Synthesis,characterization, and optoelectronic properties of two new polyfluorenes/poly(p‐phenylenevinylene)s copolymers

Two novel copolymers of polyfluorenes/poly(p‐phenylenevinylene)s copolymers with p‐tert‐butyl‐phenylenemethylene groups in the C‐9 position of alternating fluorene unit, poly[1,4‐(2,5‐dibutyloxyl)‐phenyleneviny lene‐alt‐9‐(p‐tert‐butyl‐phenylenemethylene)fluorene] and poly[1,4‐(2,5‐dioctyloxyl)‐phenylenevinylene‐alt‐9‐(p‐tert‐butyl‐phenylenemethylene)fluorine], have been synthesized via the Heck polycondensation reaction. The synthesized polymers were characterized by FTIR, NMR, DSC, TGA, UV–vis, and PL spectra. The polymers showed high glass transition temperatures and good thermal stability. A polymer light‐emitting diode with the configuration ITO/PEDOT:PSS/P2/Ca/Al has been fabricated. The device emitted a yellow light with a peak wavelength of 578 nm similar to the PL spectra of the copolymer film. A maximal luminance of 534 cd/m² was obtained at a driving voltage of 24.5 V. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3955–3962, 2006     

Electrical properties of dye‐doped colour tunable organic light emitting diode

In this work, we report on the electrical properties of dye‐doped colour tunable organic light‐emitting diode (OLED). The device structure is glass substrate/indium tin oxide/N,N′‐di(naphthalen‐1‐yl)‐N,N′‐diphenyl‐benzidine (NPB) 30 nm/Alq₃:DCM 50 nm/Aluminum (Al) 150 nm where NPB is the hole transport layer. Alq₃:DCM is the emitting layer which made of tris(8‐hydroxyquinoline) aluminium (Alq₃) doped with 4‐(Dicyanomethylene)‐2‐methyl‐6‐(4‐dimethyl‐aminostyryl)‐4H‐pyran (DCM) organic dye. The influence of doping concentration has been investigated by current density–voltage measurement, luminance intensity–voltage characteristic, electroluminescence (EL) and impedance spectroscopy, respectively. The EL spectrum exhibits the shifted of peak position from green to red region. The threshold voltage of the device decreased at the low DCM doping concentration (1 wt.%), in contrast, when the increase in the doping concentrations then the threshold voltage will be increased. The highest luminance intensity and lowest turn‐on voltage of OLED can be observed at doping concentration about of 1 wt.% of DCM. The impedance characteristics of the dye‐doped OLED can be modelled by simply adopting the conventional equivalent circuit with the simple combination of resistors and capacitors network. © 2012 Canadian Society for Chemical Engineering     

Synthesis and properties of fluorenyl–pyridinyl alternatingcopolymers for light‐emitting diodes

A novel series of well‐defined alternating poly[2,7‐(9,9‐di(2‐ethylhexyl)fluorenyl)‐alt‐pyridinyl] (PDEHFP) copolymers were synthesized using palladium(0)‐catalyzed Suzuki coupling reaction in high yields. These polymers were characterized using ¹H NMR, UV‐visible and fluorescence spectroscopies, gel permeation chromatography, thermal analysis and cyclic voltammetry. The optical properties of the copolymers, including photoluminescence (PL) and electroluminescence (EL), were studied. The difference in linkage position of pyridinyl units in the polymer backbone has significant effects on the electronic and optical properties of polymers in solution and in film state. Meta‐linkage (3,5‐ and 2,6‐linkage) of pyridinyl units in the polymer backbone is more favorable for pure blue emission and prevention of aggregation of polymer chains. PDEHFPs with 2,6‐ and 3,5‐linkage of pyridinyl units have relatively high PL efficiency of 37 and 44% in the film state. In comparison with homopolymer PDEHF, the copolymers with pyridinyl units possess low lowest unoccupied molecular orbital energy levels for easy electron injection from a cathode. Strong EL is observed and light‐emitting diodes (LEDs) exhibit typical rectifying characteristics. The emission intensity starts to increase at around 12 V. The emission peak wavelengths of the polymers roughly coincide with those of PL. This series of fluorene–pyridine‐based alternating copolymers seem to be candidates for polymeric LEDs. © 2013 Society of Chemical Industry     

A study of light‐emitting diodes constructed with copolymers having cyclohexyl thiophene and hexyl thiophene units

