Ideal host and guest system in phosphorescent OLEDs

Ideal host-guest system for emission in phosphorescent OLEDs with only 1% guest doping condition for efficient energy transfer have been demonstrated in the present investigation. Using a narrow band-gap fluorescent host material, bis(10-hydroxybenzo[h] quinolinato)beryllium complex (Bebq₂), and red dopant bis(2-phenylquinoline)(acetylacetonate)iridium (Ir(phq)₂acac), highly efficient red phosphorescent OLEDs (PHOLEDs) exhibiting excellent energy transfer characteristics with a doping concentration of 1% were developed. Fabricated PHOLEDs show a driving voltage of 3.7 V, maximum current and power efficiencies of 26.53 cd/A and 29.58 lm/W, and a maximum external quantum efficiency of 21%. Minimized electron or hole trapping at the phosphorescent guest molecules and efficient Förster and Dexter energy transfers from the Bebq₂ host singlet and triplet states to the emitting triplet of Ir(phq)₂acac guest appear to be the key mechanism for ideal phosphorescence emission.     

Orange phosphorescent organic light-emitting diodes with high operational stability

In this article we report on the performances of phosphorescent orange organic light-emitting diodes (OLEDs) having a high operational stability. The fabricated devices all consist of a “hybrid” structure, where the hole-injection layer was processed from solution, while the rest of the organic materials were deposited by vacuum thermal evaporation. A device stack having an emissive layer comprising a carbazole-based host TCzMe doped with the orange phosphor tris(2-phenylquinoline)iridium(III) [Ir(2-phq)₃] shows improved efficiencies compared to a the same device with the standard N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB) as host material. External quantum efficiency (EQE) up to 7.4% and a power efficiency of 16 lm/W were demonstrated using TCzMe. Most importantly, the operational stability of the device was largely improved, resulting in extrapolated values reaching lifetimes well above 100,000 h at initial luminance of 1000 Cd/m².     

Controlling singlet–triplet splitting in carbazole–oxadiazole based bipolar phosphorescent host materials

A rational molecular design strategy for carbazole–oxadiazole based bipolar host materials was developed to improve the device efficiency of blue phosphorescent organic light-emitting diodes (PHOLED). Steric effects of strategically placed methyl groups led to an increase of triplet energies (o-2MPCzPOXD: 2.66 eV and o-3MPCzPOXD: 2.73 eV versus the initial host material o-PczPOXD: 2.62 eV) while less pronouncedly affecting singlet energies and, therefore, retaining low driving voltages, high power efficiencies and remarkably low efficiency roll-offs in PHOLEDs. The maximum quantum efficiencies (EQE) for blue devices (FIrpic) were significantly raised for o-2MPCzPOXD (13.6%) and o-3MPCzPOXD (11.5%) versus o-PCzPOXD (9.0%) although yielding comparable values for green devices (Ir(ppy)₃; 12.9% and 15.4% versus 13.2%). Supported by theoretical calculations a structure–property relationship was established from photo-physical properties, PHOLED performance measurements and structural characterization from single crystal data.     

Extremely low driving voltage electrophosphorescent green organic light-emitting diodes based on a host material with small singlet–triplet exchange energy without p- or n-doping layer

In order to achieve low driving voltage, electrophosphorescent green organic light-emitting diodes (OLEDs) based on a host material with small energy gap between the lowest excited singlet state and the lowest excited triplet state (ΔE_ST) have been fabricated. 2-biphenyl-4,6-bis(12-phenylindolo[2,3-a] carbazole-11-yl)- 1,3,5-triazine (PIC–TRZ) with ΔE_ST of only 0.11 eV has been found to be bipolar and used as the host for green OLEDs based on tris(2-phenylpyridinato) iridium(III) (Ir(ppy)₃). A very low onset voltage of 2.19 V is achieved in devices without p- or n-doping. Maximum current and power efficiencies are 68 cd/A and 60 lm/W, respectively, and no significant roll-off of current efficiency (58 cd/A at 1000 cd/m² and 62 cd/A at 10,000 cd/m²) have been observed. The small roll-off is due to the improved charge balance and the wide charge recombination zone in the emissive layer.     

