Black-to-transmissive electrochromism of azulene-based donor–acceptor copolymers complemented by poly(4-styrene sulfonic acid)-doped poly(3,4-ethylenedioxythiophene)

A series of azulene–carbazole–2,1,3-benzothiadiazole (BTD) conjugated terpolymers were synthesized and their electrochemical and electrochromic properties were studied. The terpolymer containing a small amount of BTD units exhibits significantly higher electrochromic contrast and faster switching speed than azulene–carbazole alternating copolymer under low potentials because the BTD units act as electron acceptors, facilitating electron removal from azulene and carbazole units (electron donors) upon oxidation and hence leading to a lower oxidation potential. A complementary electrochromic device (ECD) was fabricated using the terpolymer as the anodically coloring layer and poly(4-styrene sulfonic acid)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) as the cathodically coloring layer. The ECD exhibits black-to-transmissive electrochromism as the absorption bands of the two polymers are complementary to each other in covering the whole visible region and they can be switched simultaneously under relatively low potentials.     

Observation of Meyer–Neldel rule in CdS thin films

A study of electrical transport in CdS thin films is reported. We have observed, for the first time, that CdS thin film conductivity obeys the Meyer–Neldel rule (MNR). This was deduced from linking the conductivity pre-exponential factor to the activation energy variation. CdS films were deposited by chemical bath deposition at different solution temperatures in order to vary the electrical activation energy of the films. A correlation between the MNR rule and the disorder in the film network is highlighted. The multi-trapping process in the band tail-localized states governs the conductivity in CdS films. This explains the MNR observation in CdS films. The variation of the electrical conductivity pre-exponential factor and activation energy are correlated to the disorder in the film network; this was explained in terms of polaron formation and phonon–electron coupling with disorder.     

Optical properties of CdSxTe1−x polycrystalline thin films

Thin films of CdS_xTe_1−x (0≤x≤ 1) have been prepared by vacuum evaporation from solid solutions. Rutherford backscattering spectrometry has been used to determine the thickness of the films, which is in the range 8–50 nm, and x-ray diffraction analysis has been used to determine the phase. The refractive index and extinction coefficient of the films has been calculated from reflectance and transmittance measurements for the wavelength region 250–3200 nm. Polynomial functions are given for each sample, which describe the variation in refractive index and extinction coefficient over the entire wavelength range. Least squares fitting to the absorption spectra revealed that the films all have a direct band gap, although photon energies required for indirect transitions have also been found. CdS_0.8Te_0.2 is found to have the lowest absorption coefficient at energies greater than 2.1 eV.     

Characterization of ZrTiO4 thin films prepared by sol–gel method

The electrical properties, memory switching behavior, and microstructures of ZrTiO₄ thin films prepared by sol–gel method at different annealing temperatures were investigated. All films exhibited ZrTiO₄ (111) and (101) orientations perpendicular to the substrate surface, and the grain size increased with increasing annealing temperature. A low leakage current density of 1.47×10^?6 A/cm² was obtained for the prepared films. The I–V characteristics of ZrTiO₄ capacitors can be explained in terms of ohmic conduction in the low electric field region and Schottky emission in the high electric field region. An on/off ratio of 10² was measured in our glass/ITO/ZrTiO₄/Pt structure with an annealing temperature of 600 °C. Considering the primary memory switching behavior of ZrTiO₄, ReRAM based on ZrTiO₄ shows promise for future nonvolatile memory applications.     

