave measurements.     

Laser spectroscopy of ethylene with waveguide CO2 and N2O lasers

Fifty Doppler-broadened absorption lines of ethylene have been measured within large profiles CO₂ or N₂O lase lines. These laser lines are produced by a high pressure waveguide laser and have a full width between 200 and 900 MHz. Eleven absorption lines, the more intense ones, have been assigned to the ν₇ band of C₂H₄. The other absorption lines must belong to hot bands or to the ν₇ band of H₂¹²C¹³CH₂.     

Probe into the reflection from GaP nanoparticles via different solutions of radiative transfer equation

The reflection and absorption spectra of gallium phosphide (GaP) nanoparticles were measured. The radiative transfer equation (RTE) for the medium with scattering and absorption is solved by three different solutions. The ratio of the absorption and scattering coefficients (E _a/E _s) of the GaP nanoparticles layer is calculated from the reflection spectrum via the three solutions, respectively, and the result derived with the three-flux model is closest to the exact solution given by Giovanelli. The E _a/E _s curves all exhibit the energy band gaps of GaP nanoparticles, which are consistent with the absorption spectrum measurement. The shape of the reflection spectrum is mainly determined by the absorption, and the scattering only influences its intensity. The energy band structure of the powder sample plays an important role in the reflection phenomenon, and the reflectance data can be used for quantitative analyses.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

Electronic structure and elastic moduli of the simple cubic fullerite C24—A new allotropic carbon modification

The energy band structure, equation of state, density of states, and elastic moduli of a new allotropic carbon modification, namely, fullerite C₂₄ with a simple cubic lattice (known previously as cubic graphite), are calculated by the full-potential linearized augmented-plane-wave (FLAPW) method with geometry optimization for the first time. The dependence of the total energy on the lattice constant exhibits a minimum for a ₀ = 0.60546 nm. In this case, the lengths of the C-C bonds between fullerene molecules, the lengths of the 6,6-bonds shared by hexagons, and the lengths of the 4,6-bonds shared by a square and a hexagon are equal to 0.1614, 0.1503, and 0.1637 nm, respectively. An analysis of the energy band structure and the density of states demonstrates that the simple cubic fullerite C₂₄ is a direct-band-gap insulator or a semiconductor with a band gap of 1.6 eV. The calculated bulk modulus B ₀ = 196 GPa and the elastic moduli C ₁₁ = 338 GPa, C ₁₂ = 139 GPa, and C ₄₄ = 30 GPa indicate that the fullerite under investigation is a mechanically stable material. The inference is made that the simple cubic fullerite C₂₄ is a new diamond-like molecular zeolite with a unique combination of properties, such as the porosity and nonpolarizability, on the one hand, and the mechanical strength, chemical inertness, and high thermal conductivity, on the other hand. The simple cubic fullerite C₂₄ can be considered a promising low-dielectric-constant (low-k) material (?₀ < 5.7) for use in fabricating interconnections and substrates intended for integrated circuits and nanoelectronics.     

Electronic band structure and optical absorption of nanotubular zinc oxide doped with Iron, Cobalt, or Copper

The absorption spectra of the precursor-derived solid solutions Zn_{1 ? x} M _x O (M = Fe, Co, Cu) with a tubular morphology of aggregates have been investigated in the ultraviolet and visible regions. The maximum metal concentration x in the Zn_{1 ? x} M _x O solid solutions is 0.075 for iron, 0.2 for cobalt, and 0.1 for copper. It has been found that the optical absorption and the band gap of the Zn_{1 ? x} M _x O compounds depend on the type of dopant. The obtained experimental data have been interpreted using the results of the performed ab initio calculations of the electronic band structure and optical absorption.     