Poly(2-(N-carbazolyl)ethyl acrylate) as a host for high efficiency polymer light-emitting devices

Poly(2-(N-carbazolyl)ethyl acrylate), a poly(acrylate) comprised of carbazole-side groups attached via a flexible chain to the polymer backbone (PVAK) has been tested as host for solution-processed polymer light-emitting devices (PLEDs). This non-conjugated polymer proved to be an excellent candidate to host wide-bandgap phosphors. Notably, this polymer exhibited a high thermal stability (T_d = 322 °C), a glass transition temperature (T_g) of 91 °C and a wide bandgap corresponding to the pendent carbazole units and the disrupted π-conjugation of the polymer main chain, making this polymeric host a suitable candidate for wide bandgap triplet emitters. When tested as a host for FIrpic and Ir(ppy)₃, the resulting blue and green light-emitting devices showed a maximum luminous efficiency of 18.25 and 17.74 cd/A, respectively, which are comparable to recent reports of devices made using other carbazole-based oxygen-rich polymeric hosts. The polymer was also characterized by UV–visible absorption, photoluminescence spectroscopy as well as cyclic voltammetry.     

An efficient bis(2-phenylquinoline) (acetylacetonate) iridium(III)-based red organic light-emitting diode with alternating guest:host emitting layers

We report a highly efficient electrophosphorescent bis(2-phenylquinoline) (acetylacetonate) iridium(III) [Ir(2-phq)₂(acac)]-based red organic light-emitting diode. The emission layer consists of a periodic thin layer of guest material of Ir(2-phq)₂(acac) separated by host material of 4,4′-Bis(carbazol-9-yl)biphenyl. The guest and host thicknesses were optimized independently to obtain the best performance. The current efficiency reaches to a maximum of 16.2 cd/A then drops to 15 and 11 cd/A at brightness of 10 and 100 cd/m², respectively. By reducing the thickness of the host layer, the power efficiency was further improved. Device with a maximum power efficiency of 8.3 lm/W was obtained. We also found that the concentration quenching in Ir(2-phq)₂(acac) is dominated by molecular aggregation. Excitonic quenching by radiationless Förster process is miniscule.     

A novel dimesitylboron-substituted indolo[3,2-b]carbazole derivative: Synthesis,electrochemical, photoluminescent and electroluminescent properties

A novel indolo[3,2-b]carbazole derivative containing B(Mes)₂ groups, 5,11-dibutyl-2,8-bis(dimesitylboryl) indolo[3,2-b]carbazole (DBDMBICZ), was synthesized and structurally characterized by elemental analysis, NMR, MS. The thermal, electrochemical and photophysical properties of DBDMBICZ were characterized by thermogravimetric analysis, electrochemical methods, UV–vis absorption spectroscopy and fluorescence spectroscopy. DBDMBICZ exhibited high fluorescence quantum yields (Φ_max = 0.76) in solution and excellent thermal stability (T_d = 290 °C, T_g = 170 °C) and electrochemical stability. The multi-layered OLEDs devices with the configuration of ITO/NPB/CBP/light-emitting layer/Bphen/LiF/Al are fabricated by using DBDMBICZ as light-emitting layer. The devices show the same pure blue emissions at different voltages and relative good electroluminescent performances. The results indicate that DBDMBICZ has potential applications as an excellent optoelectronic material in optical field.     

Thermally cross-linkable host materials for enabling solution-processed multilayer stacks in organic light-emitting devices

A thermally cross-linkable host material, i.e., two vinylbenzyl ether groups containing a carbazole derivative (DV-CBP), was developed for solution-processed multilayer organic light-emitting devices (OLEDs). DV-CBP was thermally cross-linked at styrene end-groups through curing at approximately 180 °C in the absence of a polymerization initiator. This cross-linking reaction rendered the emissive layer insoluble and enabled the subsequent solution deposition of an upper electron-transporting layer. Furthermore, photoluminescence quantum efficiencies of the emissive layer were maintained at greater than 75% throughout the cross-linking reaction. A solution-processed small-molecule electron-transporting layer on top of the cross-linked emissive layer led to lower driving voltages and higher efficiencies in the OLEDs compared to those of a device with a vacuum-deposited Ca electrode on the emissive layer.     

