New semi-conducting poly(phenylene vinylene-alt-anthrylene vinylene)s: Synthesis,characterization and photophysical properties

An anthracene-based semi-conducting polymer (P1) and its cyano-analogue (P2) were synthesized via the Wittig and Knoevenagel polycondensations. The polymers were soluble in common organic solvents and have number-average molecular weights of 13,750 and 6430 g mol⁻¹ for P1 and P2, respectively. The DSC analyzes show a good thermal stability and an amorphous morphology in solid state for these organic materials. The optical properties of the polymers were investigated by UV–visible absorption and fluorescence spectroscopies. The HOMO and LUMO levels were estimated using cyclic voltammetry analysis. The effect of cyano group on the photophysical properties of poly(phenylene vinylene-alt-anthrylene vinylene)s was investigated. The results demonstrate an enhancement in the ionization potential and a significant improvement of the fluorescence yield due to introduction of such groups into the π-conjugated system. Single-layer diodes based on these organic semiconductors have been fabricated and showed relatively low turn-on voltages.     

Thermophysical properties of free-standing micrometer-thick Poly(3-hexylthiophene) films

The solution of Poly(3-hexylthiophene) (P3HT) in chloroform is generally adopted for fabricating P3HT thin films or nanofibers. In this work, 4 regular P3HT solution weight percentages, 2, 3, 5 and 7 wt.%, are compounded to fabricate P3HT thin films by using spin-coating technique. Raman spectrum study suggests that the density of the P3HT thin films varies with different P3HT solution weight percentages while X-ray diffraction analysis reveals that the crystal structures are identical for all P3HT thin films. The transient electrothermal technique is employed to measure the thermal diffusivity of the P3HT thin films and an efficient temperature-resistance calibration is performed to cooperatively study the thermal conductivity. When the P3HT weight percentage changes from 2% to 7%, the thermal conductivity varies from 1.29 W/m·K to 1.67 W/m·K and the thermal diffusivity goes down from around 10^− 6 m²/s to 5 × 10^− 7 m²/s. The density of P3HT thin films is also determined from the experimental data. The relationship between the density and thermophysical properties clearly demonstrates that the thermal conductivity increases with density while the thermal diffusivity decreases.     

Film formation properties of inkjet printed poly(phenylene-ethynylene)-poly(phenylene-vinylene)s

Inkjet printing was used here as a precise and fast dispensing technique to prepare thin-film libraries of a poly-(phenylene-ethynylene)-poly(phenylene-vinylene)s copolymer. The films were prepared with a systematic variation of the ink composition, the dot spacing and the substrate temperature. Homogeneous films with a thickness of 100 nm were obtained when printed at room temperature and from a solvent mixture of toluene and ortho-dichlorobenzene in a volume ratio of 90/10. This approach can be used for optoelectronic applications, where the layer homogeneity is extremely important but where the ink compositions may vary per device, as well as the exact layer thickness. Our approach can be applied for the preparation of films by inkjet printing for any other (polymer) ink solution and represents a fast and efficient screening of the parameters to obtain homogeneous films with a precise thickness.     

Ellipsometry study of poly(o-methoxyaniline) thin films

Spin-coated poly(o-methoxyaniline) (POMA) thin films on various substrates were investigated using spectroscopic ellipsometry (SE) in the 1.5–4.5 eV photon energy range. Spin-coating process parameters are reported (spin speed and concentration). Substrates with higher surface energy were found to increase polymer film thickness and decrease roughness. An optical model was developed using SE data along with complementary data from atomic force microscopy and UV–vis spectroscopy to obtain optical properties—refractive index n and extinction coefficient k for POMA. The model includes Lorentz oscillators for the POMA film and a Bruggeman effective medium approximation for roughness. In-plane film optical anisotropy was not observed, but a small out of plane anisotropy was detected for the polymer.     

