Structural and optical properties of thermal evaporated magnesium phthalocyanine (MgPc) thin films

X-ray powder diffraction (XRD) of MgPc indicated that the material in the powder form is polycrystalline with monoclinic structure. Miller indices, h k l, values for each diffraction peak in XRD spectrum were calculated. Thermal evaporation technique was used to deposit MgPc thin films. The XRD studies were carried out for MgPc thin films where the results confirm the amorphous nature for the as-deposited films. While, polycrystalline films orientated preferentially to (1 0 0) plane with an amorphous background were obtained for films annealed at 623 K for 3 h. Optical properties of MgPc thin films were characterised by using spectrophotometric measurements of transmittance and reflectance in the spectral range from 190 to 2500 nm. The refractive index, n, and the absorption index, k, were calculated. According to the analysis of dispersion curves, the parameters, namely; the optical absorption coefficient (α), molar extinction coefficient (?_molar), oscillator energy (E_os), oscillator strength (f), and electric dipole strength (q²) were also evaluated. The recorded absorption measurements in the UV-vis region show two well defined absorption bands of phthalocyanine molecule; namely the Q-band and the Soret (B-band). The Q-band showed its splitting characteristic (Davydov splitting), and ΔQ was obtained as 0.15 eV. The analysis of the spectral behaviour of the absorption coefficient (α), in the absorption region revealed indirect transitions. The transport and the near onset energy gaps were estimated as respectively 2.74 ± 0.02 and 1.34 ± 0.01 eV.     

Enhanced nonlinear optical responses in metal-glass nanocomposites

The “engineered” nonlinear nanocomposite materials with extremely large values of optical Kerr susceptibility and fast temporal responses that can be precisely tuned to satisfy the requirements of switching applications is of current interest in photonics. Metal quantum-dot composite glasses can exhibit enhanced optical susceptibility, χ⁽³⁾, whose real and imaginary parts are related to the intensity-dependent refractive index and two-photon absorption coefficient, respectively. Classical (dielectric) and quantum confinement effects come into play in the nonlinear optical responses of these nanocomposites. Metal nanocluster-glass composites have been synthesized by 200 keV Cu⁺ and 1.5 MeV Au⁺ ion implantations in fused silica glasses at a dose of 3 × 10¹⁶ ions/cm², followed by thermal annealing in reducing atmosphere to promote cluster growth. UV-Visible spectroscopy has revealed prominent linear absorption bands at characteristic surface plasmon resonance (SPR) frequencies signifying appreciable formation of copper and gold colloids in glass matrices. Third-order optical properties of the composite materials have been studied by Z-Scan and Anti-Resonant Interferometric Nonlinear Spectroscopy (ARINS) measurements. The sign of nonlinear refraction is readily obtained from the Z-Scan signatures. The ARINS technique utilizes the dressing of two unequal-intensity counter-propagating pulsed light beams with differential nonlinear phases, which occur upon traversing the sample if it exhibits nonlinear optical response. This difference in phase manifests itself in the intensity-dependent transmission. The nonlinear refractive index, nonlinear absorption coefficient, the real and imaginary parts of the third-order optical susceptibility have been extracted.     

The high-resolution FTIR spectrum of the ν6 band of C2H3D

The absorption spectrum of the ν₆ band of C₂H₃D centered near 1125.27674 cm⁻¹ in the 1100-1250 cm⁻¹ region was recorded with an unapodized resolution of 0.0063 cm⁻¹ using a Fourier transform infrared (FTIR) spectrometer. A total of 947 infrared transitions of the A-B hybrid-type band were assigned and fitted to upper-state (ν₆ = 1) rovibrational constants using a Watson’s A-reduced Hamiltonian in the I^r representation up to eighth-order centrifugal distortion terms. The b-type infrared transitions of the band were analyzed for the first time. The root-mean-square deviation of the fit was 0.00062 cm⁻¹. The ground-state rovibrational constants up to eighth-order terms were also obtained by a fit of 617 combination differences from the present infrared measurements, simultaneously with 21 microwave frequencies with a root-mean-square deviation of 0.00055 cm⁻¹. From this work, the upper-state (ν₆ = 1) and ground-state constants of C₂H₃D were derived with the highest accuracy, so far. The a- and b-type transitions of the hybrid ν₆ band were found to be relatively free from local frequency perturbations. The ratio of the a- to b-type vibrational dipole transition moments (μ_a/μ_b) was found to be 1.05 ± 0.10. From the ν₆ = 1 rovibrational constants obtained, the inertial defect Δ₆ was calculated to be 0.3570 ± 0.0008 μŲ.     

