Analysis of the absorption and emission spectra of poly(p-phenylene vinylene) films thermally converted at a relatively low temperature

In this work, we studied the absorption and emission spectra of spin-coated poly(p-phenylene vinylene) (PPV)–dodecylbenzenesulfonic counter-ion (DBS) films. The PPV–DBS films were obtained from a soluble precursor polymer thermally converted to PPV over a comparatively short time interval (30 min), and at low temperature (110 °C), conditions that yielded films with few structural defects. The line shape of the absorption spectra of the films deposited on glass substrates was analyzed by assuming a Gaussian distribution of segments along the main chain of PPV, and a conjugation degree between 3 and 15 units. For emission studies, only PPV segments with a high conjugation degree or a lower energy gap (HOMO–LUMO transition) contributed to the feature of the spectra.     

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).     

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.     

Electronic states in a-Si:H/c-Si heterostructures

We have investigated PECVD-deposited ultrathin intrinsic a-Si:H layers on c-Si substrates using UV-excited photoemission spectroscopy (hν = 4–8 eV) and surface photovoltage measurements. For samples deposited at 230 °C, the Urbach energy is minimal, the Fermi level closest to midgap and the interface recombination velocity has a minimum. The a-Si:H/c-Si interface density of states is comparable to that of thermally oxidized silicon interfaces. However, the measured a-Si:H dangling bond densities are generally higher than in thick films and not correlated with the Urbach energy. This is ascribed to additional disorder induced by the proximity of the a-Si:H/c-Si interface and H-rich growth in the film/substrate interface region.     

Correlation between the method of preparation and the properties of the sol–gel HfO2 thin films

This work describes the preparation of HfO₂ thin films by the sol–gel method, starting with different precursors such as hafnium ethoxide, hafnium 2,4-pentadionate and hafnium chloride. From the solution prepared as mentioned above, thin films on silicon wafer substrates have been realized by ‘dip-coating’ with a pulling out speed of 5 cm min^?1. The films densification was achieved by thermal treatment for 10 min at 100 °C and 30 min at 450 °C or 600 °C, with a heating rate of 1 °C min^?1. The structural and optical properties of the films are determined employing spectroellipsometric (SE) measurements in the visible range (0.4–0.7 μm), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The main objective of this paper was to establish a correlation between the method of preparation (precursor, annealing temperature) and the properties of the obtained films. The samples prepared from pentadionate and ethoxide precursors are homogenous and uniform in thickness. The samples prepared starting from chloride precursor are thicker and proved to be less uniform in thickness. Higher non-uniformity develops in multi-deposition films or in crystallized films. A nano-porosity is present in the quasi-amorphous films as well in the crystallized one. For the samples deposited on silicon wafer, the thermal treatment induced the formation of a SiO₂ layer at the coating–substrate interface.     

Structural investigations of nitrided Nb2O5 and Nb2O5–SiO2 sol–gel derived films

Sol–gel derived xNb₂O₅–(100 ? x)SiO₂ films (where x = 100, 80, 60, 50, 40, 20, 0 mol%) were nitrided at various temperatures (800 °C, 900 °C, 1000 °C, 1100 °C and 1200 °C). The structural transformations occurring in the films as a result of ammonolysis were studied using X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The XRD results have shown that the temperatures below 1100 °C were too low to obtain a pure NbN phase in the samples. The AFM observations indicate that the formation of the NbN phase and the size of NbN grains are related to the silica content in the layer. NbN grains become more regular and larger as the niobium content increases. The maximum grain size of about 100 nm was observed for x = 100. Preparation of the Nb₂O₅–SiO₂ sol–gel derived layers and the subsequent nitridation is a promising method of inducing crystalline NbN in amorphous matrices. It follows from the XPS results that a small amount of Nb₂O₅ remains in the films after nitridation at 1200 °C and that nitrogen reacted not only with Nb₂O₅ but also with SiO₂.     