We report visible light emission from a diode made from copolymers of 3‐alkylthiophenes. These chemically synthesized copolymers exhibit improved electroluminescence and quantum efficiencies compared to poly (3‐cyclohexylthiophene). Good solubility of copolymers allows the fabrication of the light emitting diodes by spin‐cast polymer film. The devices emit greenish‐blue light in wavelength region of 550–580 nm, which is easily visible in poorly lighted room. The quantum efficiencies are in the range of 0.002 to 0.01% (photons per electron) at room temperature; which are significantly higher than corresponding values for poly(3‐cyclohexylthiophene) based light emitting diodes. The charge carrier mobility in the device is found to be 5.6 × 10⁻⁴ cm²/Vs. ©2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1051–1055, 2000     

Synthesis of charge transporting block copolymers containing 2,7-dimethoxycarbazole units for light emitting device

The block copolymers consisting of 2,7-dimethoxycarbazole- and oxadiazole-containing segments as hole and electron transporting units, respectively, were synthesized by NMRP manner. OLED devices were fabricated using block copolymer, random copolymer, and polymer blend for matrix of the emitting layer with Ir(ppy)₃ as a phosphorescent dopant in order to investigate morphological effect on the performance. From the finding that the block copolymer system overwhelmed the others in EQE, we assumed that a morphology with dimethoxycarbazole units assembled to the surface of PEDOT:PSS played a considerable role for effective recombination of charges as well as sufficient charge injection into the emitting layer.     

Electrodeposition of Cu-doped ZnO nanowire arrays and heterojunction formation with p-GaN for color tunable light emitting diode applications

Copper-doped zinc oxide (ZnO:Cu) nanowires (NWs) were electrochemically deposited at low temperature on fluor-doped tin oxide (FTO) substrates. The electrochemical behavior of the Cu–Zn system for Cu-doped ZnO electrodeposition was studied and the electrochemical reaction mechanism is discussed. The synthesized ZnO arrayed layers were investigated by using SEM, XRD, EDX, photoluminescence and Raman techniques. X-ray diffraction analysis demonstrates a decrease in the lattice parameters of Cu-doped ZnO NWs. Structural analyses show that the nanomaterial is of hexagonal structure with the Cu incorporated in ZnO NWs probably by substituting zinc in the host lattice. Photoluminescence studies on pure and Cu-doped ZnO NWs shows that the near band edge emission is red-shifted by about 5 or 12 nm depending on Cu(II) concentration in the electrolytic bath solution (3 or 6 μmol l⁻¹). Cu-doped ZnO NWs have been also epitaxially grown on Mg doped p-GaN single-crystalline layers and the (ZnO:Cu NWs)/(p-GaN:Mg) heterojunction has been used to fabricate a light-emitting diode (LED) structure. The emission was red-shifted to the visible violet spectral region compared to pure ZnO. The present work demonstrates the ability of electrodeposition to produce high quality ZnO nanowires with tailored optical properties by doping. The obtained results are of great importance for further studies on bandgap engineering of ZnO, for color-tunable LED applications and for quantum well preparation.     

Hyperbranched polymer for light‐emitting applications

A light‐emitting partially conjugated hyperbranched polymer (2,5‐dimethoxy‐substituted hyperbranched poly(p‐phenylene vinylene), MOHPV) based on rigid fluorescent conjugated segments, 2,5‐dimethoxy‐substituted distyrylbenzene (a derivative of oligo‐poly(p‐phenylene vinylene)), and flexible non‐conjugated spacers, trioxymethylpropane, was synthesized via an A₂ + B₃ approach. The weight‐average molecular weight was 2.48 × 10⁴ g mol^?1. The introduction of two methoxy groups into central rings of the oligo‐poly(p‐phenylene vinylene) imparted to MOHPV better solubility in common organic solvents and processability than its analogues reported in our previous work, especially the fully conjugated hyperbranched polymers. The effect of the molar ratio of monomer A₂ to monomer B₃ on the molecular weight and molecular weight distribution was investigated. A single‐layer light‐emitting diode was fabricated employing MOHPV as an emitter. A double‐layer light‐emitting diode was also fabricated by doping an electron transport material, 2‐(4‐biphenylyl)‐5‐phenyl‐1,3,4‐oxadiazole, into the emitting layer and inserting a thin layer of tri(8‐hydroxyquinoline)aluminium as electron‐transporting/hole‐blocking layer. A maximum luminance of 1500 cd m^?2 at 12 V and a maximum electroluminescence efficiency of 1.38 cd A^?1 at 14 mA cm^?3, which are approximately 43.5 and 12.9 times greater, respectively, than those of the single‐layer device, were achieved. The synthetic simplicity, excellent solubility and solution processability, and less of a propensity to aggregation make MOHPV a novel type of emitter for polymer light‐emitting displays. Copyright © 2010 Society of Chemical Industry     

