Controlling the absorption and emission properties of polyparaphenylenevinylene films

In this work we used the conversion process of a precursor polymer into polyparaphenylenevinylene (PPV) at low temperatures in order to control the effective conjugation degree of spin-casted PPV films. The absorption and emission spectra of the films were studied by following a partial substitution of chloride counterions from poly(xylylidene tetrahydrothiophenium chloride) (PTHT), used as a precursor, by sodium acid dodecylbenzenesulfonate (DBS), added as a surfactant salt. Upon controlling the DBS amount and conversion temperature (T_c) of PTHT/DBS to PPV films, the band gap of PPV changed from 409 to 506 nm, and 505 to 532 nm, values obtained from absorbance and emission measurements, respectively. Based on these experimental data, we proposed a physical model which represents the chemical structure of PPV as a distribution of conjugated chain segments (like oligomers) alternated by non-conjugated segments (structural defects and/or from the precursor polymer).     

Effects of thermal conversion on the metal/polymer interface of layer-by-layer PPV/DBS films

In this paper, the thermal conversion effects on the metal/polymer interface of poly(p-phenylene vinylene) (PPV) films were investigated. The substrates studied were: aluminum, indium–tin oxide, gold and glass (BK7). Layer-by-layer PPV films were processed from poly(xylylidene tetrahydrothiophenium chloride) and dodecylbenzenesulfonate with 5 and 20 layers. The thermal conversion treatment was performed at 110 °C and 230 °C. The films were investigated through emission spectra. Selectively, the emission occurred in large PPV segments and it showed a significant dependence on the film/metal interface. It was clear that this synthesis process reduced the metal degradation in the interface. The Huang–Rhys factor was estimated to demonstrate this effect.     

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd–PSS films were processed using the acid of poly(styrene sulfonate) – H–PSS and neodymium nitrate – Nd(NO₃)₃; the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV–Vis–NIR spectral region presents typical electronic transitions of Nd³⁺ ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N–O groups in the range of 1400–720 cm^?1, prove the permanence of Nd(NO₃)_x, with x = 1, 2 and/or 3, in the H–PSS matrix. UV–Vis site selective photoluminescence data indicate that the incorporation of Nd³⁺ introduces a blue shift in PSS emission (325–800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd³⁺ reabsorption and energy transfer effects between the PSS matrix and Nd³⁺ were also observed. The IR emission of Nd–PSS films at 1076 nm (⁴F_3/2 → ⁴I_11/2) present constant efficiency, independent on Nd³⁺ concentration. The Judd–Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd³⁺. Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix.     

Optical absorption in amorphous InN thin films

Amorphous indium nitride (a-InN) thin films were deposited onto different substrates at temperatures <325 K using RF magnetron sputtering at a rate 0.3–0.4 Å/s. X-ray diffraction patterns reveal that the films grown on the substrates are amorphous. The optical absorption edge, ‘bandgap’ energy, E_g, of a-InN has been determined by spectroscopic ellipsometry over the energy range 0.88–4.1 eV. The absorption coefficient was obtained by the analysis of the measured ellipsometric spectra with the Tauc–Lorentz model. The E_g was determined using the modified Tauc and Cody extrapolations. The corresponding Tauc and Cody optical bandgaps were found to be 1.75 and 1.72 eV, respectively. These values are in excellent agreement with the values of the bandgap energy obtained as fitting parameters in the Tauc–Lorentz model: 1.72 ± 0.006 eV as well as by using spectrophotometry (1.74 eV) and photoluminescence (1.6 eV). The spectral dependence of the polarized absorptivities was also investigated. We found that there was a higher absorptivity for wavelengths <725 nm. This wavelength, ∼725 nm, therefore indicates that the absorption edge for a-InN is about 1.70 eV. Thus, the average value of the measured optical absorption of a-InN film is approximately 1.68 ± 0.071 eV.     

