Enhancement of electroluminescence properties of red diketopyrrolopyrrole-doped copolymers by oxadiazole and carbazole units as pendants

Two novel diketopyrrolopyrrole (DPP)-based copolymers P1-2 were prepared by doping red emitting DPP monomer (1 mol%) into benzothiadiazole, alkoxybenzene and 9,9-dialkylfluorene-based copolymers through base-free Suzuki polymerization. P1 contained the pendants of electron-transport oxadiazole and hole-transport carbazole, but P2 did not contain them. P1 had higher glass transition temperature than P2. The electroluminescence (EL) devices of P1 and P2 (ITO/PEDOT:PSS/polymer/CsF/Al) exhibited red emission with external quantum efficiency of 0.63% and 0.18%, and with brightness of 2681 and 885 cd/m², respectively. The results show that the EL properties of P1 are much better than that of P2 due to the introduction of oxadiazole and carbazole as the pendants. The pendants could restrain aggregation which might induce fluorescence quenching and are of benefit to keep high charge mobility. The efficient energy transfer existed among the pendants, polymer backbone and DPP unit. These factors should be responsible for the higher EL performance of P1.     

Synthesis and characterization of fluorine–thiophene-based π-conjugated polymers using coupling reaction

A solution processible fluorine–thiophene-based copolymers, namely poly[2,7-bis(4-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P1), poly[2,7-bis(3-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P2), poly[2,7-bis(3,3′-dioctyl-5,5′-bithien-2yl)-9,9′-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P3) were synthesized using Suzuki and Stille coupling reaction. The polymers showed weight loss starting around 400 °C indicative of good thermal stability. UV–vis properties and photoluminescence (PL) properties were investigated in toluene. P1, P2 and P3 exhibited the absorption maximum at 450, 428 and 435 nm and their PL spectrum peaked at 587, 559 and 560 nm, respectively. And all polymers, P1, P2 and P3, showed electroluminescence (EL) spectrum peaked at 592, 595 and 607 nm in the range of orange red. The polymers were electrochemically active in oxidation regions. P3 especially showed high oxidation stabilities in 1.17 V vs. Ag/Ag⁺. And P1 and P3 showed higher crystallinity than P2, because they have a repeated unit of 3,3-dialkyl-quaterthiophene.     

A soluble self-doped conducting polyaniline graft copolymer as a hole injection layer in polymer light-emitting diodes

We demonstrate that a novel soluble self-doped conducting polyaniline graft copolymer can be used for a hole injection layer (HIL) in polymer light-emitting diodes (PLEDs). The work function of the material (5.18 eV) was similar to that (5.20 eV) of a conventional conducting polymer dispersion, poly(3,4-ethylenedioxythiophene) (PEDOT) doped with polystyrene sulfonate (PSS). When we fabricated PLEDs by using this material, the current-voltage-luminescence characteristics were very similar to those of the device using the PEDOT/PSS. When the material was blended with PSS, the luminous efficiency was further improved up to 11.9 cd/A. Since this kind of soluble type HIL has advantages over the conventional PEDOT/PSS dispersion in terms of the solution processibility and film quality, this soluble graft-type conducting polymer can be one of the promising candidates for a HIL in PLEDs.     

Analysis of various electron blocking layers to improve efficiency in green light-emitting diodes

Efficiency of GaN-based green light-emitting diodes with various electron blocking layers has been studied numerically. By employing conventional AlGaN, graded AlGaN, quaternary AlGaInN and ternary AlInN electron blocking layers, performance of each device has been evaluated. The device characteristics presented include carrier transport, radiative recombination rate, electrostatic field, emission spectra and efficiency.     