Effect of vacuum annealing on charge transport and trapping in a-Si1 − xCx:H/c-Si heterostructures

The processes of charge transport and trapping in amorphous Si_1 ? xC_x:H films deposited on crystalline p-type Si wafers and annealed in vacuum in the temperature range 300–650 °C have been evaluated. Current–voltage (I–V), capacitance–voltage (C–V) and admittance–temperature (G–T) characteristics were measured in the temperature range 100–350 K. The spectrum of thermal effusion of hydrogen was measured from room temperature up to 1000 °C.C–V characteristics indicate a slight increase of the dielectric constant k and a large hysteresis after annealing at 450 °C. The hysteresis is believed to be associated with mobile hydrogen effusion from the a-SiC:H film, and it is not seen after a 650 °C anneal. From I–V data the maximum rectification ratio is observed after annealing at 450 °C. Variable-range hopping (VRH) conduction at the Fermi level is found to dominate the forward current of the as-deposited structure. After annealing at 450 °C the forward current can be described by space-charge limited (SCL) mechanisms with trapping at shallow levels with energy of about 0.12 eV. After annealing at 650 °C the process of VRH conduction appears again, but the density of hopping sites is much higher than in the as-grown sample. From admittance spectra, the energy position of respective traps in a-SiC:H is at (E_V + 0.45) eV for as-deposited material and it decreases slightly after vacuum annealing. On the basis of these results, an energy band diagram of the a-Si_1 ? xC_x:H/p-Si structure annealed at 450 °C is proposed.     

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.     

Systematic study of spectroscopic properties and thermal stability of lead germanate glass doped with rare-earth ions

Glasses with composition 50GeO₂–(50?x)PbO–5PbF₂–xLnF₃ (Ln = Pr³⁺–Yb³⁺) were prepared from commercial raw materials. The content of PbF₂ was constant and amounted to 5 mol% whereas the concentration of luminescent ions was diverse (0.2 and 2 mol%). Thermal stability of the glasses were monitored by differential thermal analysis (DTA). It has been found that increase of rare-earth fluoride content from 0.2 mol% to 2 mol% brings about a shift of the glass crystallization onset from 450 °C to 487 °C for Nd-doped samples and from 466 °C to 482 °C for Tm-doped samples. Optical absorption and emission spectra of Ln active ions in oxyfluoride glass have been investigated at room temperature in the ultraviolet (UV), visible (VIS) and near-infrared (NIR) region. Oscillator strengths, phenomenological Judd–Ofelt intensity parameters Ω_2,4,6, radiative transition probabilities, branching ratios and radiative lifetimes of luminescent levels have been estimated. Analysis of decay curves of luminescence revealed that the increase of rare-earth fluoride content from 0.2 mol% to 2 mol% shortens the lifetime of the ⁴F_3/2 level of Nd³⁺ from 224 μs to 90 μs.     

Effect of isothermal annealing and visible-light illumination on the AC-impedance behavior of undoped selenium thin films

The effect of post-deposition isothermal annealing (30 °C ? T_A ? 70 °C) and visible-light illumination on the complex AC-impedance of undoped selenium thin films deposited at the substrate temperatures T_S = 30, 50, 70 °C has been studied in the frequency range 0.2–12 kHz. The AC-impedance of amorphous selenium (a-Se) films (T_S, T_A < 50 °C) was mainly capacitive, with no loss peaks being observed in their Z″(ω)–ω curves, irrespective of illumination. This behavior was ascribed to a dominant charge-carrier trapping effect of bulk/surface charged defects usually present in a-Se. On the other hand, the measured Z″(ω)–Z′(ω) diagrams of illuminated polycrystalline Se samples (50 °C ? T_S, T_A ? 70 °C) exhibited almost full semicircles, whereas their Z″(ω)–ω curves revealed prominent loss peaks at well-defined frequencies. As the annealing temperature or light intensity is increased the loci of the points determined by intersections of these semicircles with the Z′-axis at the low-frequency side shift greatly towards the origin, while the loss-peak positions shift to higher frequencies. These experimental findings were explained in terms of a significant increase in electrical conductivity of selenium films due to thermally-induced crystallization at temperatures beyond glass-transformation region of undoped selenium and to creation of electron–hole pairs by visible-light illumination.     