Surface morphology of spin-coated As–S–Se chalcogenide thin films

Surface morphology and roughness of amorphous spin-coated As–S–Se chalcogenide thin films were determined using atomic force microscopy. Prepared films were coated from butylamine solutions with thicknesses d ∼ 100 nm and then annealed in a vacuum furnace at 45 °C and 90 °C for 1 h for their stabilization. The root mean square surface roughness analysis of surfaces of as-deposited spin-coated As–S–Se films indicated a very smooth film surface (with R_q values 0.42–0.45 ± 0.2 nm depending on composition). The nanoscale images of as-deposited films confirmed that surface of the films is created by domains with dimensions 20–40 nm, which corresponds to diameters of clusters found in solutions. The domain character of film surfaces gradually disappeared with increasing annealing temperature while the solvent was removed from the films. Middle-infrared transmission spectra recorded a decrease of intensities of vibration bands connected to N–H (at 3367 and 3292 cm⁻¹) and C–H (at 2965, 2935 and 2880 cm⁻¹) stretching vibrations. Temperature regions of solvent evaporation T = 60–90 °C and glass transformation temperatures T_g = 135–150 °C of spin-coated As–S–Se thin films were determined using a modulated differential scanning calorimetry.     

Fabrication and ionic conductivity of amorphous Li–Al–Ti–P–O thin film

Li⁺ ion conducting Li–Al–Ti–P–O thin films were fabricated on ITO-glass substrates at various temperatures from 25 to 400 °C by RF magnetron sputtering method. When the substrate temperature is higher than 300 °C, severe destruction of ITO films were confirmed by XRD (X-ray diffraction) and the abrupt transformation of one semi-circle into two semi-circles on the impedance spectra. These as-deposited Li–Al–Ti–P–O solid state electrolyte thin films have an amorphous structure confirmed by XRD and a single semicircle on the impedance spectra. Good transmission higher than 80% in the visible light range of these electrolyte thin films can fulfill the demand of electro-chromic devices. Field emission scanning electron microscopy and atomic force microscopy showed the denser, smoother and more uniform film structure with the enhanced substrate temperature. Measurements of impedance spectra indicate that the gradual increased conductivity of these Li–Al–Ti–P–O thin films with the elevation of substrate temperature from room temperature to 300 °C is originated from the increase of the pre-exponential factor (σ₀). The largest Li-ion conductivity can come to 2.46 × 10^? 5 S cm^? 1. This inorganic solid lithium ion conductor film will have a potential application as an electrolyte layer in the field such as lithium batteries or all-solid-state EC devices.     

Luminescence of Dy3+-doped GexGa5Se(95−x) glasses

Dysprosium doped Ge_xGa₅Se_(95?x) (x = 15–30) chalcogenide glasses were synthesized in this present work. The Vis–NIR transmission spectra, photoluminescence spectra and lifetime were measured. Glasses (x = 27.5, 29.17 and 30) doped with 0.2 wt% dysprosium ions shows relatively strong emission bands at 1146 and 1343 nm when pumped at 808 nm. The emission lifetime ranged from 440 to 540 μs. The oscillator strengths and intensity parameters Ω_t (t = 2, 4 and 6) were calculated using Judd–Ofelt theory.     

Optical characterization of sputtered amorphous aluminum nitride thin films by spectroscopic ellipsometry

We have measured and analyzed the optical constants and polarized optical properties of amorphous aluminum nitride (a-AlN) thin films deposited by RF reactive magnetron sputtering onto silicon(1 1 1) and glass substrates. The optical constants were obtained by analysis of the measured ellipsometric spectra in the wavelength range 300–1400 nm, using the Cauchy–Urbach model. Refractive indices and extinction coefficients of the films were determined to be in the range 1.80–2.11 and 8.6 × 10⁻³–1.5 × 10⁻⁵, respectively. Analysis of the absorption coefficient, in the wavelength range 200–1400 nm, shows the bandgap of a-AlN thin films to be 5.84 ± 0.05 eV. From the angle dependence of the p-polarized reflectivity we deduce a Brewster angle of 61° and a principal angle of 64°. Measurement of the polarized optical properties reveals a high transmissivity and very low absorptivity for a-AlN films in the visible and near infrared regions. X-ray diffraction analysis confirmed the amorphous nature of the films under study.     