Improving the image of an organic light‐emitting diode using a dye‐polariser

The present work investigated the image improvement of an organic light‐emitting diode (OLED) by using a dye‐polariser on the panel of an OLED. There are many key vision indexes that can be used to indicate the image performances of flat panel displays (FPDs), such as pixel solution, brightness, view angle, visual reflective sensitivity, contrast ratio, colour saturation and response time. In this study, a dye‐polariser was applied on the panel of an OLED and experiments were conducted to examine the image performances using some relative key vision indexes. The results clearly show the effectiveness of the dye‐polariser used. The OLED showed a reduction in visual reflective sensitivity by 86.6%, improved the contrast ratio of the image to 2.4 and 2.7 times in an indoor (or office) ambience (490 cd/m²) and an outdoor ambience (1375 cd/m²), respectively, increased colour saturation from 59.4% to 66.7%, and reinforced the weaknesses of the red and blue organic fluorescent materials. © 2011 Canadian Society for Chemical Engineering     

Synthesis and electroluminescent properties of a novel copolymer with short alternating conjugated and non‐conjugated blocks

A new electroluminescent copolymer [poly(1,5‐di(3,5‐dimethyloxystyrylene)naphthalene‐block‐tri(ethylene oxide)) (DSN–TEO)], containing alternating rigid, conjugated light‐emitting units and flexible tri(ethylene oxide) ionic conductive units, was synthesized via the Wittig reaction. The polymer has fairly good solubility in chloroform, tetrahydrofuran, toluene, etc, and excellent film‐forming ability. The decomposition temperature and the glass transition temperature were 409 °C and 42.2 °C, respectively. A light‐emitting diode (LED) device with configuration ITO/PEDOT–PSS/DSN–TEO/Ca(Al) and light‐emitting electrochemical cell (LEC) device with ITO/DSN–TEO + PEO (LiTf)/Al were prepared, and the photoluminescence and electroluminescence (EL) properties were investigated. Efficient blue‐green light emission (EL maximum emissive wavelength at 508 nm) was found with onset voltage at 6 V. The maximum light efficiency was 0.107 cd A^?1 at 20 V for LED, and the onset voltage 2.5 V and the maximum light efficiency was 4.2 cd A^?1 at 2.8 V for LEC, respectively. The response time of the LEC was less than 5 s. The EL efficiency of LEC device was improved by 44 as compared with the relative LED device. © 2003 Society of Chemical Industry     

Performance of white light emitting diodes prepared by casting wavelength‐converting polymer on InGaN devices

UV‐curable siloxane oligomers prepared by a hydrosilylation reaction were used as encapsulant. Two fluorescent copolymers with emission covering the range of green and red light were synthesized and blended with the UV‐curable siloxane oligomers and photoinitiator to make the wavelength‐converting polymer (WCP). WCP was casted on blue light emitting InGaN diodes and UV cured to fabricate white light emitting diodes (WLEDs). Effects of monomer compositions on the fluidity of uncured oligomer, together with the optical, thermal, and mechanical properties of the cured polysiloxane were studied. We also investigated the influence of red fluorescent polymer which was comprised of repeating units of dioctylfluorene, bisthienyl‐benzothiadiazole, and benzothiadiazole segments on the color rendering index, correlated color temperature, and luminous efficacy of WLED. Because of the good match between the absorption and emission features of the segments in the fluorescent copolymers, white LEDs can be produced by fluorescent copolymer blends which can support incomplete energy transfer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45210.     

