Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

Effect of magnetic annealing on phonon behaviors of nanocrystalline BiFeO3

Influence of magnetic annealing at 823 K up to 10 T (T) on the phonon behaviors of nanocrystalline BiFeO₃ was investigated by Raman spectroscopy. The frequencies of fundamental Raman modes increase obviously with increasing annealing magnetic field, and the intensity of the 1260 cm⁻¹ two-phonon mode decreases. The pronounced anomalies of Raman phonon modes under magnetic annealing are attributed to the change of the spin-phonon coupling due to the modulation of spiral spin order. Furthermore, the temperature dependence of Raman peak positions, for the two prominent modes (147 and 176 cm⁻¹), show no notable anomaly around T_N except the sample annealed under 10 T magnetic field; meanwhile, in this sample, another obvious phonon anomaly occurs at ∼150 K (another magnetic phase transition point), which indicate that stronger magnetic annealing with 10 T intensely enhances the spin-phonon coupling, and possibly increases magnetoelectric coupling of nanocrystalline BiFeO₃ due to severely modulation of spiral spin order.     

Raman spectra of the orthorhombic semiconductor compound Cu2SnTe3

The optical phonon spectrum of the semiconductor Cu₂SnTe₃, that crystallizes in the orthorhombic structure with space group Imm2 (), have been studied by measuring unpolarized Raman scattering between 10 and 300 K. The experimental frequencies of the phonon modes observed were compared to those calculated by using simplified lattice dynamical models reported in the literature. From combined analysis of these results together with the factor group analysis of the zone-center vibrational modes, valuable information about these modes was obtained and their possible symmetry was assigned. A₁ modes at 71, 123, 167, 176 and 190 cm⁻¹; A₂ modes 115 and 131 cm⁻¹; B₁ modes at 76, 142 and 152 cm⁻¹; B₂ modes at 89, 100 and 206 cm⁻¹; a overtone at 246 cm⁻¹, and combinations at 218, 270 and 292 cm⁻¹; have been observed in this compound.     

Laser spectroscopy of the A[16.4]8.5-X7.5, A[16.4]8.5-Y[0.15]8.5, and A[16.4]8.5-Z[0.85]7.5 transitions of dysprosium monochloride

Laser-induced fluorescence spectra have been obtained at low resolution using a laser ablation source and pulsed dye laser, and at high resolution using a Broida oven and cw ring dye laser. Dispersed fluorescence spectra from two different excited states, A[16.4]8.5 and B[15.4]Ω (unknown Ω) (the states are labelled [10⁻³T₀]Ω according to their energy and Ω assignment) showed transitions to the same four low lying electronic states, X7.5, Y[0.15]8.5, Z[0.85]7.5, and an unassigned state at 970 cm⁻¹. High resolution excitation spectra of the A-X 0-0, A-Y 0-0 and 0-1, and A-Z 0-0 and 0-1 transitions were obtained and a global fit to all the data yielded rotational constants for both ¹⁶²Dy³⁵Cl and ¹⁶⁴Dy³⁵Cl. From the band origins, vibrational frequencies of 291 and 284 cm⁻¹ were obtained for the Y[0.15]8.5 and Z[0.85]7.5 states, respectively, suggesting that these two states originate from the Dy⁺(4f¹⁰6s)Cl⁻ configuration. The ¹⁶²Dy-¹⁶⁴Dy and ³⁵Cl-³⁷Cl isotope effects were studied and both indicated a ground state, X7.5, vibrational frequency of ∼230 cm⁻¹ which was reinforced by the observation, in dispersed fluorescence from the B[15.4] state, of a weak transition to a state 233 cm⁻¹ above the ground state. The observed electronic states and their configurational origin are discussed in terms of ligand field theory predictions.     