Influence of composition on electrical and optical properties of new chalcogenide thin films from Ge-Se-Tl system

Bulk Ge₂₀Se_80−xTl_x (x ranging from 0 to 15 at%) chalcogenide glasses were prepared by conventional melt quenching technique. Thin films of these compositions were prepared by thermal evaporation, on glass and Si wafer substrates at a base pressure of 10⁻⁶ Torr. X-ray diffraction studies were performed to investigate the structure of the thin films. The absence of any sharp peaks in the X-ray diffractogram confirms that the films are amorphous in nature. The optical constants (absorption coefficient, optical band gap, extinction coefficient and refractive index) of Ge₂₀Se_80−xTl_x thin films are determined by absorption and reflectance measurements in a wavelength range of 400-900 nm. In order to determine the optical gap, the absorption spectra of films with different Tl contents were analyzed. The absorption data revealed the existence of allowed indirect transitions. The optical band gap showed a sharp decrease from 2.06 to 1.79 eV as the Tl content increased from 0% to 15%. It has been found that the values of absorption coefficient and refractive index increase while the extinction coefficient decreases with increase in Tl content in the Ge-Se system. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. DC electrical conductivity of Ge₂₀Se_80−xTl_x thin films was carried out in a temperature range 293-393 K. The electrical activation energy of these films was determined by investigating the temperature dependence of dc conductivity. A decrease in the electrical activation energy from 0.91 to 0.55 eV was observed as the Tl content was increased up to 15 at% in Ge₂₀Se_80−xTl_x system. On the basis of pre-exponential factor, it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges.     

High-resolution FTIR measurement of the ν4 band of methylene fluoride-d2

A high-resolution (0.002 cm⁻¹) infrared absorption spectrum of methylene fluoride-d₂ (CD₂F₂) of the lowest fundamental mode ν₄ in the region from 460 to 610 cm⁻¹ has been measured on a Bruker IFS 120-HR Fourier transform infrared spectrometer. More than 3500 transitions have been assigned in this B-type band centered at 521.9 cm⁻¹. The data have been combined with upper state pure rotational measurements in a weighted least-squares fit to obtain molecular constants for the upper state resulting in an overall standard deviation of 0.00018 cm⁻¹. Accurate value for the band origin (521.9578036 cm⁻¹) has been obtained and inclusion of transitions with very high J (?60) and K_a (?34) values has resulted in improved precision for sextic centrifugal distortion constants, in particular D_K, H_KJ, and H_K.     

Optical,spectral and thermal properties of organic nonlinear optical single crystal: 2,3-Dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate

The potential organic nonlinear optical single crystal of 2,3-dimethoxy-10-oxostrychnidinium hydrogen oxalate dihydrate has been grown by slow evaporation solution growth technique (SEST) using ethanol–water solution at room temperature. The powder X-ray diffraction study reveals that the crystal belongs to orthorhombic system with non-centrosymmetric space group P2₁2₁2₁ and the cell parameters are a = 7.61 Å, b = 10.73 Å, c = 29.49 Å, V = 2410.75 Å³. The functional groups of the synthesized compound have been identified by FT-Raman and FTIR analyses. Photoluminescence spectroscopy study is determined to explore its efficacy towards device fabrications. Birefringence measurement has been carried out in order to analyze the optical homogeneity of the grown crystal. The optical constants such as reflectance (R) and extinction coefficient (K) have been determined from the transmittance data. The relative second harmonic efficiency of the compound is found to be 4 times greater than that of KDP. DTA-DSC measurements indicate that the crystal is thermally stable up to 174 °C.     

Y2O2S:Eu nanocrystals, a strong quantum-confined luminescent system

Trivalent europium-doped yttrium oxysulfide nanocrystals synthesized using sol-gel thermolysis show significant blue shifts in the excitation bands corresponding to fundamental absorption, charge-transfer absorption. A significant blue shift observed in the fundamental absorption edge for the nanocrystals having an average crystallite size (φ) in the range 9-15 nm indicates a strong quantum confinement with a Bohr exciton radius of 5-13 nm. Also, the diffuse reflectance spectra and the corresponding Kubelka-Munk plot indicate the possibility of profound decrease in the absorption coefficient of Eu³⁺-ligand charge-transfer species necessitating further studies in this wide-gap semiconductor nanocrystalline system.     