Optical studies of TiO2–lead phthalocyanine nanocomposite thin films prepared by electron beam evaporation

The nanocomposite thin films of titanium dioxide (TiO₂)–lead phthalocyanine (PbPc) have been prepared on glass substrates by the electron beam evaporation technique. The optical properties of TiO₂/PbPc nanocomposite thin films have been investigated using a spectrophotometric measurement of the absorbance and transmittance at normal incident of light in the wavelength region 300–800 nm. Surface morphology of thin films has been characterized using field emission scanning electron microscopy (FESEM). The UV–vis analysis has been performed to determine the type of electronic transition and the optical energy band gap. The analysis of the spectral behavior of the absorption coefficient in the intrinsic absorption region reveals that the absorption mechanism is due to direct transition. Moreover, by studying the absorption coefficient spectra just below the fundamental absorption edge, the width of band tails of localized states (Urbach energy), steepness parameter and width of the defect states have been evaluated. The obtained results of this novel nanocomposite (TiO₂/PbPc) support the desirable features for the optoelectronic devices.     

Optical and electrochemical gas sensing properties of yttrium–silver co-doped lithium iron phosphate thin films

The new sensing material, LiFe_0.995Y_0.0025Ag_0.0025PO₄ was synthesized using hydro-thermal methods, and characterized by X-ray diffraction, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as prepared products were subsequently utilized in a self assembled optical waveguide gases testing apparatus and a WS-30A electro-chemical gas sensing apparatus for xylene detection. A glass optical waveguide gas sensor was fabricated by spin-coating a LiFe_0.995Y_0.0025Ag_0.0025PO₄ thin film on the surface of single-mode tin-diffused glass Optical Waveguide. The sensing elements for electro-chemical gas sensor were made by dip-coating a LiFe_0.995Y_0.0025Ag_0.0025PO₄ thin film on the surface of an alumina ceramic tube, assembled with platinum wire. The experimental results indicated that, at room temperature, LiFe_0.995Y_0.0025Ag_0.0025PO₄ thin film/tin-diffused optical waveguide sensing element exhibited higher response to xylene in the range of 0.1–100 ppm; at an optimum operating temperature (300 °C), the response (S_r) of LiFe_0.995Y_0.0025Ag_0.0025PO₄ to 100 ppm of xylene was 5.29, as measured by the WS-30A electro-chemical gases sensing apparatus.     

Optical and electrical properties of nickel oxide thin films synthesized by sol–gel spin coating

Nickel oxide thin films were prepared by the sol–gel technique combined with spin coating onto glass substrates. The as-deposited films were pre-heated at 275 °C for 15 min and then annealed in air at different temperatures. The effects of the annealing temperature on the structural and optical properties of the films are studied. The results show that 600 °C is the optimum annealing temperature for preparation of NiO films with p-type conductivity and high optical transparency. Then, by using these optimized deposition parameters, NiO thin films of various thicknesses were deposited at the same experimental conditions and annealed under different atmospheres. Surface morphology of the films was investigated by atomic force microscopy. The surface morphology of the films varies with the annealing atmosphere. Optical transmission was studied by UV–vis spectrophotometer. The transmittance of films decreased as the thickness of films increased. The electrical resistivity, obtained by four-point probe measurements, was improved when NiO layers were annealed in N₂ atmosphere at 600 °C.     

Electrical properties of Copper(Ⅱ) phthalocyanine derivative thin films

This paper reports an investigation on the electrical properties of thin film devices made by Copper(Ⅱ) phthalocyanine derivative and polycarbonate (PC) composite. The conducting and injection mechanism are further discussed. Materials of a variety composition were prepared into the thin film via spin-coating. ITO and aluminum were used as the bottom and top electrode respectively. J-V characteristic was measured and the result demonstrates that at a small bias region an Ohmic contact was achieved. As the forward bias increased,the current became space charge limited. The result of AC impedance measurement indicates the device could be equivalent to a parallel RC system. The introduction of PC into the CuPc possibly reduces the charge overlapping between the aromatic rings and led to a reduction in the molecular interaction.Hence,the ac conductivity decreases sharply as PC composition increases. But no change in the transport mechanism is found.     