Analysis of Raman scattering of Ga1−xMnxAs dilute magnetic semiconductor

Ferromagnetic Ga_1−xMn_xAs layers (where x=1.4-3.0%) grown on (1 0 0) GaAs substrates by molecular beam epitaxy were characterized using Raman spectroscopy. As Mn is introduced into GaAs, a marked increase in disorder in the material occurs, as indicated by the growth of the disorder-allowed transverse-optical Raman line. Another important result is that as the Mn concentration in Ga_1−xMn_xAs increases further beyond ca. 2%, Raman-active coupled-plasmon-longitudinal-optical phonon modes arise, which signals the increasing presence of holes, and thus provides a useful tool for determining their concentration. Using the depletion-layer approach from the Raman spectroscopy data, we determined the carrier concentration for samples with x=2.2% and 3.0% was to be 7.2×10¹⁹ and 8.3×10²⁰ cm⁻³, respectively.     

High-resolution infrared analysis of the ν7 band of cis-ethylene-d2 (cis-C2H2D2)

The spectrum of the ν₇ band of cis-ethylene-d₂ (cis-C₂H₂D₂) has been recorded with an unapodized resolution of 0.0063 cm⁻¹ in the 740-950 cm⁻¹ region using a Bruker IFS 125 HR Fourier transform infrared spectrometer. By fitting 2186 infrared transitions of ν₇ with a standard deviation of 0.00060 cm⁻¹ using a Watson’s A-reduced Hamiltonian in the I^r representation, accurate rovibrational constants for ν₇ = 1 state have been derived. The band center of ν₇ has been found to be 842.20957 ± 0.00004 cm⁻¹. In a simultaneous fit of 1331 infrared ground state combination differences from the present ν₇ transitions, together with 22 microwave frequencies, ground state constants have been improved. The rms deviation of the ground state fit was 0.00027 cm⁻¹.     

Effect of Cr implantation on structural and optical properties of AlN thin films

Molecular beam epitaxy (MBE) grown AlN thin layer on sapphire substrates have been implanted with Cr⁺ ions for various dose from 10¹³ to 10¹⁵ cm⁻². The analyses were carried out by an X-ray diffractometer (XRD), Raman spectroscopy, a spectrophotometer and spectroscopic ellipsometry (SE) for structural and optical analyses. E₂(high) and A₁(LO) Raman modes of AlN layer have been observed and analyzed. The behavior of Raman shift and the variation in intensity and in peak width of Raman modes as a function of ions flux are explained on the basis of chromium substituting aluminum atom and implantation-induced lattice damage. Both Raman and X-ray analyses reveal that the incorporation of chromium atoms increases in the host lattice with the increasing of Cr ions fluence. The band gap energy was determined by using transmission spectra. It was found that the band gap energy decreases as the ion dose increases. The band gap of the unimplanted AlN is 6.02 eV and it decreases down to 5.92 eV for the Cr⁺-implanted AlN with a ion dose of 1×10¹⁵ cm⁻². Optical properties such as optical constants of the samples were examined by using a spectroscopic ellipsometer. It was observed that the refractive index (n) decreases with the increasing of ion dose.     

High-resolution FTIR spectrum of the ν12 band of ethylene-d (C2H3D)

The infrared absorption spectrum of the ν₁₂ fundamental band of ethylene-d (C₂H₃D) has been recorded with an unapodized resolution of 0.004 cm⁻¹ in the wavenumber range of 1340-1460 cm⁻¹ using the Fourier transform technique. By assigning and fitting a total of 870 infrared transitions using a Watson’s A-reduced Hamiltonian in the I^r representation, three rotational and five quartic centrifugal distortion constants for the upper state (v₁₂ = 1) were determined for the first time. The rms deviation of the fit was 0.00044 cm⁻¹ which is close to the experimental precision of the absorption lines. The A-type ν₁₂ band centred at 1400.762811 ± 0.000041 cm⁻¹was found to be relatively free from local frequency perturbations. The inertial defect Δ₁₂ was found to be 0.20928 ±  0.00002 μŲ.     