Friction Spot Joining of aluminum AA2024/carbon-fiber reinforced poly(phenylene sulfide) composite single lap joints: Microstructure and mechanical performance

Friction Spot Joining is a promising alternative joining technology for polymer–metal hybrid structures. In this work, the feasibility of Friction Spot Joining of aluminum AA2024-T3 (bare and alclad)/carbon-fiber reinforced poly(phenylene sulfide) is reported. The process temperature and the microstructure of the joints were investigated. Lap shear tensile strength as high as 27 MPa was achieved by using aluminum bare specimens. Sand blasting was also performed as an effective mechanical surface pre-treatment on aluminum surfaces, which resulted in higher surface roughness and accordingly improved mechanical performance for the selected conditions. In addition, the alclad specimens exhibited promising mechanical performance (lap shear strength of up to 43 MPa) that justifies further investigations. Finally, the bonding and failure mechanisms of the joints are briefly discussed.     

Synthesis and characterization of novel photoactive poly(arylene ether ketone) with azobenzene pendants

A novel azobenzene-functionalized poly(arylene ether ketone) (azo-PAEK) with azo moieties on the pendants was prepared by post-esterification reaction of acid-containing poly(arylene ether ketone) (acid-PAEK) with 4-((4-nitrophenyl)diazenyl)phenol (NAP). DSC and TGA measurements indicate the azo-PAEK has high glass transition temperature of 152 °C and good thermal stability with 5% weight loss at 319 °C. Irradiated by 360 nm UV light, the azo-PAEK shows a significant photoisomerization effect. Under the illumination of linearly polarized laser beam, significant surface-relief-gratings (SRGs) with the surface modulation depth of 37 nm were fabricated rapidly on the azo-PAEK film.     

Electronic transport properties of 1-(p-R-phenacyl)-4-{[(1′-ethylcarboxylate)-(3′-p-R′-phenacyl)]-7′-indolizinyl}pyridinium bromides in thin films

The temperature dependences of electrical conductivity, σ, and Seebeck coefficient, S, for some new pyridium monoquaternary salts derivatives, 1-(p-R-phenacyl)-4-{[(1′-ethylcarboxylate)-(3′-p-R′-phenacyl)]-7′-indolizinyl}pyridinium bromides have been studied.The film samples (d = 0.08-0.28 μm) have been deposited onto glass by an immersion technique (dimethylformamide was used as a solvent).The investigated compounds behave as typical p-type polycrystalline semiconductors. The activation energy of electrical conduction ranged between 0.65 and 1.72 eV, while the ratio of charge carrier mobilities laid in the range (0.60-0.83).The model based on band gap representation is suitable in explaining the electronic transport in present compounds in the higher temperature range (385-500 K).     

Fabrication of conducting poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) thin films by ultrasonic spray-assisted mist deposition method

Transparent conducting polymer, poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) thin films were fabricated by a vapor-deposition technique, ultrasonic spray-assisted mist deposition method. The thickness was well controlled from 40 to 600 nm, keeping reasonable conductivity of 300-450 S/cm. The films with thickness less than 180 nm have high (> 80%) transmission over a wide (270-800 nm) spectral region. In addition, formation of ring-dot electrode pattern with a hard-mask was demonstrated, achieving lithography-less patterning. The results encourage that this deposition method is developed as an actual process technology of transparent electrodes in devices.     

Optical properties and DC electrical conductivity of Ge28−xSe72Sbx thin films

Thin films of Ge_28−xSe₇₂Sb_x (x=0, 8, 16, 24 at%) with thickness of 200 nm are prepared by thermal evaporation onto glass substrates under vacuum of 5.3×10⁻⁵ mbar. Optical reflectance and transmittance of these films are measured at room temperature in the light wavelength region from 200 to 1100 nm. The estimated optical energy gap, E_g, is found to decrease from 2 eV (0 at% Sb) to 1.5 eV (24 at% Sb), whereas the band tail width, E_e, increases from 0.062 to 0.077 eV, respectively. The refractive index, n, and extinction coefficient, κ, are determined as functions of wavelength. The DC electrical conductivity, σ, of films is measured as a function of temperature in the range from 300 to 360 K. The extracted value of activation energy, ΔE, is found to decrease from 0.95 eV (0 at% Sb) to 0.74 eV (24 at% Sb). Optical and electrical behavior of films can be explained in terms of cohesive energy (CE) and Se-Se defect bonds.     