The study of visual image improvement of an organic light‐emitting diode by dye‐polarizer composed of optical film

The visual image improvement of an organic light‐emitting diode (OLED), which is based on some theoretical frameworks and the optical property of the dye‐polarizer composed of optical film, is investigated. The key performance indexes of visions, i.e., visual reflective sensitivity, contrast ratio, and color saturation are focused. First, the reflectance and color saturation of an OLED were simulated and calculated by using the transfer matrix method with thin‐film optical filters and the definition rule of color performances in the 1931 index proposed by the Commission International de l'Eclairage (CIE₁₉₃₁). The results clearly showed excellent performance when using the dye‐polarizer on the panel of an OLED in the theoretical calculation and practical application. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1755–1763, 2012     

Synthesis and properties of novel deep red‐emitting copolymers based on a poly(p‐phenylenevinylene) derivative

A series of novel copolymers based on a poly(p‐phenylenevinylene) (PPV) derivative with different content of narrow band‐gap unit 2,1,3‐benzoselenadiazolevinylene (BSeV) was prepared via Stille coupling reaction. The copolymers emit light from deep red to near‐infrared (NIR) depending on BSeV content in the copolymers. The electroluminescence (EL) emission peaked at 752 nm for the copolymer with the content of 30 mol % BSeV is among the longest reported so far for the PPV polymers. The best device performance is observed for the copolymer with 1 mol % BSeV content with external quantum efficiency (QE_ext) of 0.26% and CIE coordinate 0.65, 0.34 (x,y). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4321–4327, 2006     

Application of styrene‐acrylonitrile random copolymer–polyarylate block copolymer as reactive compatibilizer for polyamide and acrylonitrile‐butadiene‐styrene blends

Styrene‐acrylonitrile random copolymer (SAN) and polyarylate (PAr) block copolymer were applied as a reactive compatibilizer for polyamide‐6 (PA‐6)/acrylonitrile‐butadiene‐styrene (ABS) copolymer blends. The SAN–PAr block copolymer was found to be effective for compatibilization of PA‐6/ABS blends. With the addition of 3.0–5.0 wt % SAN–PAr block copolymer, the ABS‐rich phase could be reduced to a smaller size than 1.0 μm in the 70/30 and 50/50 PA‐6/ABS blends, although it was several microns in the uncompatibilized blends. As a result, for the blends compatibilized with 3–5 wt % block copolymer the impact energy absorption reached the super toughness region in the 70/30 and 50/50 PA‐6/ABS compositions. The compatibilization mechanism of PA‐6/ABS by the SAN–PAr block copolymer was investigated by tetrahydrofuran extraction of the SAN–PAr block copolymer/PA‐6 blends and the model reactions between the block copolymer and low molecular weight compounds. The results of these experiments indicated that the SAN–PAr block copolymer reacted with the PA‐6 during the melt mixing process via an in situ transreaction between the ester units in the PAr chain and the terminal amine in the PA‐6. As a result, SAN–PAr/PA‐6 block copolymers were generated during the melt mixing process. The SAN–PAr block copolymer was supposed to compatibilize the PA‐6 and ABS blend by anchoring the PAr/PA‐6 and SAN chains to the PA‐6 and ABS phases, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2300–2313, 2002     

Synthesis and studies of blue light emitting polymers containing triphenylamine‐substituted fluorene and diphenylanthracene moiety

Photoluminescent (PL) polymers containing triphenylamine‐substituted fluorene and diphenylanthracene (DPA) units were synthesized by aromatic nucleophilic substitution reaction. The light emitting polymers (LEPs) contains hole‐transporting triphenylamine (TPA) groups at the C‐9 position of fluorene and DPA‐emitting segments in the main chain. The obtained polymers were soluble in various organic solvents and thermally stable. The synthesized polymers were successfully characterized by elemental analyses, FTIR and, ¹H NMR spectroscopy. The electrochemical measurements and optical properties of the polymers were also studied. The obtained polymers showed significant blue emission. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Organic light‐emitting diode (OLED) technology: materials,devices and display technologies

Since the breakthrough by Kodak in 1987, organic light‐emitting diodes (OLEDs) have been seen as one of the most promising technologies for future displays. A number of materials have been developed and improved in order to fulfil the requirements of this application. The materials differ from one another by their structure but also by the mechanism involved in the electroluminescence produced (fluorescence versus phosphorescence). When properly stacked, these materials result in a device that can achieve the required high efficiency and long lifetime. Such red, green and blue devices can then be combined in matrices to become the core of a display. Building up these structures onto a display backplane is one of the challenges facing the industry. The circuitry for driving the pixels can be adapted to the OLED, sometimes at the expense of the simplicity of the display, but bearing in mind that the fabrication process must remain industrially viable. Copyright © 2006 Society of Chemical Industry     

Pyrrole‐based narrow‐band‐gap copolymers for red light‐emitting diodes and bulk heterojunction photovoltaic cells