The AB2-XA1 electronic transition of NO2: A rovibronic survey covering 14 300-18 000 cm

More than 250 rotationally resolved vibrational bands of the A²B₂-X²A₁ electronic transition of ¹⁵NO₂ have been observed in the 14 300-18 000 cm⁻¹ range. The bands have been recorded in a recently constructed setup designed for high resolution spectroscopy of jet cooled molecules by combining time gated fluorescence spectroscopy and molecular beam techniques. The majority of the observed bands has been rotationally assigned and can be identified as transitions starting from the vibrational ground state or from vibrationally excited (hot band) states. An exceptionally strong band is located at 14 851 cm⁻¹ and studied in more detail as a typical benchmark transition to monitor ¹⁵NO₂ in atmospheric remote sensing experiments. Standard rotational fit routines provide band origins, rotational and spin rotation constants. A subset of 177 vibronic levels of ²B₂ vibronic symmetry has been analyzed in the energy range between 14 300 and 17 250 cm⁻¹, in terms of integrated density and using Next Neighbor Distribution. It is found that the overall statistical properties and polyad structure of ¹⁵NO₂ are comparable to those of ¹⁴NO₂ but that the internal structures of the polyads are completely different. This is a direct consequence of the X²A₁-A²B₂ vibronic mixing.     

Structural and electrical transport properties of ZnxFe3−xO4 thin film deposited on Si (1 1 1) by pulsed-laser deposition

Polycrystalline thin films of Fe_3−xZn_xO₄ (x = 0.0, 0.01 and 0.02) were prepared by pulsed-laser deposition technique on Si (1 1 1) substrate. X-ray diffraction studies of parent as well as Zn doped magnetite show the spinel cubic structure of film with (1 1 1) orientation. The order–disorder transition temperature for Fe₃O₄ thin film with thickness of 150 nm are at 123 K (Si). Zn doping leads to enhancement of resistivity by Zn²⁺ substitution originates from a decrease of the carrier concentration, which do not show the Verwey transition. The Raman spectra for parent Fe₃O₄ on Si (1 1 1) substrate shows all Raman active modes for thin films at energies of T_2g¹, T_2g³, T_2g², and A_1g at 193, 304, 531 and 668 cm⁻¹. It is noticed that the frequency positions of the strongest A_1g mode are at 668.3 cm⁻¹, for all parent Fe₃O₄ thin film shifted at lower wave number as 663.7 for Fe_2.98Zn_0.02O₄ thin film on Si (1 1 1) substrate. The integral intensity at 668 cm⁻¹ increased significantly with decreasing doping concentration and highest for the parent sample, which is due to residual stress stored in the surface.     

Raman study of BiFeO3 with different excitation wavelengths

Raman spectra of bismuth ferrite (BiFeO₃) over the frequency range of 100-1500 cm⁻¹ have been systematically investigated with different excitation wavelengths. The intensities of the two-phonon modes are enhanced obviously under the excitation of 532 nm wavelength. This is attributed to the resonant behavior when incident laser energy closes to the intrinsic bandgap of BiFeO₃. The Raman spectra of BiFeO₃ excited at 532 nm were measured over the temperature range from 77 to 678 K. Besides the abnormal changes of the peak position and the linewidth of the A₁ mode at 139 cm⁻¹, the prominent frequency shift, the line broadening and the decrease of the intensity for the two-phonon mode at 1250 cm⁻¹ were observed as the temperature increased to Néel temperature (T_N). All these results indicate the existence of strong spin-phonon coupling in BiFeO₃.     