Crystal-field induced mixing of electron states in C60 crystals at high pressure

Optical absorption spectra of thin fullerene (C₆₀) crystals in the range 1.7 to 3.8 eV have been measured at T=300 K and at pressures up to 2.5 GPa. The spectrum shifts toward the red with pressure, and the electron absorption intensity is redistributed among its bands. The intensity of the band associated with the lowest direct electron interband transition monotonically increases with pressure, whereas the intensity of the upper interband feature decreases. Bands related to weak edge absorption in the range between 1.7 and 2.2 eV gradually merge with the band associated with the lowest interband transition, whose intensity rises with pressure. A similar redistribution of intensity among electron transition bands has been observed when comparing the spectrum of an isolated C₆₀ molecule and that of a C₆₀ crystal. The results indicate that the crystal-field induced mixing of electron states is present in solid C₆₀, and they can be discussed in terms of the Craig-McClure model, which was suggested to describe crystal-field induced mixing of electron states in anthracene and naphthalene molecular crystals. Zh. éksp. Teor. Fiz. 113, 313–322 (January 1998)     

Temperature dependence of the fine structure of the C and E absorption bands in RbMnF3 below the Néel temperature

The variation in the parameters (width, position, intensity) of the fine structure lines in the C[⁶ A _1g → ⁴ A _1g , ⁴ E _g(⁴ G)] and E[⁶ A _1g → ⁴ E _g(⁴ D)] bands in RbMnF₃ with temperature is studied in the temperature range 10–70 K. In the C band, two narrow (<6 cm^?1) lines are are distinguished at distances of 77 and 80 cm^?1 from the exciton line at T = 10 K. The other lines in the C band and all lines in the E band are more than 20 cm^?1 wide. It is demonstrated that the narrow lines become allowed because of the spin-exchange interaction within a long-range magnetic order model and originate from the excitation of exciton-magnon bound states and that the other lines are made allowed by the exchange-vibronic mechanism within a short-range magnetic order model and originate from the excitation of bound states composed of an exciton, magnon, and oddparity phonon. The vibrational replicas of the main exciton-magnon-phonon lines are due to the quadratic vibronic interaction with odd-parity vibrations. Variations of the intensities and widths of the absorption lines with temperature indicate that these parameters are affected by relaxation and delocalization of the bound states.     

A comparative study of ion-induced damages in C60 and C70 fullerenes

The stability of fullerenes (C₆₀ and C₇₀) under swift heavy ion irradiation is investigated. C₆₀ and C₇₀ thin films were irradiated with 120 MeV Ag ions at fluences from 1×10¹² to 3×10¹³ ions/cm². The damage cross-section and radius of damaged cylindrical zone were found to be higher for C₆₀ than C₇₀ as evaluated by Raman spectroscopy, which shows that the C₇₀ molecule is more stable under energetic ion impact. The higher damage cross-section of the C₆₀ molecule compared with that of the C₇₀ molecule is explained on the basis of thermal conductivity in the framework of the thermal spike model. The surface morphology of pristine C₆₀ and C₇₀ films is studied by atomic force microscopy. UV-visible absorption studies revealed that band gap for C₆₀ and C₇₀ fullerenes thin films decreases with increasing ion fluence. Resistivity of C₆₀ and C₇₀ thin films decreases with increasing ion fluence but the decrease is faster for C₆₀ than C₇₀, indicating higher damage in C₆₀. Irradiation at a fluence of 3×10¹³ ions/cm² results in complete damage of fullerenes (C₆₀ and C₇₀) into amorphous carbon.     

Disorder and density of defects in hydrogenated amorphous silicon-carbon

We report subgap absorption measurements by photothermal deflection spectroscopy in a-Si_1-xC_x: H alloys in the whole range of composition. We observe that incorporation of carbon in the silicon matrix increases both the inverse of the slope of the exponential absorption tail (which is due to the valence band tail) and the subgap absorption around 1.3 eV (due to defects). This result is correlated with former results on the broadening of the conduction band tail deduced from transport measurements in these alloys. It is concluded that carbon incorporation induces disorder and defect creation in the amorphous silicon matrix.     