A series of narrow‐band‐gap conjugated copolymers (PFO‐DPT) derived from pyrrole, benzothiadiazole, and 9,9‐dioctylfluorene (DOF) is prepared by the palladium‐catalyzed Suzuki coupling reaction with the molar feed ratio of 4,7‐bis(N‐methylpyrrol‐2‐yl)‐2,1,3‐benzothiadiazole (DPT) around 1, 5, 15, 30, and 50%. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300 nm to 600 nm with two absorbance peaks at around 380 nm and 505 nm. The PL emission consists mainly of DPT unit emission at around 624–686 nm depending on the DPT content in solid film. The EL emission peaks are red‐shifted from 630 nm for PFO‐DPT1 to 660 nm for PFO‐DPT50. Bulk heterojunction photovoltaic cells fabricated from composite films of copolymer and [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively, in device configuration: ITO/PEDOT : PSS/PFO‐DPT : PCBM/Ba/Al shows power conversion efficiencies 0.15% with open‐circuit voltage (V_oc) of 0.60 V and short‐circuit current density (J_sc) of 0.73 mA/cm² under AM1.5 solar simulator (100 mW/cm²). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Biodegradable poly(L‐lactide) and polycaprolactone block copolymer networks

New biodegradable block copolymer networks were synthesized from methacrylate‐terminated poly(L ‐lactide) (mLA) and polycaprolactone (mCL) macromers. This allowed the realization of a series of materials in which the macromer ratio can be used to tailor the physical and mechanical properties of the materials. The synthesis of the macromers was characterized using Fourier transform infrared (FTIR) spectroscopy and ¹H NMR spectroscopy. Poly(mCL) and poly(mLA) networks were prepared by photopolymerization of the macromers, and copolymers were also prepared from the two macromers in various proportions. The phase microstructure of the new systems and the network architecture were investigated using differential scanning calorimetry, FTIR spectroscopy, dynamic mechanical analysis and thermogravimetry studies. Copyright © 2010 Society of Chemical Industry     

Cationic copolymerization of epoxy siloxane monomer with liquid poly‐butadiene and its light emitting diode encapsulation

A novel epoxy siloxane hybrid was prepared using epoxy siloxane monomers of 1,3‐bis[2‐(3‐{7‐oxabicyclo[4.1.0]heptyl})ethyl]‐tetramethyldisiloxane (BEPDS) with hydroxyl terminated hydrogenated polybutadiene (GI‐1000), in different proportions. Apparent polymerization reactivity was decreased with increasing GI‐1000 concentration but the normalized reactivity per epoxy group was slightly increased due to reaction between hydroxyl group and epoxy group. Increasing GI‐1000 concentration showed significant flexibility improvement in epoxy siloxane hybrid. At 30 wt % of GI‐1000 addition, glass transition temperature was decreased from 116 to 21°C and shore D hardness was decreased from 75 to 46.5% weight loss temperature of these epoxy siloxane hybrid was decreased with increasing GI‐1000 concentration, whereas thermal discoloration was increased. LED encapsulation with this epoxy siloxane demonstrated no crack when GI‐1000 was 30 wt % or more. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Non‐catalytic anhydride curing of hydrogenated bisphenol‐A glycidyl ether with 1,2,4‐cyclohexanetricarboxylic anhydride and light emitting diode encapsulation

Noncatalytic anhydride curing of hydrogenated bisphenol‐A glycidyl ether (YX8000) using hydrogenated trimellic anhydride (1,2,4‐cyclohexanetricarboxylic anhydride, H‐TMAn) and methylhexahydrophthalic anhydride (MeHHPA) were studied. Differential scanning calorimetry data shows no exthothermal under 190°C using MeHHPA without catalyst because of the low reactivity. On the other hand, H‐TMAn had higher reactivity and it can be cured without catalyst. The effect of anhydride concentration both on curing and on properties was studied in detail. For example, the highest T_g was found when YX8000 : H‐TMAn = 100 : 75 or YX8000 : MeHHPA = 100 : 100. The highest curing exothermal was found at similar ratio. Following, the encapsulation of light emitting diode (LED) was prepared with two anhydrides. Surface volume decrease was observed with MeHHPA by its evaporation, but H‐TMAn gave flat surface. After thermal cycle test of these LED, H‐TMAn was found to have better crack resistance than MeHHPA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 962–966, 2006