Optimal growth conditions for GdBa2Cu3O7 thin-film coated conductors characterized by polarized Raman scattering spectroscopy

High temperature superconducting GdBa₂Cu₃O₇ (GdBCO) thin films were grown by pulsed laser ablation. Textured MgO on metal substrates was used as a template for second generation wire applications. Growth conditions of GdBCO thin films were investigated for substrate temperature (T_s) and oxygen partial pressure (PO₂) during deposition. Superconducting critical currents of the films were obtained in the films grown at 790–810 °C of T_s and at 100–700 mTorr of PO₂. Scanning electron micrographs of the films revealed uniform and well-connected grains with some outgrown structures. X-ray θ–2θ scans of the films grown at 810 °C and 300–500 mTorr exhibited c-axis oriented texture. In-plane alignment and c-axis mosaic spread of the films were determined from X-ray Φ scans and rocking curves, respectively. Polarized Raman scattering spectroscopy was used to characterize optical phonon modes, oxygen content, cation disorder, and some possible second phases of the films. The Raman spectra of the films with large critical current density showed modes at 326–329 cm⁻¹, 444–447 cm⁻¹, 500–503 cm⁻¹ related to vibration of oxygen atoms. Origin of small peaks near 600 cm⁻¹ will be discussed as well. The information obtained from Raman scattering measurements will be useful for quality control of the conductors as well as optimization of the process conditions.     

The ν12 band of ethylene-1-C (CCH4) by high-resolution FTIR spectroscopy

The Fourier transform infrared (FTIR) spectrum of the ν₁₂ fundamental band of ethylene-1-¹³C (or ¹³C¹²CH₄) was recorded with an unapodized resolution of 0.0063 cm⁻¹ in the wavenumber region of 1360-1520 cm⁻¹. Rovibrational constants for the upper state (ν₁₂ = 1) up to five quartic and two sextic centrifugal distortion terms were derived for the first time by assigning and fitting a total of 879 infrared transitions using a Watson’s A-reduced Hamiltonian in the I^r representation. The root-mean-square deviation of the fit was 0.00066 cm⁻¹. The ground state rovibrational constants were also determined by a fit of 523 combination-differences from the present infrared measurements, with a rms deviation of 0.00090 cm⁻¹. The A-type ν₁₂ band which is centred at 1439.34607 ± 0.00004 cm⁻¹ was found to be relatively free from local frequency perturbations. From the ν₁₂ = 1 rovibrational constants obtained, the inertial defect Δ₁₂ was found to be 0.242826 ± 0.000002 μŲ.     

Infrared emission studies of the AΣ-XΠ electronic transition of the SiC radical

The gas phase infrared emission spectrum of the A³Σ⁻-X³Π electronic transition of SiC has been observed using a high resolution Fourier transform spectrometer. Three bands ν′ − ν″ = 0-1, 0-0, and 1-0 have been observed in the 2770, 3723, and 4578 cm⁻¹ regions, where the 0-1 and 0-0 bands were observed for the first time. The SiC radical was generated by a dc discharge in a flowing mixture of hexamethyl disilane [(CH₃)₆Si₂] and He. A total of 1074 rotational transitions assigned to the 0-1, 0-0, and 1-0 bands have been combined in a simultaneous analysis with previously reported pure rotational data to determine the molecular constants for SiC in the two electronic states. The principal equilibrium molecular constants for the A³Σ⁻ state are: B_e = 0.6181195(18) cm⁻¹, α_e = 0.0051921(20) cm⁻¹, r_e = 1.8020884(26) Å, and T_e = 3773.31(17) cm⁻¹, with one standard deviation given in parentheses. The effect of a perturbation was recognized between the ν = 4 level of X³Π and the ν = 0 level of A³Σ, and the analysis was carried out to determine the interaction parameter between the two states.     

Raman scattering in TlInS2xSe2(1−x) layered mixed crystals (0.25≤x≤1): Compositional dependence of the mode frequencies and line widths

The Raman spectra of TlInS_2xSe_2(1−x) layered mixed crystals were studied for a wide composition range (0.25≤x≤1) in the frequency region 10-360 cm⁻¹ at room temperature. The shift of Raman-active phonon frequencies versus mixed crystals composition x were established. The effect of crystal disorder on the line width broadening of three high-frequency Raman-active modes is reported.     