Electronic band structure, optical absorption, and photocatalytic activity of iron-doped anatase

Quasi-one-dimensional solid solutions of the composition Ti_{1 ? x} Fe _x O_{2 ? x/2} (0.005 ≤ x ≤ 0.050) with the anatase-type structure and extended aggregates have been prepared by the precursor method. The absorption spectra of the solid solutions have been investigated in the ultraviolet and visible regions, and the photocatalytic activity in the oxidation reaction of hydroquinone in water has been estimated. It has been found that the synthesized solid solutions serve as photocatalysts only under ultraviolet irradiation, and their photoactivity increases with an increase in the dopant concentration. The first-principles calculations of the electronic band structure and optical absorption in iron-doped anatase and rutile have been performed using the pseudopotential method LSDA + U (with the VASP software package). The on-site exchange-correlation parameters have been calibrated in the calculations of the electronic band structure of hematite α-Fe₂O₃ and ilmenite FeTiO₃. It has been shown that, despite the appearance of impurity states within the band gap of anatase and rutile, doping with iron does not cause substantial absorption in the visible region, which correlates with the increase in photocatalytic activity only under ultraviolet irradiation. The most probable cause of the experimentally observed absorption in the visible region is the presence of finely dispersed hematite impurities in the obtained samples.     

Manifestation of resonance dipole-dipole interaction in spectra of low-temperature molecular mixtures of C2F6 in CF4 and CF4 in C2F6

We have measured IR absorption spectra of solutions C₂F₆ in CF₄ (T = 178 K) and CF₄ in C₂F₆ (T = 173 K) in the overtone range of the spectrum. We have studied how the resonance dipole-dipole interaction affects the formation of contours of bands that correspond to transitions to states involving the vibrations ν₁₀(C₂F₆) and ν₃(CF₄), which are strong in the dipole absorption. For the system C₂F₆ in liquid CF₄, the state ν₂ + ν₁₀(C₂F₆) resonantly interacts with the state ν₂(C₂F₆) + ν₃(CF₄), and, for the system CF₄ in liquid C₂F₆, the state ν₁ + ν₃(CF₄) resonantly interacts with the state ν₁(CF₄) + ν₁₀(C₂F₆). The contours of the bands ν₂ + ν₁₀ (C₂F₆) in the spectrum of the mixture with CF₄ and of the bands ν₁ + ν₃(CF₄) in the spectrum of the mixture with C₂F₆ have been calculated.     

Absolute line wavenumbers in the near infrared: 12C2H2 and 12C16O2

40 absolute line wavenumbers in the 3v ₃ band of ¹²C¹⁶O₂ between 6927 cm^?1 and 6989 cm^?1 and 626 absolute line wavenumbers in the near infrared absorption spectrum of ¹²C₂H₂ between 7060 cm^?1 and 9900 cm^?1 have been measured using high resolution Fourier transform spectroscopy. The calibration of the CO₂ line wavenumbers relied on heterodyne frequencies available in the v ₁ + v ₃ band of ¹²C₂H₂ near 6556 cm^?1. The absolute uncertainty of the calibrated CO₂ line wavenumbers is estimated to 0.000 08 cm^?1. The acetylene spectra were calibrated using heterodyne frequencies available in the 2—0 band of ¹²C¹⁶O and the line wavenumbers obtained in the 3v ₃ band of ¹²C¹⁶O₂. The absolute uncertainty of the calibrated acetylene line wavenumbers is estimated to range from 0.0003 cm^?1 to 0.006 cm^?1 for strong to very weak isolated lines. Comparison with absolute line wavenumbers obtained independently at JPL in the 3v ₃ band of ¹²C₂H₂ near 9649 cm^?1, calibrated using absolute wavenumbers available in the 2—0 and 3—0 (near 6350 cm^?1) bands of ¹²C¹⁶O, shows very good agreement. Also, the vibration—rotation constants for the observed upper vibrational states of ¹²C₂H₂ were determined, but without accounting for the perturbations affecting these states.     

