Amorphous Ge‐Sb‐Se thin films fabricated by co‐sputtering: Properties and photosensitivity

Amorphous Ge–Sb–Se thin films were fabricated by a rf‐magnetron co‐sputtering technique employing the following cathodes: GeSe₂, Sb₂Se₃, and Ge₂₈Sb₁₂Se₆₀. The influence of the composition, determined by energy‐dispersive X‐ray spectroscopy, on the optical properties was studied. Optical properties were analyzed based on variable angle spectroscopic ellipsometry and UV‐Vis‐NIR spectrophotometry. The results show that the optical bandgap range 1.35‐2.08 eV with corresponding refractive index ranging from 3.33 to 2.36 can be reliably covered. Furthermore, morphological and topographical properties of selenide‐sputtered films studied by scanning electron microscopy and atomic force microscopy showed a good quality of fabricated films. In addition, structure of the films was controlled using Raman scattering spectroscopy. Finally, irreversible photoinduced changes by means of change in optical bandgap energy and refractive index of co‐sputtered films were studied revealing the photobleaching effect in Ge‐rich films when irradiated by near‐bandgap light under Ar atmosphere. The photobleaching effect tends to decrease with increasing antimony content.     

Strongly Photosensitive and Fluorescent F8T2 Electrospun Fibers

Electrospun fibers of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐bithiophene] (F8T2) with exceptional electro‐optical performance are obtained. The I/T characteristics measured in fibers with 7–15 µm diameter and 1 mm length show a semiconductor behavior; their thermal activation energy is 0.5 eV and the dark conductivity at RT is 5 × 10^?9 (Ω cm)^?1. Besides exhibiting a photosensitivity of about 60 under white light illumination with a light power intensity of 25 mW · cm^?2, the fibers also attain RT photoluminescence in the cyan, yellow, and red wavelength range under ultraviolet, blue, and green light excitation, respectively. Optical microscope images of F8T2 reveal homogeneous electrospun fibers, which are in good agreement with the uniformly radial fluorescence observed.

     

Photophysical properties of fluorene‐based copolymers synthesized by connecting twisted biphenyl units with fluorene via para‐ and meta‐linkages

BACKGROUND: Wide bandgap semiconducting polymers are of great interest in the development of organic and polymeric emissive materials for display purposes since they can be used to generate light of all colors either by irradiation of luminescent dyes or by energy transfer to emissive dopants. The aim of the present work is to construct new fluorene‐based semiconducting polymers with a wide bandgap. RESULTS: A novel polyfluorene derivative, poly[(9,9‐dihexyl‐2,7‐fluorene)‐alt‐(5,7‐dihydrodibenz[c,e]oxepin)], with a wide bandgap, was synthesized by connecting rigidly twisted biphenyl monomers with dihexylfluorene via para‐linkages and it was compared with poly[(9,9‐dihexyl‐2,7‐fluorene)‐alt‐(spirocyclohexane‐1,6′‐dibenzo[d,f][1,3]dioxepin)], which has meta‐linkages. Both polymers emit in the ultraviolet and blue regions. Electronic spectral absorption data and electrochemical measurements demonstrate that ca 40° torsion angle of the biphenyl units induces an increase in the HOMO–LUMO gap of 0.18 eV, and that meta‐linkage of the twisted segment in the polymer induces another increase of 0.24 eV compared to polydihexylfluorene. CONCLUSION: The new twisted biphenyl compounds are efficient segments to tune the bandgaps of conjugated polymers. The two fluorene‐based copolymers have wide bandgaps and exhibit potential as host materials. Copyright © 2008 Society of Chemical Industry     

Preparation and microstructure properties of tetrahedral amorphous carbon films by pulsed laser deposition using camphoric carbon target

The properties of tetrahedral amorphous carbon (ta-C) films grown by pulsed laser deposition (PLD) using camphoric carbon (CC) target and their respective effects of diamond percentages by weight in the target (Dwt.%) are discussed. Scanning electron microscopy (SEM), atomic force microscopy (AFM), Visible-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated that the Dwt.% noticeably modified the sp³ bonds content and the morphology of the ta-C films. The optical gap (E_g) and electrical resistivity (ρ) increase with Dwt.% up to 1.6 eV and 5.63×10⁷ (Ω cm), respectively, for the ta-C films deposited using target with higher of 50 Dwt.%. We found that the Dwt.% has modified the surface morphological, structural, bonding and physical properties of the camphoric carbon films.     