Electrodeposited and characterization of Ag–Sn–S semiconductor thin films

Thin film of silver tin sulfides (Ag–Sn–S) has been deposited on indium tin oxide coated glass (ITO) substrates using potentiostatic cathodic electrodeposition technique. New procedure for the growth of Ag–Sn–S film is presented. An electrolyte solution containing Silver Nitrate (AgNO₃), Tin(II) Chloride (SnCl₂) and Sodium Thiosulfate (Na₂S₂O₃)in acidic solution (pH ~2) and at temperature of the bath 55 °C were used for the growth of Ag–Sn–S thin film. Prior to the deposition, a cyclic voltammetry technique was performed in binary (Ag–S, Sn–S) and ternary (Ag–Sn–S) systems. This study was carried out to examine the behavior of electroactive species at the electrode surface. Based on these results, the cathodic applied potential was fixed at −1000 mV versus Ag/AgCl to obtain a uniform and good adhesion of ternary thin film. After that, structural, morphological and optical performances of films have been investigated. The X-ray diffraction patterns of the samples demonstrate the presence of the orthorhombic phase of Ag₈SnS₆ at applied potential of −1000 mV versus Ag/AgCl. Based on the scanning electron microscopy (SEM), it was found that the surface morphology and grain size were strongly influenced by the presence of Sn and/or Ag in the electrolyte bath. The band gaps of binaries and ternary compound are evaluated from optical absorption measurements. Band gap of Ag₈SnS₆ determined from transmittance spectra is in the range 1.56 eV. Flat-band potential and free carrier concentration have been determined from Mott–Schottky plot and are estimated to be around 0.18 V and 2.21×10¹⁴ cm⁻³ respectively. The photoelectrochemical test of Ag₈SnS₆ was studied and the experimental observations are discussed in detail.     

Charge transfer in thin films of donor–acceptor complexes studied by infrared spectroscopy

The degree of charge transfer in thin films of organic charge transfer (CT)-complexes, which are deposited via thermal evaporation, is examined via infrared-spectroscopy. We demonstrate a linear relationship between the shift in the excitation energy of the CN-stretching mode of CT-complexes with the acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and the charge transfer. The measured correlation corresponds very well with DFT calculations. For Na-TCNQ we observe a splitting in the peak of the CN-stretching mode, which can be explained by the coupling of two modes and was confirmed by the calculations. In CT-complexes with partial charge transfer the appearance of an electronic excitation is demonstrated.     

Investigation of optical and electronic properties in Al–Sn co-doped ZnO thin films

Al-Sn co-doped ZnO thin films were deposited onto quartz substrates by sol-gel processing. The surface morphology and electrical and optical properties were investigated at different annealing temperatures. The surface morphology showed a closely packed arrangement of crystallites in all the doped films. As prepared co-doped films show a preferred orientation along an (0 0 2) plane. This preferred orientation was enhanced by increasing the annealing temperature to between 400 °C and 500 °C, but there was a shift to the (1 0 1) plane when the annealing temperature rose above 500 °C. These samples show, on average, 91.2% optical transmittance in the visible range. In this study, the optical band gap of all the doped films was broadened compared with pure ZnO, regardless of the different annealing temperature. The carrier concentration and carrier mobility of the thin films were also investigated.     

Low-voltage organic ferroelectric field effect transistors using Langmuir–Schaefer films of poly(vinylidene fluoride-trifluororethylene)

Langmuir–Schaefer transfer was used to fabricate ultrathin films of ferroelectric copolymer, poly(vinylidene fluoride-trifluoroethylene) (70–30 mol%), for non-volatile memory application at low operating voltage. Increasing the number of transferred monolayers up to 10 led to improved film crystallinity in the “in-plane” direction, which reduced surface roughness of the semicrystalline film. Treatment of the substrate surface by plasma results in different film coverage which was subsequently found to be governed by interaction of the deposited film and surface condition. Localized ferroelectric switching was substantially attained using piezo-force tip at 10 V on 10-monolayer films. Integrating this film as a dielectric layer into organic capacitor and field effect transistor yields a reasonably good leakage current (<10^?7 A/cm²) with hysteresis in capacitance and drain current with ON/OFF ratio of 10³ for organic ferroelectric memory application at significantly reduced operating voltage of |15| V.     