Novel copolymers for electroluminescent devices

Two novel luminescent block copolymers (CE–PPV and CE–DMPPV), containing alternating distyrylbenzene [poly(phenylene vinylene) model oligomer] as light‐emitting units and crown‐ether segments as ionic conductive and spacer units were synthesized by use of a Wittig reaction between the dialdehyde monomer and 1,4‐xylylene‐bis(triphenylphosphonium bromide) or 1,4‐bis(triphenylphosphoniomethyl)‐2,5‐dimethoxybenzene dichloride. The synthesized polymers were characterized with FTIR, ¹H‐NMR, UV–Vis, differential scanning calorimetry, and gel permeation chromatography. The number‐average molecular weights were 6896 with a polydispersity index of 1.75 for CE–PPV, and 9301 with a polydispersity index of 2.474 for CE–DMPPV, respectively. The decomposition temperatures and the glass‐transition temperatures were in the range of 395–411°C and 75–77°C, respectively. The electrochemical properties of the copolymers were evaluated and the highest occupied molecular orbital and the lowest unoccupied molecular orbit energy levels of the copolymers were estimated by cyclic voltammetry. Efficient light‐emitting diodes were successfully fabricated. The synthesis, characterization, and electroluminescent properties of the polymers are reported in this study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3316–3321, 2002     

New host copolymers containing pendant triphenylamine and carbazole for efficient green phosphorescent OLEDs

A series of vinyl copolymers (P1-P6) containing pendant hole-transporting triphenylamine (11-88 mol%) and carbazole chromophores were synthesized by radical copolymerization to investigate the influence of triphenylamine groups upon optoelectronic properties. The copolymers were readily soluble in common organic solvents and their weight-average molecular weights (M_ws) were between 1.41 × 10⁴ and 2.24 × 10⁴. They exhibited moderate thermal stability with T_d = 402-432 °C at 5% weight loss. The emission spectra (both PL and EL) of the blends [P1-P6 with 4 wt% Ir(ppy)₃] showed dominant green emission (517 nm) attributed to Ir(ppy)₃ due to efficient energy transfer from P1-P6 to Ir(ppy)₃. The HOMO levels of P1-P6, estimated from onset oxidation potentials in cyclic voltammeter, were −5.42 to −5.18 eV, which are much higher than −5.8 eV of conventional poly(9-vinylcarbazole) (PVK) host owing to high hole-affinity of the triphenylamine groups. The optoelectronic performances of phosphorescent EL devices, using P1-P6 as hosts and Ir(ppy)₃ as dopant (ITO/PEDOT:PSS/P1-P6:Ir(ppy)₃ (4 wt%):PBD (40 wt%)/BCP/Ca/Al), were greatly improved relative to that of PVK. The best performance was obtained with P4 device, in which the maximum luminance and luminance efficiency were 11?501 cd/m² and 10.6 cd/A, respectively.     

AlGaInP light-emitting diodes with SACNTs as current-spreading layer

Transparent conductive current-spreading layer is important for quantum efficiency and thermal performance of light-emitting diodes (LEDs). The increasing demand for tin-doped indium oxide (ITO) caused the price to greatly increase. Super-aligned carbon nanotubes (SACNTs) and Au-coated SACNTs as current-spreading layer were applied on AlGaInP LEDs. The LEDs with Au-coated SACNTs showed good current spreading effect. The voltage bias at 20 mA dropped about 0.15 V, and the optical power increased about 10% compared with the LEDs without SACNTs.     

Improved light extraction of InGaN/GaN blue LEDs by GaOOH NRAs using a thin ATO seed layer

ABSTRACT: We investigated the effect of gallium oxide hydroxide (GaOOH) nanorod arrays (NRAs) on the light extraction of InGaN/GaN MQW blue light-emitting diodes (LEDs). The GaOOH NRAs were prepared on the indium tin oxide electrode (ITO) layer of LEDs by the electrochemical deposition method. The GaOOH NRAs with preferred orientations were grown on the ITO surface by sputtering a thin antimony-doped tin oxide (ATO) seed layer, which enhances heterogeneous reactions. The surface density and coverage were also efficiently controlled by the different growth voltages. For the LEDs with GaOOH NRAs grown at -2 V, the light output power was increased by 22% without suffering from any serious electrical degradation and wavelength shift, compared to the conventional LEDs.     