Synthesis and characterization of conjugated poly (amino benzyl alcohol) and poly (ethylene glycol) for solid polymer electrolyte

A solid polymer electrolyte chemically bonded to a π-conjugated polymer was prepared for the use as a designed ladder-type structure by the graft copolymerization of poly (aminobenzyl alcohol) (PABA) with poly (ethylene glycol) (PEG). PABA was used as the frame for the ladder and the PEG as the rungs. The expected synergic effect afforded by the introduction of the ionic salts into the crosslinked conjugated polymer and PEG network was investigated as a function of its structure, morphology, and ionic conductivity. The insertion of the ionic salts into the PABA-PEG-PABA network led to the enhancement of the ionic conductivity compared to that of PEG/LiClO₄. The synergic effect may be explained by the more efficient segmental motion of the polymer chains or better ion mobility in the network due to the interrupted crystallization of the PEG chains. The fine tuning of the crosslinked conjugated polymer gel might enable it to show a faster response to electrochemical stimuli.     

Optical properties of N,N′-bis(3-phenoxy-3-phenoxy-phenoxy)-1,4,5,8-naphthalene-tetracarboxylic diimide by spectroscopic ellipsometry

Optical properties of N,N′-bis(3-phenoxy-3-phenoxy-phenoxy)-1,4,5,8-naphthalene-tetracarboxylic diimide were investigated using variable angle spectroscopic ellipsometry in the visible light range. An oscillator model with one Tauc–Lorentzian and three Gaussian oscillators was constructed and found physically consistent with the experimental results. No measurable optical anisotropy is found in-plane or out of the film plane, indicating a random arrangement of molecules in spin cast thin films. Refractive index n and absorption index k are reported in the 1.5–4.5 eV (840 nm to 280 nm) optical range.     

Vacuum vapour phase polymerised poly(3,4-ethyelendioxythiophene) thin films for use in large-scale electrochromic devices

Large-scale electrochromic devices were manufactured using vacuum vapour phase polymerised (VPP) poly(3,4-ethylenedioxythiophene) (PEDOT). Homogeneous 3,4-ethylenedioxythiophene (EDOT) and water vapour distribution within the large 115 L VPP chamber is paramount for the reproducible synthesis of high conductivity PEDOT thin films. Obtaining these conditions, however, was not trivial. The issue was resolved by synthesising PEDOT under vacuum, however, this altered the dynamics of the polymerisation process. As a result, surfactant addition, monomer and water vapour distribution, monomer and chamber temperature, and polymerisation times were all systematically investigated. Controlling these parameters has resulted in PEDOT with conductivity exceeding 1100 S · cm⁻¹, with a best of 1485 S · cm⁻¹, and electrochromic devices with an optical switch of Δ%Tx ≥ 50%. The resulting high conductivity and optical range are due to long undisrupted PEDOT polymer chains coupled with low levels of oligomers within the matrix.     

Optical and morphological characterisation of a silver nanoparticle/fluorescent poly(phenylenethynylene) composite for optical biosensors

Thiol silver nanoparticles prepared by the phase transfer method have been mixed with a fluorescent poly(phenylenethynylene) sequenced with dithioester-diethylsulfide moieties in order to develop a nanocomposite for its possible application in optical biosensors for the detection and attack of fungi such as Paecilomyces variotii. Films have been prepared by dipping technique and characterized by AFM, XPS, UV-Visible and fluorescence spectroscopy. Optical Absorption properties of the nanocomposite are similar to those of the polymer with an absorption tail in the visible which supports the presence of silver nanoparticles. Despite the lack of fluorescence of the nanoparticles, the composite emits in the yellow green region and the intensity of the fluorescence of the nanocomposite film decreases after the immersion in the culture thus permitting the detection of the fungus by this technique. The fungus can be deposited on films of both the polymer and nanocomposite, nevertheless only in the latter case, an attack on mycelium is observed revealing the fungicidal effect of silver nanoparticles in the nanocomposite.     