A new approach for selective surface modification of fluoropolymers by remote plasmas

Ethylene‐co‐tetrafluoroethylene (ETFE) and poly (vinylidene fluoride) (PVDF) films were exposed to the remote Ar, H₂, and O₂ plasmas. The modified polymer surfaces were characterized by X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurement. The plasma exposure led to weight loss and changes in the chemical composition on the polymer surface. Selective surface modification of fluoropolymers introduces various functional groups without altering the bulk properties. The results may be summarized as follows: the remote hydrogen plasma was the most effective in alternation from C? F to C? H (abstraction of fluorine). On the other hand, the remote oxygen plasma was unfavorable to abstract fluorine atoms, but effective in dehydrogenation (abstraction of hydrogen). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1012–1020, 2004     

Structural,optical, and electrical characterization of the poly[9,9‐dioctylfluorenyl‐2,7‐diyl]‐co‐1,4‐benzo‐(2,1,3)‐thiadiazole thin film fabricated by electrostatic spray technique

The article presents the efficient fabrication of the Poly[9,9‐dioctylfluorenyl‐2,7‐diyl]‐co‐1,4‐benzo‐(2,1,3)‐thiadiazole (F8BT) thin film using the electrostatic spray technique. Electrostatic atomization of the in‐house developed F8BT polymer ink was achieved at considerable low voltage. The structural and optical characterizations of the fabricated F8BT thin film were thoroughly investigated. Furthermore, the organic diode structure with electrostatic spray deposited F8BT thin film was fabricated and its performance was analyzed by performing current voltage measurement. The current–voltage characteristic curve of the organic diode showed nonlinear diode like behavior, thereby confirming the proper interference established between organic diode adjacent layers. The space charged limited current mechanism has been found to be dominant in the fabricated organic device with carrier mobility value of 5.65 e^?4 cm²V^?1s^?1. POLYM. ENG. SCI., 54:675–681, 2014. © 2013 Society of Plastics Engineers     

Influence of MWCNTs in Improving the Optical,DC Conductivity,and Mechanical Properties of CMC/PAAM Blends

Enhancing the optical, electrical, and mechanical properties of polymeric materials, by blending with another material and doping with nano-fillers, is crucial for improving their performance in optoelectronic, biological, and medical applications. In this work, the influence of adding multi-walled carbon nanotubes (MWCNTs) on the physical properties of carboxymethyl cellulose/polyacrylamide blends is reported. Scanning electron microscopy was used for investigating films' surface morphology and revealed good distribution of MWCNTs on the blend surface. UV–vis-IR spectroscopy showed that absorption and refractive indices, and other dispersion parameters could be controlled by adjusting the films' compositions. Loading 2 wt% MWCNTs narrowed the optical bandgap of the blend from 5.1 to 4.1 eV. Doping with MWCNTs raised the DC conductivity by about two orders of magnitude by forming three-dimensional pathways within the blend matrix. The storage modulus increased with MWCNTs loading by 39.3% for the 2 wt% ratio while decreasing with increasing temperature. POLYM. ENG. SCI., 60:996–1005, 2020. © 2020 Society of Plastics Engineers     

Thin film morphology and ion interaction behaviour of functional polymers for iontronic applications

Based on comprehensive studies by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) we report on the morphology and the ion-ion as well as the ion-polymer interaction properties of thin spin-cast films comprising an oligo(ethylene oxide) (OEO) grafted poly(p-phenylene) blended with either lithium- or tetrabutylammonium trifluoromethanesulfonate. Assuming that the ionic species intercalate within the OEO side-chain matrix, the covalent attachment of OEO appears to be an appropriate strategy to overcome the generally observed phenomenon of large-scale phase-separations between conjugated polymers and solid-state electrolytes. XPS turns out to be a suitable approach to study the basics of the ion-ion and the ion-polymer interactions of these model systems directly for the thin, spin-cast films.     