New fluorene–pyrazino[2,3‐g]quinoxaline‐conjugated copolymers: Synthesis,optoelectronic properties,and electroluminescence characteristics

New donor–acceptor conjugated copolymers called poly}2,7‐(9,9′‐dihexylfluorene)‐co‐5,10‐[pyrazino(2,3‐g)quinoxaline]{s or PFPQs [where F represents the 2,7‐(9,9′‐dihexylfluorene) moiety and PQ represents the 5,10‐(pyrazino[2,3‐g]quinoxaline) moiety], synthesized by the palladium‐catalyzed Suzuki coupling reaction, are reported. The PQ contents in the PFPQ copolymers were 0.3, 1, 5, and 50 mol %, and the resulting copolymers were named PFPQ0.3, PFPQ01, PFPQ05, and PFPQ50, respectively. Absorption spectra showed a progressive redshift as the PQ acceptor content increased. The relatively small optical band gap of 2.08 eV for PFPQ50 suggested strong intramolecular charge transfer (ICT) between the F and PQ moieties. The photoluminescence emission peaks of the PFPQ copolymer films also exhibited a large redshift with enhanced PQ contents, ranging from 551 nm for PFPQ0.3 to 592 nm for PFPQ50. However, the PFPQ copolymer based electroluminescence (EL) devices showed poor device performances probably due to the strong confinement of the electrons in the PQ moiety or significant ICT. This problem was resolved with a binary blend of poly[2,7‐(9,9‐dihexylfluorene)] (PF) and PFPQ with a volume ratio of 95/5 (BPQ05). Multiple emission peaks were observed at 421, 444, 480, 516, and 567 nm in the BPQ05‐based EL devices because the low PQ content led to incomplete energy transfer. The Commission Internationale de L'Eclairage 1931 coordinates of the BPQ05‐based EL device were (0.31, 0.32), which were very close to the standard white emission of (0.33, 0.33). Furthermore, the maximum luminescence intensity and luminescence yield were 524 cd/m² and 0.33 cd/A, respectively. This study suggested that a pure white light emission was achieved with the PFPQ copolymers or PF/PFPQ blends through the control of the energy transfer between F and PQ. Such PFPQ copolymers or PF/PFPQ blends would be interesting for electronic and optoelectronic devices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Simple and Fast Organic Device Encapsulation Using Polyisobutene

Summary: We demonstrate the use of polyisobutene (PIB) in a glass encapsulation method suitable for organic devices. The PIB viscosity at environmental temperatures provides a fast and non‐aggressive passivant layer formation method for device protection with glass. Due to its fully aliphatic character, PIB is suitable for passivating organic light‐emitting and photovoltaic devices. The observed preservation of encapsulated Ca films demonstrates the PIB suitability for air‐unstable metals passivation. Stable I(V) characteristics and increased operational lifetime were observed in PIB‐encapsulated organic devices. This encapsulation method is cheap, simple, and dispenses intensive equipment use, so that it is appropriate even for laboratories with restricted experimental facilities.

Setup used for Ca samples testing. The right Ca contact was encapsulated with PIB and a glass cover plate (dashed square). The electrical diagram of the apparatus used to obtain the resistance behavior is also shown.     

Luminescence enhancement of Cr3+ doped garnet phosphor for high-performance LED towards smart NIR light source

Cr³⁺ doped phosphor shows great potential for near-infrared (NIR) light-emitting diodes (LED), but it suffers from low quantum efficiency and poor thermal stability. Herein, a novel Cr³⁺ doped broadband NIR garnet Ca₃Sc₂Ge₃O₁₂ phosphor was developed. The multisite structure of the emission band is investigated by site-selective spectroscopy and is attributed to the octahedral Cr³⁺ perturbed by defects. Moreover, we propose different strategies to enhance the luminescence of the phosphor, including enhancement of crystallinity and elimination of defects. Compared with the initial sample, the emission intensity of the optimized phosphor is improved for 8.6 times. The optimal Ca₃Sc₂Ge₃O₁₂: 0.06Cr³⁺ phosphor exhibits excellent thermal stability. At 423 K, the integral emission intensity of the optimal sample remains 94.7% of that at room temperature. Finally, high-performance NIR LED was fabricated using a blue LED and the title phosphor. The packaged LED lamp has high radiance (109.3 mW@300 mA) and photoelectric efficiency (15.96%@40 mA). Our study not only provides a boulevard for enhancing the luminescence of Cr doped NIR phosphor, but also gives a new perspective for understanding the multisite luminescence of Cr³⁺ in garnet host.     