Nanostructural and optical features of amorphous AlxSi0.45−xO0.55 (0 ⩽ x ⩽ 0.05) thin films prepared by RF-magnetron sputter techniques

The nanostructural, chemical, and optical features of Al_xSi_0.45−xO_0.55 (0 ⩽ x ⩽ 0.05) thin films were investigated in terms of Al concentration and post-deposition annealing conditions; the films were prepared by co-sputtering a Si main target and Al-chips, and the annealing was carried out at temperatures of 400–1100 °C. The a-Si_0.45O_0.55 films prepared without Al-chips and annealed at 800 °C contain ∼3.5 nm-sized Si nanocrystallites. The photoluminescence (PL) intensity as well as the volume fraction of Si nanocrystallites increased with increasing the concentration of Al to a certain level. In particular, the intensity of the PL spectra of the Al_0.025Si_0.425O_0.550 films which were annealed at 800 °C increased significantly at wavelengths of ∼580 nm. It is highly likely that the observed increase in the PL intensity is caused by the raise in the total volume of the ∼3.5 nm-sized nanocrystallites in the films. The addition of Al as well as the post-deposition annealing allow adjustment and control of the nanostructural and light-emission features of the a-SiO_x films.     

Semi-interpenetrating polymer networks based on polyurethane and poly(2-hydroxyethyl methacrylate): Dielectric study of relaxation behavior

The study of molecular dynamics by broadband dielectric spectroscopy (BDS) is presented for polyurethane (PU), poly(2-hydroxyethyl methacrylate) (PHEMA) and for semi-IPNs based on PU and PHEMA synthesized by photopolymerization. The dielectric properties were performed in wide range of frequencies and temperatures with the goal to establish the relation between the relaxations and the structure. Five relaxation phenomena were finally detected for PHEMA : γ-, βsw-, β-relaxations at low temperatures and α-relaxation at 150 °C at high frequencies plus ionic conductivity relaxation which starts at 0 °C. For semi-IPNs the overlapping of γ- and βsw-relaxations of PHEMA (?125/?75 °C), then with increasing the temperature α-relaxation in PU (?75/0 °C), next ionic conductivity relaxation which starts at 0 °C, and finally the α-relaxation of PHEMA (+125/+170 °C) were detected. The α-relaxation of PHEMA in semi-IPNs shifts to lower temperatures and became broader with increasing amount of PU due to incomplete phase separation in the system and formation of interphases. The dielectric relaxation phenomena were fitted with Havriliak–Negami equation. Activation energy, τ_o and α parameters were calculated. For α-relaxations corresponding dielectric characteristics have been determined from Vogel–Fulcher–Tammann equation. The relaxation map for investigated PU, PHEMA and semi-IPNs was built.     

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.     

Dielectric relaxation and electro-optical switching behavior of nematic liquid crystal dispersed in poly(methyl methacrylate)

Polymer dispersed liquid crystal composite films were prepared from poly(methyl methacrylate) and nematic liquid crystal E44 by solvent induced phase separation method. In the present investigation we report effect of liquid crystal concentration on the electro-optical and dielectric properties of the composite films. The results were interpreted in terms of phase separation of liquid crystal and polymer, shape and size of liquid crystal droplet, interfacial charge layer effect, liquid crystal loading and miscibility of liquid crystal in the polymer matrix. The miscibility between two phases at interface was investigated by employing Fourier‐Transform Infrared Spectroscopy and differential scanning calorimetry. Morphological study showed that liquid crystal phase is embedded in a spongy poly(methyl methacrylate) matrix and homogeneous distribution increased with increasing E44 content. Electro optical behavior of these composite films under the condition of an externally applied AC electric field (0–200 Vp-p, 50–1000 Hz) and wide range of temperature was determined using He–Ne laser (wave length 632.8 nm) as a light source. It was found that Poly(methyl methacrylate)/E44 (30/70) wt.% composite has more significant properties than the other concentrations. The performance of all composites showed variations with respect to applied voltage as well as temperatures. Dielectric measurement of polymer dispersed liquid crystals has been carried out in the frequency range from 20 Hz to 20 MHz and over the temperature range from 24 °C to 100 °C. The Maxwell–Wagner effect due to interfacial charge accumulation between boundaries of liquid crystal droplets and surrounding of polymer matrix has been observed.     

ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.     

Thermo-mechanical behavior of uniaxially drawn and crystallized poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) films

Thermo-mechanical properties of poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) films in the amorphous state, uniaxially stretched and thermally crystallized were compared and show different microstructure–property relationships. The glass transition temperature shifts to higher temperatures when films are stretched above T_g at 160 °C, in relation with a crystallinity increase and subsequent confinement effects of the amorphous phase, but films stretched below T_g at 100 °C show an opposite trend while drawing. This is discussed in relation with the highly mobile structural state arising from plastic deformation of the amorphous phase. The confinement effects were particularly assessed by the estimation of a ‘rigid amorphous fraction’ (RAF). Crystallinities and RAF were estimated from DSC data for the uniaxially drawn and thermally crystallized films respectively. It was observed that the RAF was higher in thermally crystallized films than in uniaxially drawn samples in relation to a lamellar semi-crystalline morphology. In addition to this detailed thermo-mechanical characterizations, low stress creep measurements were carried out during heating scans. They can be related to the microstructure and thermal transitions of the films. In particular, for the uniaxially stretched films, the measured shrinkage decreases when the draw ratio increases because the crystalline entities developed during the draw process are locking the chain motions.     

Diffusion barrier properties of amorphous ZrCN films for copper metallization

A novel amorphous zirconium carbon nitrides (ZrCN) material was deposited by reactive sputtering using a ZrC target (99.5% in purity) in a mixture of Ar and N₂ ambient. The microstructure and mechanical properties of the ZrCN films were examined with respect to N₂ pressure. For thermal stability characterization, the stacked structure of Cu/ZrCN/Si was subsequently subject to thermal treatments at temperatures from 300 °C to 900 °C for 30 min in a vacuum tube with the base pressure of 3 × 10⁻⁵ torr. The results show that the amorphous ZrCN films exhibit superior mechanical properties to either ZrN or ZrC including hardness and elastic modulus. The stacked samples were shown to be thermally stable up to about 800 °C from Auger electron spectroscopy and X-ray diffraction, where the ZrCN still remains its amorphous phase. The device completely fails at 900 °C and the mechanism is discussed in the paper.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Plasma enhanced chemical vapor deposition of ZnO thin films

Zinc oxide thin films were deposited on silicon and corning-7059 glass substrates by plasma enhanced chemical vapor deposition at different substrate temperatures ranging from 36 to 400 °C and with different gas flow rates. Diethylzinc as the source precursor, H₂O as oxidizer and argon as carrier gas were used for the preparation of ZnO films. Structural and optical properties of these films were investigated using X-ray diffraction, reflection high energy electron diffraction, atomic force microscopy and photoluminescence. Highly oriented films with (0 0 2) preferred planes were obtained on silicon kept at 300 °C with 50 ml/min flow rate of diethylzinc without any post annealing. Reflection high energy electron diffraction pattern also showed the crystalline nature of these films. A textured surface with rms roughness ∼28 nm was observed by atomic force microscopy for the films deposited at 300 °C. A sharp peak at 380 nm in the PL spectra indicated the UV band-edge emission.     

Epitaxial growth of the metastable phase ytterbium monoxide on gallium nitride surfaces

Molecular beam deposition systems allow for unparalleled control of film composition and structure. This article addresses the capacity for controlling metal and oxidant fluxes in the Yb/O₂ system to access the metastable phase ytterbium monoxide (YbO). Experiments exploring the growth of polycrystalline YbO_x films by molecular beam deposition demonstrate that a 2:1 molar ratio of Yb:O₂ fluxes is necessary to achieve preferential growth of the divalent oxide. Applying similar deposition conditions to a (0 0 1) GaN surface leads to the growth of epitaxial (1 1 1) YbO films. Similar to other rocksalt oxides grown on GaN surfaces, YbO films display a 3D growth mechanism that leads to a grainy morphology with crystallites of 50 nm lateral dimensions. Rocking curves in ω and φ have full-width half-maximum values of 1.77° and 4.1°, respectively; further improvements in crystal quality appear to be limited by the thermal stability of the YbO phase.