O2A-band line parameters to support atmospheric remote sensing

Numerous satellite and ground-based remote sensing measurements rely on the ability to calculate O₂A-band [b¹Σ_g⁺←X³Σ_g⁻(0,0)] spectra from line parameters, with combined relative uncertainties below 0.5% required for the most demanding applications. In this work, we combine new ¹⁶O₂A-band R-branch measurements with our previous P-branch observations, both of which are based upon frequency-stabilized cavity ring-down spectroscopy. The combined set of data spans angular momentum quantum number, J′ up to 46. For these measurements, we quantify a J-dependent quadratic deviation from a standard model of the rotational distribution of the line intensities. We provide calculated transition wave numbers, and intensities for J′ up to 60. The calculated line intensities are derived from a weighted fit of the generalized model to an ensemble of data and agree with our measured values to within 0.1% on average, with a relative standard deviation of ≈0.3%. We identify an error in the calculated frequency dependence of the O₂A-band line intensities in existing spectroscopic databases. Other reported lineshape parameters include a revised set of ground-state energies, self- and air-pressure-broadening coefficients and self- and air-Dicke-narrowing coefficients. We also report a band-integrated intensity at 296 K of 2.231(7)×10⁻²² cm molec⁻¹ and Einstein-A coefficient of 0.0869(3) s⁻¹.     

Anisotropic nonlinear optical absorption of gold nanorods in a silica matrix

Nanocomposite films consisting of gold nanospheres or gold nanorods embedded in a silica matrix have been prepared using a hybrid deposition technique consisting of plasma-enhanced chemical vapor deposition of SiO₂ and co-sputtering of gold, followed by annealing at 900 °C. Subsequent irradiation with 30 MeV heavy ions (Cu⁵⁺) was used to form gold nanorods. Linear and nonlinear optical properties of this material are closely related with the surface plasmon resonance in the visible. The nonlinear absorption coefficient (α₂@532 nm) for the films containing gold nanospheres was measured by Z-scan and P-scan techniques, and it was found to be isotropic and equal to −4.8 × 10⁻² cm/W. On the contrary, gold nanorods films exhibited two distinct surface plasmon resonance absorption bands giving rise to a strong anisotropic behavior, namely a polarization-dependent linear absorption and saturable absorption. Z-scan and P-scan measurements using various light polarization directions yielded nonlinear absorption coefficient (α₂@532 nm) values varying from −0.9 × 10⁻² cm/W up to −3.0 × 10⁻² cm/W. Linearity of the P-scan method in the context of nanocomposite saturable absorption is also discussed.     

Optical properties of methane to 288 GPa at 300 K

Optical properties of solid methane (CH₄) were studied at high pressure and room temperature using a diamond anvil cell. Reflectivity and transmission measurements were used to measure the refractive index to 288 GPa. Fabry-Perot interferometery was used to measure the sample thickness to 172 GPa. This data was fitted to the derived expression of thickness vs. pressure that was then used to calculate the thickness to 288 GPa. This in turn was combined with optical absorption experiments to obtain the absorption coefficient and hence the extinction coefficient k^*. From combined reflection and absorption experiments the refractive index n=n_s+ik^* was obtained. The index of refraction and the ratio of molar refraction to molar volume showed a large increase between 208 and 288 GPa. This behavior indicated that a phase transformation of insulator-semiconductor might have occurred in solid CH₄ by 288 GPa.     

Measurements of optical parameters of phantom solution and bulk animal tissues in vitro at 650 nm

Optical parameters of bulk animal tissue in vitro, including absorption coefficient (μ_a), reduced scattering coefficient (μ′_s) or scattering coefficient (μ_s), total attenuation coefficient (μ_t), anisotropy factor (g) and refractive index (n) are measured at wavelength of 650 nm. Clinical Intralipid-10% is diluted in distilled water into different concentrations to use as tissue phantoms. Four types of animal tissues in vitro are studied. The relationships among the optical parameters are analyzed systemically. For animal tissues, μ_a, μ′_s or μ_s and n rely on muscle fiber orientations. μ_s and μ_t range from 10 to 20 mm⁻¹, μ_a from 10⁻² to 10⁻³ mm⁻¹ and g from 0.95 to 0.99.     