Thiophene‐based copolymers synthesized by electropolymerization for application as hole transport layer in organic solar cells

Electrically conducting thiophene‐based copolymers were synthesized by electropolymerization. The potential range used has a strong influence on the film structure and properties. The extent of oxidation of the copolymers was determined from the ratio of the oxidation to reduction charge, Q_ox/Q_red. The use of wide potential range leads to reduced films, whereas the narrow range leads to partially oxidized films. The copolymers exhibit a characteristic band in UV–vis spectra at ～ 410 nm, which shifts to higher wavelengths for the more doped material. The electrical conductivity of the copolymers was correlated to their morphology and their structure. The copolymer with higher conductivity is partially reduced, has compact morphology and higher ratio of quinoid to benzenoid rings. The energy gap of the copolymers is reversely proportional to their electrical conductivity. The optical and electrical properties of the copolymers make them very well suited for use as hole transport layers (HTL) in organic opto‐electronic devices. We prepared polymer : fullerene solar cells with copolymer HTLs. The solar cell performance was tested with very encouraging initial results. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Excimer and electromer suppression of tetraphenylsilane‐based blue‐light‐emitting polymers

Excimer and electromer suppression of tetraphenylsilane‐derivative‐based blue polymer light‐emitting devices (PLEDs) was investigated. Tetraphenylsilane with a rigid bulky structure certainly but not completely suppressed excimer formation among polymer‐chain segments. A poor solvent, toluene, resulted in excimer formation in the solid film during the spin‐coating process, which could not be suppressed by the incorporation of a bulky moiety onto the polymer backbone. In addition, electromers or electroplexes formed by the strong interaction between the oxadiazole and diphenyl(4‐tolyl)amine groups could not be prevented by the tetraphenylsilane moiety. The influences of the bulky moiety, bipolar unit, and device fabrication conditions on the suppression of excimers or electromers in PLEDs are discussed in detail. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Electroluminescence of ordered ZnO nanorod array/p-GaN light-emitting diodes with graphene current spreading layer

Ordered ZnO nanorod array/p-GaN heterojunction light-emitting diodes (LEDs) have been fabricated by introducing graphene as the current spreading layer, which exhibit improved electroluminescence performance by comparison to the LED using a conventional structure (indium-tin-oxide as the current spreading layer). In addition, by adjusting the diameter of ZnO nanorod array in use, the light emission of the ZnO nanorod array/p-GaN heterojunction LEDs was enhanced further. This work has great potential applications in solid-state lighting, high performance optoelectronic devices, and so on.

PACS

78.60.Fi; 85.60.Jb; 78.67.Lt; 81.10.Dn     

Multicolor emission and thin film transistor properties of 1,8-diethynylcarbazole-based conjugated copolymers

1,8-Carbazole-based conjugated copolymers are synthesized by the Sonogashira polycondensation between the 1,8-diethynylcarbazole derivative and dibromo comonomers. The resulting polymers are fully characterized by GPC, and ¹H NMR and IR spectroscopies, and their high thermal stability with the 5% decomposition temperature exceeding 350 °C by thermogravimetric analyses. The optical properties of the carbazole polymers reveal that the comonomer structures significantly affect the absorption and emission spectra. For example, a bathochromic shift of the spectra is achieved when electron-accepting comonomers are selected, finally leading to the production of additive primaries. The mixtures of three carbazole polymers with red, green, and blue emission colors provide a white light emission both in solutions and in thin solid films. In addition, the thin film transistor properties of the carbazole polymers are investigated. The 1,8-carbazole-based polymers display an intermediate mobility between the 2,7-carbazole and 3,6-carbazole-based counter polymers. All these results suggest the potential application possibilities of the 1,8-carbazole-based conjugated polymers in optoelectronic devices.     