Synthesis and photoluminescent properties of doped ZnS nanocrystals capped by poly(vinylpyrrolidone)

Zinc sulfide semiconductor nanocrystals doped with selected transition metal ions (Mn²⁺, Cu²⁺, and Ni²⁺) have been synthesized via a solution-based method utilizing low dopant concentrations (0–1%) and employing poly(vinylpyrrolidone) (PVP) as a capping agent. UV/Vis absorbance spectra for all of the synthesized nanocrystals show an exitonic peak at around 310 nm, indicating that the introduction of the dopant does not influence the particle size. Calculated particle sizes for undoped and doped nanocrystals are in the 4.3 nm size range. Photoluminescence spectra recorded for undoped ZnS nanocrystals, using an excitation wavelength of 310 nm, exhibit an emission peak centered at around 460 nm. When a dopant ion is included in the synthesis, peaks in the corresponding photoluminescence spectra are red-shifted. For Mn-doped nanocrystals, an intense peak centered at approximately 590 nm is found and is seen to increase in photoluminescence intensity with an increase in dopant concentration. In contrast, for Cu-doped and Ni-doped nanocrystals, weaker peaks centered at around 520 and 500 nm, respectively, are observed and are noticed to decrease in photoluminescence intensity with an increase in dopant concentration. These results clearly show that careful control of synthetic conditions must be employed in the synthesis of doped semiconductor nanocrystals in order to obtain materials with optimized properties.     

Morphological and physicochemical properties of spin-coated poly(3-octylthiophene)/polystyrene composite thin films

Poly(3-octylthiophene) (P3OT) was synthesized by direct oxidation of 3-octylthiophene with FeCl₃ as oxidant. Molecular weight of P3OT polymer was measured by size exclusion chromatography. Homogeneous poly(3-octylthiophene) (P3OT) and polystyrene (PS) composite films have been synthesized by spin-coating technique from toluene with different polymer concentrations. The doped films were obtained by immersion for 30 s in a 0.3 M ferric chloride (FeCl₃) solution in nitromethane. A classical percolation phenomenon was observed in the electrical properties of these blends, it was smaller than 5% of P3OT in the blend. Surface topographical changes were studied by atomic force microscopy (AFM). AFM images of the composite films revealed surface morphology variation as a function of different P3OT concentration in PS, phase segregation was observed, and PS is shown to segregate to the surface of the films. The higher PS solubility, in comparison with the P3OT solubility, in toluene resulted in PS/P3OT bilayers. The films exhibited pit and island like topography, the pit size changed with the polymer concentration. Optical absorption properties of the polymeric films were analyzed in pristine and doped state. In doped state, the bipolaronic bands at 0.5 and 1.6 eV are shown in a 4% conductive polymer in the PS/P3OT film. Finally thermogravimetric analysis was also made on the simple and composite polymers.     

Synthesis and characterization of nitrated and aminated poly(phenylene sulfide) derivatives for advanced applications

Nitrated and aminated poly(phenylene sulfide) (PPS) derivatives with different extent of modification were synthesized in a one-pot reaction in suspension. Their substitution degree was determined from both elemental analysis and TGA curves. FT-IR and NMR spectra demonstrated the effectiveness of the functionalization reactions, showing the appearance of bands related to the substituent groups. A progressive reduction in thermal stability was observed as the number of functional groups increased. Aminated derivatives were thermally less stable and exhibited higher solubility in aprotic polar solvents than the corresponding nitrated polymers. DSC thermograms revealed a diminution in the crystallization temperature and a rise in the glass transition with increasing functionalization degree, since the presence of substituent groups inhibits the rotation of consecutive elements of the polymer chain. The level of crystallinity decreased upon increasing chain modification, as evidenced from X-ray diffractograms. The steric hindrance of the substituents disrupts the chain packing, leading to smaller crystals. These derivatives are expected to have applications in electromembranes and as matrix materials for the fabrication of high-performance composites suitable for structural and non-structural components.     