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.     

Pulsed laser deposition of polyhydroxybutyrate biodegradable polymer thin films using ArF excimer laser

We demonstrated the pulsed laser deposition (PLD) of high quality films of a biodegradable polymer, the polyhydroxybutyrate (PHB). Thin films of PHB were deposited on KBr substrates and fused silica plates using an ArF (λ = 193 nm, FWHM = 30 ns) excimer laser with fluences between 0.05 and 1.5 J cm⁻². FTIR spectroscopic measurements proved that at the appropriate fluence (0.05, 0.09 and 0.12 J cm⁻²), the films exhibited similar functional groups with no significant laser-produced modifications present. Optical microscopic images showed that the layers were contiguous with embedded micrometer-sized grains. Ellipsometric results determined the wavelength dependence (λ ∼ 245-1000 nm) of the refractive index and absorption coefficient which were new information about the material and were not published in the scientific literature. We believe that our deposited PHB thin films would have more possible applications. For example to our supposal the thin layers would be applicable in laser induced forward transfer (LIFT) of biological materials using them as absorbing thin films.     

Cavity ring down absorption spectroscopy of the BΣ-XΣ transition of YO

The absorption spectrum of the (2, 0) and (2, 1) bands of the B²Σ⁺-X²Σ⁺ transition of YO between 442 and 478 nm were recorded using laser vaporization/reaction with free-jet expansion and cavity ring down laser absorption spectroscopy. Local rotational perturbations have been found for both spin components of the v = 2 level of the B²Σ⁺ state. The observed perturbations could be ascribed to a degenerate perturbing state interacting with the B²Σ⁺ state. Least-squares fit of the observed upper state term values yielded molecular constants for the v = 2 level of the B²Σ⁺ state and the perturbing ²Π state. Earlier ab initio calculations [J. Chem. Phys. 89 (1988) 2160] indicated that the C²Π state is nearby, it is plausible that the C²Π state is the perturbing state.     

The synthesis, characterization and optical properties of novel 1,3,4-oxadiazole-containing imidazo[1,5-a]pyridine derivatives

A series of novel substituted 1,3,4-oxadiazole derivatives were synthesized by the reaction of 3-butyl-1-chloroimidazo[1,5-a]pyridine-7-carbohydrazide with propionyl chloride and substituted benzoic chloride in the presence of phosphorus oxychloride. The compounds were characterized using IR, ¹H NMR, ¹³C NMR and HRMS. Absorption and fluorescence spectra were measured in dichloromethane; an intense absorption maxima was noted at ca. 290 nm and emission maxima was noted at ca. 470 nm. The absorption spectra of the 1,3,4-oxadiazole derivatives reveal that a phenyl and an ethyl group attached to the 1,3,4-oxadiazole ring markedly influenced the maximum absorption. The structures based on density function theory (DFT) calculation show planar configurations for the compounds. The calculated molecular orbital correlates well with their absorption.     

Nonlinear optical studies of a newly synthesized copolymer containing oxadiazole and substituted thiophenes

We investigated the third-order nonlinear optical properties of a newly synthesized soluble copolymer containing oxadiazole and thiophene units using Z-scan and Degenerate Four Wave Mixing (DFWM) techniques. The measurements were performed at 532 nm with 7 ns pulses from a Nd:YAG laser. We found a good agreement between the values of χ⁽³⁾ determined from both experiments. Z-scan results indicate a negative nonlinear refractive index, n₂, whose magnitude is of the order of 10⁻¹⁰ esu. The copolymer exhibits strong nonlinear absorption and good optical limiting properties at 532 nm, and hence may be a potential material for optical limiting applications.     