CVD-growth of CNT with the use of catalutic Ct–Me–N–O thin films incorporated in the technology

The process of the formation of carbon nanotube arrays on Ct–Me–N catalytic alloys of low nickel content (10–20 at %) by chemical vapor deposition, where Ct is a catalytic metal from the group of Ni, Co, Fe, and Pd, and Me is a transition metal of group IV–VII of the periodic table, was investigated. It is shown that CNT grow effectively when the alloy contains Ti, V, Cr, Zr, Hf, Nb, and Ta. The addition of nitrogen and oxygen to the alloy’s composition gives rise to a buildup of oxynitrides, expelling of the catalyst, and formation of its clusters on the surface. The replacement of metals in the alloy has an effect on the diameter of the CNT. Moreover, the alloy films 10–500 nm thick can be used for the CNT growth, which is responsible for high degree of homogeneity and the repeatability of the process. CNT growth was not observed when the alloy contained W and Re.     

Electrically-driven metal–insulator transition of vanadium dioxide thin films in a metal–oxide-insulator–metal device structure

We report the successful growth of vanadium dioxide (VO₂) films on SiO₂ buffered metal electrode and the fabrication of metal–oxide-insulator–metal (MOIM) junction. The VO₂ film has an abrupt thermal-induced metal–insulator transition (MIT) with a change of resistance of 2 orders of magnitude. The electrically-driven MIT (E-MIT) switching characteristics have been investigated by applying perpendicular voltage to VO₂ based MOIM device at particular temperatures, sharp jumps in electric current were observed in the I–V characteristics under a low threshold voltage of 1.6 V. The Ohmic behavior, non-Ohmic super-linear one, and metallic regime are sequentially observed in the MOIM device with the increase of voltage. It is expected to be of significance in exploring ultrafast electronic devices incorporating correlated oxides based MOIM structure.     

Structure of BaTiO3 thin films modified by film–substrate interaction

Substrate-free crystallization of BaTiO₃ thin films was investigated. It was found that the substrate-free crystallized BaTiO₃ films attain a hexagonal structure, whereas the substrate-supported films always crystallize in the tetragonal phase. The substrate-free crystallized hexagonal BaTiO₃ demonstrates detectable pyroelectric effect and does not exhibit phase transitions in the 25–423 K temperature range. Therefore, the substrate-free crystallized BaTiO₃ represents a previously unreported phase of BaTiO₃.     

Phase transformation kinetics and optical properties of Ga–Se–Sb phase-change thin films

Phase transformation kinetics in Ga₂₅Se_75?xSb_x glasses have been determined by non-isothermal differential scanning calorimetric measurements at heating rates of 5, 10, 15, 20 and 25 K/min. The values of glass transition (T_g) and crystallization temperature (T_c) are found to be composition and heating rate dependent. The activation energy of crystallization and glass transition have been determined from the dependence of T_c and T_g on the heating rate. Thin films of Ga₂₅Se_75?xSb_x glasses have been prepared by vacuum evaporation technique with thickness 400 nm. These thin films were crystallized by thermal annealing and laser-irradiation. The phase change phenomena have been studied by measuring optical absorption of as-prepared and crystallized thin films in the wave length region 400–900 nm. The optical absorption data indicate that the absorption mechanism is non-direct transition. Optical band gap values decrease with increase in Sb contents in Ga–Se as well as with increase in annealing temperature and laser-irradiation time. The optical band gap is shifted due to crystallization by annealing/laser-irradiation. As the phase of the films changes from amorphous to crystalline, a non sharp change of the optical band gap is observed. This gradual decrease in optical band gap was explained to be a result of an amorphous–crystalline phase transformation.     