Carbon-K NEXAFS measurements of a-CNx films formed from decomposition of BrCN in electron cyclotron resonance plasmas of He,Ne, and Ar

Amorphous carbon nitride (a-CN_x) films were formed from the decomposition of BrCN in the electron cyclotron resonance plasmas of He, Ne, and Ar. The local structures of these films were investigated by the carbon-K near edge X-ray absorption fine structure. It was found that the density of C=C bond in the film prepared with Ar plasma was 7–9 times larger than that with He or Ne plasmas. The [N]/([C] + [N]) ratios of films were estimated from the X-ray photoelectron spectra as 0.34 ± 0.05, 0.35 ± 0.04, and 0.28 ± 0.05 for the He, Ne, and Ar plasmas, respectively. It was found that C atoms in the sp²-hybridized state were incorporated into the two-dimensional and/or one-dimensional conjugated structures composed of ? C=N? in the cases of the He and Ne plasmas and of ? C=C? in the case of the Ar plasma. The compositions and the local structures of films can be explained in terms of a model based on the cyclazine-like network structures.     

2 μm spectroscopic investigation of Tm3+-doped tellurite glass fiber

TmF₃ doped TeO₂–ZnO–La₂O₃ (TZL) glasses and fibers have been prepared by the conventional melt-quenching and suction casting methods, respectively. 2 μm emission properties and energy transfer mechanisms of the TZL glasses and fibers have been analyzed and discussed. The oscillator strength, Judd–Ofelt parameters, radiative transition probability and radiative lifetime of Tm³⁺ have been calculated based on the absorption spectra and Judd–Ofelt theory. The maximum emission cross-section of Tm³⁺ is 6.9 × 10^?21 cm² near 2 μm. Emission spectra have been obtained from both TZL fibers and bulk glass when excited with a 794 nm pump. The results of 2 μm emission spectra indicate that the line width of Tm³⁺ measured in fibers is narrower than that in the bulk glass sample. The peak position of the emission spectra shifts to longer wavelength with increment of the fiber length.     

Broadband near-infrared emission from Bi–Er–Tm Co-doped germanate glasses

Bi–Er–Tm co-doped germanate glasses and Bi, Er, Tm singly doped glasses were prepared and characterized through absorption spectra, NIR emission spectra and decay lifetime. A super broadband near-infrared emission from 1000 nm to 1600 nm, covering the whole O, E, S, C, and L bands, was observed in the Bi–Er–Tm co-doped samples due to the result of the overlapping of the Bi related emission band (centered at 1300 nm), the emission from Er^{3+ 4}I_13/2 → ⁴I_15/2 transition (centered at 1534 nm) as well as the emission from Tm^{3+ 3}H₄ → ³F₄ transition (centered at 1440 nm), which is essential for broadly tunable laser sources and broadband optical amplifiers. The energy transfer process was also discussed at the end of the paper.     

Optical properties of microcrystalline 3C–SiC:H films measured by resonant photothermal bending spectroscopy

Optical absorption coefficient spectra of hydrogenated microcrystalline cubic silicon carbide (μc-3C–SiC:H) films prepared by Hot-Wire CVD method have been estimated for the first time by resonant photothermal bending spectroscopy (resonant-PBS). The optical bandgap energy and its temperature coefficient of μc-3C–SiC:H film is found to be about 2.2 eV and 2.3 × 10⁻⁴ eV K⁻¹, respectively. The absorption coefficient spectra of localized states, which are related to grain boundaries, do not change by exposure of air and thermal annealing. The localized state of μc-3C–SiC:H has different properties for impurity incorporation compared with that of hydrogenated microcrystalline silicon (μc-Si:H) film.     