Absolute line intensities of HONO and DONO in the far-infrared and re-determination of the energy difference between the trans- and cis-species of nitrous acid

Relative line intensities of trans- and cis-HONO and -DONO have been measured using absorption spectra in the far-infrared previously recorded by high-resolution Fourier-transform spectroscopy [A. Dehayem-Kamadjeu, O. Pirali, J. Orphal, I. Kleiner, P.-M. Flaud, J. Mol. Spectrosc. 234 (2005) 182-189]. These relative, experimental line intensities (120 lines for trans-HONO and 94 for cis-HONO, as well as 46 lines for trans-DONO and 31 for cis-DONO) were then least-squares fitted leading to the determination of “relative” permanent dipoles moments (b-component) and their rotational corrections for the trans- and cis-HONO and -DONO species. Then these “relative” permanent dipoles moments and their rotational corrections were scaled to the absolute values derived from Stark effect measurements [M. Allegrini, J.W.C. Johns, A.R.W. McKellar, P. Pinson, J. Mol. Spectrosc. 79 (1980) 446-454] and used to generate “absolute” line intensities. These “absolute” line intensities were used to derive the concentrations of the trans- and cis-species in the absorption cell. It was then possible, assuming thermodynamic equilibrium, to use the ratio of the concentrations of the trans- and cis-species to re-determine the energy differences (ΔE) between the ground vibrational states of trans- and cis-HONO: these energy differences are 99 ± 25 cm⁻¹ for HONO and 136 ± 30 cm⁻¹ for DONO. Finally applying zero-point-energy corrections we report an average value for ΔE_HONO of 107 ± 26 cm⁻¹. This value is in good agreement with previous experimental studies and with recent high-level ab initio calculations.     

Adsorption and photocatalytic degradation of methylene blue on Zn1−xCuxS nanoparticles prepared by a simple green method

Nanoparticles of Zn_1−xCu_xS with various dopant contents (0 ≤ x ≤ 0.15) were prepared in water by refluxing for 90 min at about 95 °C. Powder X-ray diffraction (XRD) patterns of the nanoparticles demonstrate that loading of Cu²⁺ ions does not change the crystal structure of ZnS. Scanning electron microscopy (SEM) images demonstrate that size of the nanoparticles decreases with increasing Cu²⁺ ions. UV-Vis diffuse reflectance spectra (DRS) of the nanoparticles show significant absorption in visible light region. Adsorption capacity of the nanoparticles for methylene blue (MB) increases with mole fraction of copper ions. Photocatalytic activity of the nanoparticles toward photodegradation of MB was evaluated under visible light irradiation. The results indicate that Zn_0.85Cu_0.15S nanoparticles exhibit highest photocatalytic activity among the prepared samples. Moreover, effects of refluxing time applied for preparation of the nanoparticles and calcination temperature were investigated.     

Opto-thermal modulation in biological photonic crystals

Photonic structures of biological origin have been well studied for their optical and morphological properties, but light-induced effects have not yet been explored. In this study, we report sizeable modulation in reflectance on iridescent areas of the wing of a butterfly Morpho didius. Chitin, the primary constituent of the sample, exhibits the large thermo-optic effect typically seen in biopolymers. Measurements yield a thermo-optic coefficient of dn/dT = −4.7 × 10^− 4 °C^− 1. Relatively low intensity levels (~ 0.05 W/cm²) are therefore required to induce measurable reflectance changes, which take place only in the iridescence spectral range and only in areas where chitin is periodically textured. This confirms that the effect originates from photonic band-shifting. For comparison purposes, Kerr nonlinearity is also investigated in chitin and chitosan films.     

Effect of annealing on the properties of N-doped ZnO films deposited by RF magnetron sputtering

N-doped ZnO films were deposited by RF magnetron sputtering in N₂/Ar gas mixture and were post-annealed at different temperatures (T_a) ranging from 400 to 800 °C in O₂ gas at atmospheric pressure. The as-deposited and post-annealed films were characterized by their structural (XRD), compositional (SIMS, XPS), optical (UV-vis-NIR spectrometry), electrical (Hall measurements), and optoelectronic properties (PL spectra). The XRD results authenticate the improvement of crystallinity following post-annealing. The weak intensity of the (0 0 2) reflection obtained for the as-deposited N-doped ZnO films was increased with the increasing T_a to become the preferred orientation at higher T_a (800 °C). The amount of N-concentration and the chemical states of N element in ZnO films were changed with the T_a, especially above 400 °C. The average visible transmittance (400-800 nm) of the as-deposited films (26%) was increased with the increasing T_a to reach a maximum of 75% at 600 °C but then decreased. In the PL spectra, A⁰X emission at 3.321 eV was observed for T_a = 400 °C besides the main D⁰X emission. The intensity of the A⁰X emission was decreased with the increasing T_a whereas D⁰X emission became sharper and more optical emission centers were observed when T_a is increased above 400 °C.