Thermal resistance of cycloaliphatic epoxy hybrimer based on sol‐gel derived oligosiloxane for LED encapsulation

Cycloaliphatic epoxy hybrimer bulk was successfully fabricated by thermal curing of cycloaliphatic epoxy oligosiloxane resin synthesized by a sol‐gel condensation reaction with methylhexahydrophthalic anhydride (MHHPA) and tetrabutylphosphonium methanesulfonate (TBPM). The composition of MHHPA and TBPM in the resin was optimized to minimize yellowness of the cycloaliphatic epoxy hybrimer bulk. The sample with the optimized composition showed little discoloration upon thermal aging at 120°C for 360 h under an air atmosphere. On the basis of its high thermal stability with appropriate hardness and a high refractive index of 1.55, cycloaliphatic epoxy hybrimer bulk can be used as a LED encapsulant for white LEDs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of red, green, and blue organic light-emitting diodes using m-MTDATA as a common hole-injection layer

Organic light-emitting diodes (OLEDs) of metal-semiconductor-metal (MSM) structure have been fabricated by using m-MTDATA [4,4′,4′’-tris (3-methylphenylphenylamino) triphenylamine] as a hole-injection layer (HIL). The m-MTDATA is shown to be an effective hole-injecting material for the OLED, in that the insertion of m-MTDATA greatly reduces the roughness of anode surface, lowers the turn-on voltage, and increases the luminous efficiency. Red, green and blue OLEDs were fabricated, and their color coordinates in CIE chromaticity were found to be (0.600, 0.389), (0.240, 0.525) and (0.171, 0.171), respectively. The luminous efficiencies of the fabricated OLEDs were 1.4 lm/W at 106 cd/m² for red, 1.4 lm/W at 100 cd/m² for green, and 2.0 lm/W at 104 cd/m² for blue.     

Synthesis and characterization of new blue‐photoluminescent copolymer derived from bisphenol A

A new copolymer with short alternating conjugated and nonconjugated blocks, derived from bisphenol A (BPAEt₂‐PPV) containing separated phenylenevinylene (PV) units has been synthesized by Wittig condensation. The copolymer is fully soluble in common organic solvents and has a number‐average molecular weight of 3200 with a polydispersity index of 1.53. The structure of the polymer was confirmed by ¹H NMR, ¹³C NMR, FTIR and Raman spectroscopic analysis. Thermogravimetric analysis and differential scanning calorimetry indicate that BPAEt₂‐PPV is stable up to 400°C in air and displays a glass transition temperature of 107°C. The fluorescence spectrum of the polymer film shows an emission in the blue region (428, 456, and 488 nm). The band‐gap energy, estimated from the edge absorption of the film, is about 2.9 eV. A single‐layer diode device of the configuration ITO/BPAEt₂‐PPV/Al has been fabricated and has a relatively low turn‐on voltage of 3.7 V. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Influence of the introduction of phenylene units into the polymer backbone on bandgap of conjugated poly(heteroarylene methines)

A series of conjugated poly(heteroarylene methines) containing alternating aromatic and quinoid phenylene-thiophene moieties in the main chain have been synthesized. These polymers are soluble in common organic solvents, such as chloroform, THF. The optical and electrochemical properties of the conjugated poly(heteroarylene methines), such as band gap, redox potentials, ionization potential, and electron affinity, were found to be significantly modified by the size of lateral groups on phenylene units and the number of phenylene units on the phenylene-thiophene moieties. With the increase of the size of lateral groups on phenylene units, the polymers show much bigger conjugated length. And the introduction of two phenylene units between two thiophene units lowers much more band gap than that of one phenylene unit.