Dielectric properties of bis(2,4 pentanedionato)copper(II) crystalline films grown on Si substrate for low-k applications

Bis(acetylacetonato)copper(II) thin films were prepared by sublimation at about 245 °C in vacuum on p-Si and glass substrates for dielectric and optical investigations. They were characterized by the X-ray diffraction (XRD) and energy-dispersion X-ray fluorescence (EDXRF) methods. The XRD pattern reveals that the prepared films were polycrystalline of monoclinic P2₁/n structure. The optical absorption spectrum of the prepared film was not identical to that of the molecular one, which identified by a strong absorption peak at 635 nm. The onset energy of the optical absorption of the complex was calculated by using Hamberg et al. method, which is usually used for common solid-state semiconductors and insulators. The dielectric properties for the complex as insulator were investigated on samples made in form of a metal-insulator-semiconductor (MIS) structure. The dielectric properties were studied in frequency range 1–1000 kHz and temperature range 298–333 K. The dielectric relaxation was analyzed in-terms of dielectric modulus M¹(ω). Generally, the present study shows that films of the complex grown on Si substrate are a promising candidate for low-k dielectric applications; it displays low-k value around 1.7 ± 0.1 at high frequencies.     

Spectroscopic properties of Yb3+ ions in halogeno-sulfide glasses

In this work, we report the optical properties of Yb³⁺ ions in halogeno-sulfide glasses of composition (75 − x)GeS₂–25Ga₂S₃–xCsCl (x = 5%, 10%, 15%, 20%, and 25% CsCl). This study includes an analysis of the influence of halide concentration on the absorption and emission cross-sections and lifetimes of Yb³⁺ ions. A blue shift of the absorption and emission bands and a decrease of the absorption and emission cross-sections and transition probability are observed as the halide concentration increases in the glass.     

Observation of HfO2 thin films by deep UV spectroscopic ellipsometry

Deep UV spectroscopic ellipsometry (SE) is used for structure change observations in thin hafnia (HfO₂) layers deposited by p-MOCVD on silicon substrate. The absorption edge E_g and most of the critical point transitions in HfO₂ are above 6 eV, which makes the extension to Deep UV SE (5–9 eV) very suitable. The phase mixture changes as function of thickness and deposition process temperature, deduced from SE correspond well to XRD and Angle Resolved (AR)-XPS spectroscopy observations. From the absorption spectra at 4.5 eV, defects such as oxygen vacancies are detected, whereas from XPS spectra the estimation of the O/Hf ratio follows the same trend. Deep UV SE reveals differences in the dielectric function with orthorhombic/monoclinic phase mixtures essentially with peaks at 7.5 and 8.5 eV. Quantum confinement originated from the grain size of the films and the excitonic origin of the 6 eV feature are discussed.     

FTIR and UV–VIS optical absorption spectra of gamma-irradiated MoO3-doped lead borate glasses

Structure and optical properties of MoO₃-doped lead borate glasses which contain high PbO content (60, 70 and 80%) have been studied using Fourier transform infrared (FTIR) and ultraviolet–visible (UV–VIS) spectroscopic tools. FTIR spectra reveal absorption bands which are characteristic for various structural units of borate network, mainly BO₃ triangles and BO₄ tetrahedra, in addition to the PbO_n (where n = 3 and/or 4) structural units. UV–VIS optical absorption spectra reveal broad intense charge transfer UV bands due to Pb^2 + ions in the range 320–385 nm. Within this range, molybdenum ions, preferably Mo^3 + and Mo^5 +, can interfere at about 360–385 nm. Additionally, molybdenum ions give a weak visible band at about 850–860 nm. The optical absorption spectra of the studied glasses show marked resistance to successive gamma irradiation up to 5 Mrad. This shielding behavior can be related to the present high content of the high atomic mass Pb^2 + ions. Changes in the atomic structure before and after gamma irradiation are described and explained.     