Electronic energy structure and x-ray spectra of wide-gap AlN and BN crystals and B<Subscript>x</Subscript>Al<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N solid solutions

The electronic energy structure of 2H and 3C AlN and BN crystals and B_xAl_1?xN solid solutions is calculated on the basis of the local coherent potential method using the cluster version of the MT approximation and the theory of multiple scattering. The features of the electronic structure of 2H-AlN crystals are compared with x-ray K and L absorption and emission spectra of aluminum and nitrogen. An interpretation of these features is given. The concentration dependences of the width of the upper subband of the valence band and the band gap in B_xAl_1?xN solid solutions (x = 0.25, 0.5, 0.75) are investigated. Charge transfer from aluminum to nitrogen atoms is shown to occur and increase with boron doping in both crystallographic modifications.     

Optical properties of silylene-biphenylene copolymer films

We have measured absorption, photoluminescence, and photoluminescence excitation spectra, and the photoluminescence time response for films of silylene-biphenylene copolymer, ((C₆H₄)₂(Si(CH₃)₂)_m)_n with m=1,2,4, and 6. The excitation spectra clearly reveal that the lowest absorption band in each copolymer consists of two bands, i.e., a band at 4.7 eV and a band of which energy depends on m. Since the latter band is absent in the copolymer with m=1, the former band is attributed to the lowest π−π* transition in biphenylene subunits. The latter band is attributed to the lowest σ−σ* transition in the silylene subunits, considering its dependence on m. In contrast to the result for solution, the peak energy of photoluminescence band is independent of m. The band has a Stokes shift of more than 1 eV and a large band width of 0.5 eV. The time responses of photoluminescence intensity consist of more than two decay components and the intensity decays more slowly at smaller energy. The large Stokes shift is explained as due to excimer formation between biphenylene subunits. In order to explain the energy dependence of time responses, energy migration is discussed.     

Triplet exciton in a non-reactive bis-triphenyllead (or tin) diacetylene crystal. A spectroscopic study

The lowest triplet exciton state of crystals formed by (C₆H₅)₃?X?C ≡ C?C ≡ C?X?(C₆H₅)₃ where X is Pb or Sn and an equimolecular amount of CH₂Cl₂ solvent molecules, is studied through the analysis of absorption and of phosphorescence emission and excitation spectra at low temperatures. In the lead compound, the origins of absorption and emission are identical, showing the dominance of free exciton emission and the absence of crystal lattice relaxation in the excited state; the splitting is accounted for by symmetry considerations in the different crystalline phases; the triplet exciton band is several cm^-1 wide, although the nearest diacetylene-diacetylene distance is about 10 Å. There is evidence for triplet exciton motion, through the detection of trap (presumably X-trap) emission in the tin compound, and through the analysis of the excitation spectrum lineshape, showing the effect of exciton-exciton interaction in the lead compound.     

Radiation-stimulated modification of C60 films on Si-oxide surfaces

The electronic structure of C₆₀/SiO_x/Si(1 0 0) interface was studied by photoemission (valence-bands, C 1s, and Si 2p core levels) and near-edge X-ray absorption fine structure (C 1s threshold) spectroscopies. It was concluded that the SiO_x/Si surface is non-reactive with respect to the interaction with C₆₀. The exposure of the C₆₀/SiO_x/Si system under non-monochromatic synchrotron radiation causes modification of the electronic structure of this system. It is explained by polymerization of the C₆₀ molecules and arising a strong ionic-like interaction of the polymerized C₆₀ with the SiO_x surface. Annealing of this system up to temperatures of 550–625 °C leads to complete desorption of the C₆₀ molecules from the non-irradiated sample areas while the modified by radiation fullerenes remain attached to the substrate.