The ν12 band of C2D4

The Fourier transform infrared (FTIR) absorption spectrum of the ν₁₂ fundamental band of ethylene-d₄ (C₂D₄) was recorded in the 1017-1137 cm⁻¹ region with an unapodized resolution of 0.0063 cm⁻¹. Upper state (v₁₂ = 1) rovibrational constants consisting of three rotational and five quartic constants were improved by assigning and fitting 2103 infrared transitions using Watson’s A-reduced Hamiltonian in the I^r representation. The band centre of the A-type ν₁₂ band is found to be 1076.98480 ± 0.00002 cm⁻¹. The present analysis covering a wider wavenumber range and higher J and K_c values yielded upper state constants including the band centre which are more accurate than previously reported. The rms deviation of the upper state fit is 0.00045 cm⁻¹. Improved ground state rovibrational constants were also determined from the fit of 1247 ground state combination differences (GSCD) from the presently-assigned infrared transitions of the ν₁₂ band of C₂D₄. The rms deviation of the GSCD fit is 0.00049 cm⁻¹. In the rovibrational analysis, local frequency perturbations were not detected even at high J and K_a values. The calculated inertial defect Δ₁₂ is 0.32551 ± 0.00001 μŲ. The line intensities of the individual transitions in the ν₁₂ band were measured and the band strength of 39.8 ± 2.0 cm⁻² atm⁻¹ was derived for the ν₁₂ band of C₂D₄.     

Fano line shape and anti-crossing of Raman active E2g peaks in the charge density wave state of NbSe2

Low energy Raman scattering from the ab-plane of the 2H polytype single crystal NbSe₂ has been investigated in the normal (N), incommensurate charge density wave (ICDW) and superconducting (SC) phases. The temperature dependence of the polarization resolved Raman response has been obtained for the excitation wavelength of 647 nm and fitted to phenomenological models for the E_2g and A_1g symmetry channels. The A_1g response can be fitted by a simple damped oscillator peak superimposed on continuous background. The E_2g response displays an anti-resonance interference pattern between the inter-layer phonon and the CDW-induced mode such that a hybridized configuration (Fano line shape [1]) is required for modelling. The polarization specific peak maxima positions and line widths as a function of temperature, deduced in this manner, are presented. Partial suppression of the electronic continuum scattering in the Raman shift range up to 110 cm⁻¹ in the A_1g symmetry channel and beyond 300 cm⁻¹ in the E_2g symmetry channel is indicative of high energy electronic states far away from the Fermi surface participating in the ICDW formation.     

Analysis of rotational structure in the high-resolution infrared spectrum and assignment of vibrational fundamentals of butadiene-2,3-C2

The 2,3-¹³C₂ isotopomer of butadiene was synthesized, and its fundamental vibrational fundamentals were assigned from a study of its infrared and Raman spectra aided with quantum chemical predictions of frequencies, intensities, and Raman depolarization ratios. For two C-type bands in the high-resolution (0.002 cm⁻¹) infrared spectrum, the rotational structure was analyzed. These bands are for ν₁₁ (a_u) at 907.17 cm⁻¹ and for ν₁₂ (a_u) at 523.37 cm⁻¹. Ground state and upper state rotational constants were fitted to Watson-type Hamiltonians with a full quartic set of centrifugal distortion constants and two sextic ones. For the ground state, A₀ = 1.3545088(7) cm⁻¹, B₀ = 0.1469404(1) cm⁻¹, and C₀ = 0.1325838(2)  cm⁻¹. The small inertial defects of butadiene and two ¹³C₂ isotopomers, as well as for five deuterium isotopomers as previously reported, confirm the planarity of the s-trans rotamer of butadiene.     

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm⁻¹ (A1g), 197 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 515 cm⁻¹ (A1g), and 640 cm⁻¹ (Eg) assigned to anatase which were replaced by bands at 143 cm⁻¹ (B1g), 235 cm⁻¹ (2 phonon process), 448 cm⁻¹ (Eg) and 612 cm⁻¹ (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process.