Properties of V–Ce mixed-oxide thin films deposited by RF magnetron sputtering

Thin films of vanadium cerium mixed oxides are good counter-electrodes for electrochromic devices because of their passive optical behavior and very good charge capacity. We deposited thin films of V–Ce mixed oxides on glass substrates by RF magnetron sputtering under argon at room temperature using different power settings. The targets were pressed into pellets of a powder mixture of V₂O₅ and CeO₂ at molar ratios of 2:1, 1:1, and 1:2. For a molar ratio of 2:1, the resulting crystalline film comprised an orthorhombic CeVO₃ phase and the average grain size was 89 nm. For molar ratios of 1:1 and 1:2, the resulting films were completely amorphous in nature. Scanning electron microscopy images and energy-dispersive X-ray spectroscopy data confirmed these results. The optical properties of the films were studied using UV-Vis-NIR spectrophotometry. The transmittance and indirect allowed bandgap for the films increased with the RF power, corresponding to a blue shift of the UV cutoff. The average transmittance increased from 60.9% to 85.3% as the amount of CeO₂ in the target material increased. The optical bandgap also increased from 1.94 to 2.34 eV with increasing CeO₂ content for films prepared at 200 W. Photoacoustic amplitude (PA) spectra were recorded in the range 300–1000 nm. The optical bandgap was calculated from wavelength-dependent normalized PA data and values were in good agreement with those obtained from UV-Vis-NIR data. The thermal diffusivity calculated for the films increased with deposition power. For thin films deposited at 200 W, values of 53.556×10⁻⁸, 1.069×10⁻⁸, and 0.2198×10⁻⁸ m²/s were obtained for 2:1, 1:1, and 1:2 V₂O₅/CeO₂, respectively.     

Composition effect on the structure and optical parameters of Ge–Se–Te thin films

The present work reported the influence of Ge content variation on the optical properties of Ge_xSe₅₀Te_50-x (x=0, 5, 15, 20, 35 at%). Vacuum thermal evaporation technique was employed to prepare amorphous Ge_xSe₅₀Te_50−x thin films. The stoichiometry of the chemical composition was checked by energy dispersive X-ray spectroscopy (EDX), whereas the thin films structure was determined by an X-ray diffraction and a scanning electron microscope (SEM). The optical absorption measurements were performed at room temperature in the wavelength range of 200–900 nm. Many optical constants were calculated for the studied thin films utilizing the optical absorption data. It was observed that the optical absorption mechanism follows the rule of the allowed direct transition. The optical band gap was found to increase from 2.31 to 2.60 eV as the Ge content increases from 0 to 35 at%. This result was explained in terms of the chemical bond approach.     

Microwave properties and applications of Y–Ba–Cu–O thin films grown on various substrates

Microwave properties of YBa₂Cu₃O_7-δ (YBCO) films grown on (100) LaAlO₃ (LAO), (110) NdGaO₃ (NGO) and (001) SrLaAlO₄ (SLAO) substrates were studied in the form of a microstrip ring resonator at temperatures above 20 K. The YBCO resonator on a SLAO substrate showed microwave properties better than or comparable to other YBCO resonators on LAO substrates. For the YBCO resonators on LAO and SLAO substrates, both Q_U and f₀ appeared to decrease as the temperature was raised. Meanwhile the resonator on a NGO substrate showed different behaviors with Q_U showing a peak at ∼70 K, which are attributed to the unique temperature dependence of the loss tangent of the NGO substrate. An X-band oscillator with a YBCO ring resonator coupled to the circuit was prepared and its properties were investigated at low temperatures. The frequency of the oscillator signal appeared to change from 7.925 GHz at 30 K to 7.878 GHz at 77 K, which was mostly attributed to the change in f₀ of the YBCO ring resonator. The signal power appeared to be more than 4.5 mW at 30 K and 2.1 mW at 77 K, respectively. At 55 K, the frequency of the oscillator signal was 7.917 GHz with the 3 dB-linewidth of 450 Hz.