Vacuum-deposited poly(o-methoxyaniline) thin films: Structure and electronic properties

Thin poly(o-methoxyaniline) (POMA) films have been formed by thermovacuum deposition in the temperature range of 350–450 °C and at a pressure of 5 × 10^?5 Torr. The structure properties of vacuum deposited POMA films according to FTIR and UV–VIS spectra are similar to those observed for the emeraldine form of polyaniline. Current–voltage characteristics (I–V) of sandwichtype device ITO/POMA/A1 possess rectifying properties with the ideality factor ≈4 at room temperature. On the basis of the dependence of conductivity on frequency in the frequency range of 10 Hz to 1 MHz, it is shown that the Pollack–Pohl current flow hopping mechanism dominates in a polymer film; such mechanism is typical of non-ordered systems.     

Optical and electrical properties of as-prepared and annealed (Se80Te20)100 − xAgx (0 ≤ x ≤ 4) ultra-thin films

Optical and electrical properties of the (Se₈₀Te₂₀)_100 ? xAg_x (0 ≤ x ≤ 4) ultra-thin films have been studied. The ultra-thin films were prepared by thermal evaporation of the bulk samples. Thin films were annealed below glass transition temperature (328 K) and in between glass transition temperature and crystallization temperature (343 K). Thin films annealed at 343 K showed crystallization peaks for Se–Te–Ag phases in the XRD spectra. The transmission and reflection of as-prepared and annealed ultra-thin films were obtained in the 300–1100 nm spectral region. The optical band gap has been calculated from the transmission and reflection data. The refractive index has been calculated by the measured reflection data. It has been found that the optical band gap increases, but the refractive index, extinction coefficient, real and imaginary dielectric constant decrease with increase in Ag content. The optical band gap and refractive index show the variation in their values with increase in the annealing temperature. The extinction coefficient increases with increasing annealing temperature. The surface morphology of ultra-thin films has been determined using a scanning electron microscope (SEM). The measured dc conductivity, under a vacuum of 10^? 5 mbar, showed thermally activated conduction with single activation energy in the measured temperature range (288–358 K) and it followed Meyer–Neldel rule. The dc activation energy decreases with increase in Ag content in pristine and annealed films. The results have been analyzed on the bases of thermal annealing effects in the chalcogenide thin films.     

Optical properties of Er3+-doped alkali fluorophosphate glasses

A systematic study of the optical absorption and luminescence spectra of Er³⁺-doped alkali fluorophosphate glasses (RTFP) 50(NaPO₃)–10TeO₂–20AlF₃–19RF–1Er₂O₃ (R = Li, Na and K) has been performed. The phenomenological Judd–Ofelt intensity parameters have been determined from the spectral intensities of the absorption bands in order to calculate the radiative transition probabilities, radiative lifetimes and branching ratios for various excited luminescent states. Using the visible and near infrared emission spectra, full width at half maximum (FWHM), emission cross-sections (σ_e) and figure of merit (FOM) were evaluated and compared with other hosts. Especially, the numerical values of these parameters indicate that the emission transition ⁴I_13/2 → ⁴I_15/2 transition at 1.534 μm in Er³⁺-doped fluorophosphate glasses may be highly useful in optical communication. The decay characteristic of ⁴S_3/2 excited level has also been recorded and analyzed. The calculated and experimental lifetimes were compared in terms of quantum efficiencies and multiphonon relaxation rates.     

Radiation induced color centers in 50PbO–50P2O5 glass

The effect of γ-irradiation in the dose range of 5 kGy up to 25 kGy on the optical absorption spectra of 50PbO–50P₂O₅ glasses is reported. The spectral absorption of these glasses before and after γ-irradiation was measured in the spectral range of 300–900 nm at room temperature. The radiation induced absorption in this spectral range shown to consist of two bands centered approximately at 545 nm and 730 nm. The fundamental absorption edge shifts generally to lower energies with increasing γ-irradiation dose up to 25 kGy in this glass sample. The intensity of the induced absorption bands increases linearly with increasing γ-irradiation dose. The higher energy band (HEB) may be due to a hole in a singly bonded non-bridging oxygen distant from a modifier cation, while the lower energy band (LEB) is also due to a hole in similar oxygen which is interacting with a neighboring cation.