Dry Processes for Surface Modification of a Biopolymer: Chitosan

Standard dry surface modification reactions have been applied to partially deacetylated chitosan without affecting its bulk properties. Chitin, extracted from shells of Penaeus vannamei, yielded chitosan with a degree of acetylation of 70% and molecular weight of 250 000 D. The copolymer consists of (β‐(1‐4)‐2‐2‐acetamido‐D ‐glucose) units linked to (β‐(1‐4)‐2‐amino‐D ‐glucose) units. Since the main interest of this work was to study the surface properties of films on substrates, a method to cast this material onto Al‐coated silicon wafers had to be developed. X ray photoelectron spectroscopy (XPS) has been used to determine the surface composition of the unmodified films and to follow modification changes. The films were treated in either an oxygen plasma environment or under UV/ozone irradiation. Water advancing contact angle measurements and infrared spectroscopy (FTIR) were used to complement XPS measurements. The films appeared to orient on the silicon wafer surface in the type II chitin structure. The rates of oxidation are faster for the plasma process but they result in similar changes to those induced by UV/ozone treatment. Atomic force microscopy (AFM) clearly shows the advantage of the milder modification reaction without much change in surface morphology. The oxidation processes, as detected by XPS, proceed without much alteration of the amine nitrogen atoms but carbonyl containing moieties are formed as a function of treatment time. Specific reactions with a fluorosilane to measure the activity of hydroxyl groups indicate that at short treatment times, these groups are essentially inactive. The resulting surfaces can also serve as a potential way to induce silica‐like domains that can function as diffusion barriers. Irradiation of chitosan solutions shows that UV/ozone induces depolymerization. In both cases, i.e., plasma and UV/ozone reactions, the main active component to surface modification appears to be UV irradiation with a wavelength below 360 nm.

AFM surface profile for oxygen plasma treated film in barrel etcher for 1 min.     

Local Structure Investigation in Multiferroic BiFeO3–BaTiO3 Ceramics by XAS Technique and Their Relevant Properties

The (1?x)BiFeO₃‐xBaTiO₃ (with x = 0.1, 0.2, 0.3, and 0.4) ceramics were fabricated successfully by solid‐state reaction method. Single‐phase perovskite was obtained in all ceramics, as confirmed by XRD technique. It was observed that 0.7BiFeO₃–0.3BaTiO₃ was the morphotropic phase boundary (MPB) between rhombohedral and cubic phases, as also revealed from ferroelectric and magnetic properties. The simulated and experimental X‐Ray Absorption Spectroscopy (XAS) study revealed that BT in 0.75BF‐0.25BT is possibly taken a rhombohedral structure. Furthermore, the rounded ferroelectric hysteresis loops observed for 0.9BiFeO₃–0.1BaTiO₃ and 0.8BiFeO₃–0.2BaTiO₃ compositions could be attributed to their microstructure and surface charge effects and electron transfer between Fe³⁺ and Fe²⁺ ions. It was also found that high dielectric constant of 0.9BiFeO₃–0.1BaTiO₃ composition was a result of grain and grain‐boundary effects, as observed in SEM micrographs. In addition, a strong signature of dielectric relaxation behavior was observed in this ceramic system with the activation energy 0.467 eV obtained from the Arrhenius' law. Finally, the local structure investigation with XAS technique provided additional information to better understand the electric and magnetic properties in the BF‐BT ceramic system.     

Simple route for the preparation of graphene/poly(styrene‐b‐butadiene‐b‐styrene) nanocomposite films with enhanced electrical conductivity and hydrophobicity

This paper reports a simple route for the preparation of graphene/poly(styrene‐b‐butadiene‐b‐styrene) (SBS) nanocomposite films employing a vacuum filtration method. Graphene is exfoliated well by an electrochemical procedure and homogeneously dispersed in the polymer matrix. The prepared nanocomposite films were characterized by XRD, Fourier transform IR (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy, AFM and SEM. Morphological studies showed that graphene formed a smooth coating over the surface of SBS. The increase in graphene concentration induces the wrinkling of graphene sheets at the composite surface which causes a further increase in surface roughness. The FTIR, Raman and XPS spectra of graphene/SBS nanocomposite films indicate the strong interactions between graphene and the polymer matrix. According to the XRD patterns, introducing SBS into graphene did not modify the graphene structure additionally, i.e. the crystal lattice parameters do not depend on SBS content in graphene/SBS nanocomposite films. The graphene/SBS nanocomposite films also exhibited better hydrophobicity due to the increased surface roughness and lower sheet resistivity (reduced 10 times) compared to exfoliated graphene. © 2018 Society of Chemical Industry     

Effects of annealing on bandgap and surface plasmon resonance enhancement in Au/SnO2 quantum dots

Au/SnO₂ quantum dots (AuSQDs) were synthesized, and the effects of annealing on their structural and optical properties were examined. Significant changes were observed in the bandgap and surface plasmon resonance (SPR) of the AuSQDs after thermal treatment at different temperatures (400, 500, and 600 °C). The properties of the as-prepared and annealed samples were characterized via X-ray diffraction analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy, and diffuse reflectance spectroscopy. Annealing reduced the bandgap from 3.03 to 2.33 eV and increased the crystallinity while maintaining an average crystallite size below 10 nm. XPS valence band (VB) profiles provided information regarding the VB edge potentials, which helped to determine the conduction band edge potentials. An enhancement in the SPR of the Au nanoparticles was observed for AuSQD-500, which had the smallest bandgap among the samples investigated.     