Optical and morphological characterization by atomic force microscopy of luminescent 2-styrylpyridine derivative compounds with Poly(N-vinylcarbazole) films

The present work addresses the optical and morphological properties of organic films based on low molecular weight dyes styrylpyridine derivatives 2-styrylpyridine (A), 4-chlorophenyl-2-vinylpyridine (B) and 4-fluorophenyl-2-vinylpyridine (C), embedded in a polymeric matrix poly(N-vinylcarbazole) (PVK). The films were prepared by a spin-coating technique from solutions with dye:PVK ratios of 0.25:1, 0.5:1 and 1:1. Solvents were chloroform and toluene. The molar absorption coefficient (ε) spectra for a dye:PVK mixture in solution were a combination of the absorptions of both components separately, but for the deposited films, the shape of the spectrum showed that the poly(N-vinylcarbazole) absorption dominated. However, when the same films were dissolved again in CHCl₃, their spectra showed an absorption shape similar to that of the solution mixture before the deposition. Solution viscosity measurements were carried out with an Ubbelohde glass capillary viscometer to corroborate the results that showed a better mixture of the dye with the host in chloroform. The morphology of the prepared films was analyzed by atomic force microscopy and exhibited a solvent effect, with a pinhole-free, smooth surface when toluene was used and a wavy surface with chloroform. The ratio dye:matrix was the principal parameter for obtaining optical quality films; for 0.25:1 and 0.5:1 ratios, the films were of good quality, but for 1:1, the dye was expelled from the PVK and a crystallization was present over the surface of the films. Film thickness was also measured and films deposited from toluene solutions gave an average thickness of 54 nm while films from chloroform solutions had an average thickness greater than 160 nm that increased depending on chromophore concentration.     

共聚物聚苯硫醚-聚苯硫醚酮的合成及表征

在聚苯硫醚(PPS)的合成体系中加入不同比例的第三单体4,4二氯二苯甲酮(DCBP)从而合成了共聚物PP/SK.主要通过加入不同量的DCBP来考察产品的熔点及分子量的变化.合成工艺条件:前期反应的最高温度为T1=190℃～230℃,反应时间为t1=3h～5h;后期的反应温度最高为T2=250℃～270℃,反应时间为t2=2h～4h.n(Na2S·9H2O):n(对二氯苯/4,4二氯二苯甲酮)=1.1mol:1mol,m(N甲基吡咯烷酮):n(Na2S·9H2O)=282g:0.1mol,m(催化剂):n(Na2S·9H2O) =2g:0.1mol.根据上述加料及反应条件合成了线性的高分子量的共聚物PPS/SK,其重均分子量接近55000g/mol,产品的平均收率达到91.32％.通过一步循环回收工艺就实现了溶剂和催化剂的循环.用红外、元素分析、X-RD及热分析对产品进行了表征.     

Electro-optical properties of poly[di(2-thiophenyl)carborane] and its opto-electronic application

Electrochemical and optical properties of a hybrid carborane based polymer called poly(di(2-thiophenyl)carborane) (P1) obtained electrochemically were reported as well as its electrochromic device application. Thiophene donor units and m-carborane acceptor unit were combined under the same umbrella via donor–acceptor–donor approach to obtain di(2-thiophenyl)carborane (1). Contrary to the literature, extreme conditions like highly dried solvent or inert atmosphere were not used for polymerization and characterization. Polymer P1 has an ambipolar character since it exhibited a reversible oxidation peak at a half wave potential (E_1/2) of 1.08 V and a quasi reversible reduction peak at E_1/2 = −1.82 V vs. Ag/AgCl. The polymer film has an optical band gap of 1.95 eV with a maximum absorption band centered at 488 nm. Also, it exhibited multicolor electrochromic behavior between its reduced and oxidized states changing from dark orange to light blue. Furthermore, the electrochromic device prepared based on P1 film was stable and robust.