Structural and electrochemical characterisation of [Pd(salen)]-type conducting polymer films

The oxidative polymerisation of four structurally-related [Pd(salen)] complexes and characterisation of the resulting polymeric films by cyclic voltammetry (CV), UV-visible transmission spectroscopy, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) is reported. The voltammetric technique gives insight into the electrochemical properties of the polymeric films whereas UV-visible spectroscopy is used to characterise the electronic structure of Pd electroactive films, of particular relevance to the type of charge carriers. X-ray techniques (supported by density functional theory, DFT) provide information related to composition and structural features of [Pd(salen)] precursors and the resulting polymers. Characterisation of poly[Pd(salen)] films shows that the electrochemical response of these supramolecular systems is ligand-based and dependent upon substituents in the diimine bridge and aldehyde moieties. XAS measurements near the Pd K-edge demonstrate that polymerisation of the Pd complexes does not change the coordination sphere of the Pd centre; this is consistent with the coupling of monomers units via phenyl rings. As further evidence of ligand-based electrochemical responses, polymer doping does not impart any changes at the Pd centre or its coordination sphere. Compositional analysis by XPS confirms that C: Pd, N: Pd and O: Pd surface atomic ratios do not change significantly from monomer to undoped or doped polymer, except for small variations associated with incorporation of electrolyte and solvent upon polymerisation and polymer oxidation. Overall, the data provide a picture of a polyaromatic delocalised electroactive system, in which the metal atom plays a templating (rather than electroactive) role.     

Synthesis and surface properties of polystyrene‐graft‐poly(ethylene glycol) copolymers

Polystyrene‐graft‐poly(ethylene glycol) copolymers (PS‐g‐PEG) were successfully synthesized using the “grafting‐through” method. The graft copolymers and the surface properties of their coats were characterized by 1 H‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), static contact angle measurement, and atomic force microscopy (AFM). Both DSC and TEM indicated that the graft copolymers had a microphase separated structure. AFM showed the microphase separated structure also occurred at the coat surface, especially at high PEG content, which could also be indirectly confirmed by the XPS and contact angle results. The formation mechanism of the microphase separated structure was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1458–1465, 2007     

Preparation and tribological properties of polymer film covalently bonded to silicon substrate via an epoxy-terminated self-assembled monolayer

A covalently immobilized polymer film was constructed on silicon substrate by a two-step method. As an anchor interlayer, (3-glycidoxypropyl)trimethoxysilane (GPMS) was self-assembled on hydroxylated silicon substrate to create epoxy-terminated surface, then poly(styrene-b-acrylic acid) (PSAA) was chemically grafted to the epoxy-derivatized substrates. The formation and surface properties of the films were characterized by means of ellipsometry, water contact angle measurement, attenuated total reflectance Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, and atomic force microscope (AFM). The nano- and micro-tribological properties of the films were evaluated by AFM and ball-on-plate tribometer, respectively. The results show that GPMS–PSAA film exhibits excellent durability and wear resistance, which is attributed to the molecular components of PSAA and the firm bonding between polymer molecules and silicon substrate via epoxysilane molecular glue. The influence of interlayer between polymer and substrate surface on tribological properties of ultrathin polymer film was revealed, which has an important significance upon designing ultrathin lubrication films with excellent tribological properties for micro/nanoelectromechanical systems.     

Incorporation of polyfluorenes into poly(lactic acid) films for sensor and optoelectronics applications

Films of neat and plasticized biodegradable poly(lactic acid) (PLA) matrices containing anionic conjugated polyelectrolytes, poly[9,9‐bis(4‐phenoxybutylsulfonate)]fluorene‐2,7‐diyl‐alt‐arylenes, with 1,4‐phenylene and 4,4″‐p‐terphenylene, respectively, as arylene groups or a neutral poly(9,9‐dialkylfluorene) for comparison were prepared by solution casting. These films were characterized using differential scanning calorimetry, thermogravimetry, scanning electron microscopy and fluorescence spectroscopy. In addition, the effects of plasticizer on the thermal properties and the oxygen permeability of the PLA films were measured through the oxygen transmission rate. Results show that it is possible to obtain thin, optically transparent and luminescent films with potential in oxygen sensing, exhibiting good thermal and photochemical stability. At high polyelectrolyte content, evidence is found for phase separation and aggregate formation and it is no longer possible to obtain completely homogeneous films. The possibility of incorporating the cationic metal complex tris(2,2′‐bipyridyl)ruthenium(II) into plasticized PLA films containing conjugated polyelectrolytes for dual‐wavelength ratiometric luminescence sensing is also discussed. Copyright © 2012 Society of Chemical Industry     

Fabrication of spray derived nanostructured n-ZnO/p-Si heterojunction diode and investigation of its response to dark and light

Fluorine doped ZnO thin films were grown by chemical spray pyrolysis technique of zinc acetate and ammonium fluoride, and the effect of fluorine content on structural, optical and electrical properties were evaluated. The structural, morphological, optical properties of ZnO films were investigated by XRD (X-ray diffraction), AFM (Atomic force microscopy), SEM (Scanning electron microscop) and UV–Vis spectroscopy, respectively. According to results, it was observed that all films had polycrystalline texture with hexagonal wurtzite crystal structure and film surface were made up of nano-scale grains, varied by fluorine content. Optical properties showed that optical band gap energy of ZnO changed from 3.28 to 3.24 eV with F content. Shrinkage effect was assessed as the cause in the variation of optical band gap values. Finally, current-voltage (I-V) analysis was performed in Au/ZnO:F/p-Si device in dark and light conditions and certain diode parameters such as ideality factor, barrier height and series resistance were calculated and discussed in detail.     

Enhanced figure of merit of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) and SWCNT thermoelectric composites by doping with FeCl3

Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole (F8BT) generally has a large Seebeck coefficient, and single-walled carbon nanotubes (SWCNTs) have high electrical conductivity. In this work, we prepared F8BT/SWCNT composites to combine the good Seebeck coefficient of the polymer and the excellent electrical conductivity of SWCNTs to achieve enhanced thermoelectric properties. For the composite materials, the maximum power factor of 1 μW mK⁻² was achieved when the SWCNT content was 60%, with the maximum ZT value of 4.6 × 10⁻⁴. After ferric chloride was employed as the oxidative dopant for the composites, the electrical conductivity of the composites improved significantly. The maximum value of power factor (1.7 μW mK⁻²) was achieved when the SWCNT content was 60%, and the ZT value of 7.1 × 10⁻⁴ was about 1.5 times as high as that of the composites with undoped F8BT. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47011.     

Effect of SiO2/EVA on the mechanical properties,permeability, and residual solvent of polypropylene packaging films

The surface of nano‐silica was modified by ethylene/vinyl acetate (EVA) emulsion and then blended with polypropylene (PP) to yield a nano‐silica/PP composite material. This composite was intended to enhance the mechanical properties of PP, improve its melting point and degree of crystallinity, reduce its oxygen permeability and water vapor permeability, decrease the adsorption of PP packaging films against organic solvents, and improve the films' performance for food safety. The experiments showed that the crystallinity of PP modified by nano‐silica increased, leading to enhanced mechanical and barrier properties, while its melting point rose. Meanwhile, the residual solvent value of the modified PP films was reduced by 10–90%. POLYM. COMPOS., 101–107, 2016. © 2014 Society of Plastics Engineers     

Effect of Ar:N2 flow rate on morphology,optical and electrical properties of CCTO thin films deposited by RF magnetron sputtering

Calcium copper titanate (CCTO) thin films were deposited on indium tin oxide (ITO) substrates using radio frequency (RF) magnetron sputtering, at selected Ar:N₂ flow rates (1:1, 1:2, 1:4, and 1:6 sccm) at ambient temperature. The effect of Ar:N₂ flow rate on the morphology, optical and electrical properties of the CCTO thin films were investigated using FESEM, XRD, AFM, Hall effect measurement, and UV–Vis spectroscopy. It was confirmed by XRD analysis that the thin films were produced is CCTO with cubic crystal structure. As the flow rate of Ar:N₂ increased up to 1:6 sccm, the thin film thickness reduced from 87 nm to 35 nm while the crystallite size of CCTO thin film decreased from 27 nm to 20 nm. Consequently, the surface roughness of thin film was halved from 8.74 nm to 4.02 nm. In addition, the CCTO thin films deposited at the highest Ar:N₂ flow rate studied, at 1:6 sccm; are having the highest sheet resistivity (13.27 Ω/sq) and the largest optical energy bandgap (3.68 eV). The results articulate that Ar:N₂ flow rate was one of the important process parameters in RF magnetron sputtering that could affect the morphology, electrical properties and optical properties of CCTO thin films.