MoO3 as p-type dopant for Alq3-based p–i–n homojunction organic light-emitting diodes

Using high-work-function material MoO₃ as a p-type dopant, efficient single-layer hybrid organic light-emitting diodes (OLEDs) with the p–i–n homojunction structure are investigated. When MoO₃ and Cs₂CO₃ are doped into the conventional emitting/electron-transport material tris-(8-hydroxyquinoline) aluminum (Alq₃), respectively, a significant increase in p- and n-type conductivities is observed compared to that of intrinsic Alq₃ thin films. With optimal doping, the hole and electron mobilities in Alq₃:MoO₃ and Alq₃:Cs₂CO₃ films was estimated to be 9.76 × 10⁻⁶ and 1.26 × 10⁻⁴ cm²/V s, respectively, which is about one order of magnitude higher than that of the undoped device. The p–i–n OLEDs outperform undoped (i–i–i) and single-dopant (p–i–i and i–i–n) OLEDs; they have the lowest turn-on voltage (4.3 V at 1 cd/m²), highest maximum luminance (5860 cd/m² at 11.4 V), and highest luminous efficiency (2.53 cd/A at 100 mA/cm²). These values are better than those for bilayer heterojunction OLEDs using the same emitting layer. The increase in conductivity can be attributed to the charge transfer process between the Alq₃ host and the dopant. Due to the change of carrier concentration in the Alq₃ films, the Fermi level of Alq₃ is close to the highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO) energy levels upon p- and n-type doping, respectively, and the carrier injection efficiency can thus be enhanced because of the lower carrier injection barrier. The carriers move closer to the center energy levels of the HOMO or LUMO distributions, which increases the hopping rate for charge transport and results in an increase of charge carrier mobility. The electrons are the majority charge carriers, and both the holes and electrons can be dramatically injected in high numbers and then efficiently recombined in the p–i–n OLEDs. As a result, the improved conductivity characteristics as well as the appropriate energy levels of the doped layers result in improved electroluminescent performance of the p–i–n homojunction OLEDs.     

Uniform Aerosol Jet printed polymer lines with 30 μm width for 140 ppi resolution RGB organic light emitting diodes

We demonstrate the patterning of top emitting organic light emitting diodes (OLEDs) by direct-write Aerosol Jet printing in air from non-halogenated solvents. Indane was determined to be a suitable single solvent to dissolve the archetypal host poly(N-vinylcarbazole) and guest emitting dopants complexes for red, green, and blue OLEDs, and to print on both PEDOT:PSS and MoO₃ transport layers. The Aerosol Jet deposition parameters were studied, including: atomization flow rate, exhaust flow rate, focusing sheath flow rate, nozzle-to-substrate distance, nozzle speed, and substrate temperature. A line width of 30 μm and thickness of 30 nm was achieved, resulting in RGB OLEDs fabricated side-by-side with a pixel density of 140 ppi.     

Synthesis,photoluminescence and electroluminescence properties of iridium complexes with bulky carbazole dendrons

We synthesized solution-processable iridium complexes having bulky carbazole dendrons, fac-tris[2-{3-(3,5-bis(3,6-di-n-butylcarbazol-9-yl)phenyl)Phenyl)pyridine]iridium (III) (mCP)₃Ir and fac-bis[2-{3-(3,5-bis(3,6-di-n-butylcarbazol-9-yl)phenyl)phenyl}pyridine][2-{3-(3,5-di(4-pyridyl)phenyl)phenyl}pyridine]iridium (III) (mCP)₂(bpp)Ir. Photoluminescence quantum efficiencies (PLQEs) of (mCP)₃Ir and (mCP)₂(bpp)Ir in their diluted solutions were 91% and 84%, respectively. They showed high PLQEs of 49% for (mCP)₃Ir and 29% for (mCP)₂(bpp)Ir even in a neat film. The triplet exciton energy level of the dendronized ligand (2.8 eV), 2-[3-{3,5-bis(3,6-di-n-butylcarbazol-9-yl)phenyl}]pyridine 10, and the dendron (2.9 eV), 3,5-bis(3,6-di-n-butylcarbazol-9-yl)benzene 7, are enough higher than that of the core complex Ir(ppy)₃ (2.6 eV). External quantum efficiency (EQE) of single layer light-emitting device with (mCP)₂(bpp)Ir was much higher than that of (mCP)₃Ir because of better affinity of (mCP)₂(bpp)Ir to cathode metal. When an electron transporting and hole-blocking material was used, the EQEs of double layer devices were dramatically improved to 8.3% for (mCP)₃Ir and 5.4% for (mCP)₂(bpp)Ir at 100 cd/m².     

Iridium-based semi-transparent current spreading layer on short-period-superlattice (SPS) tunneling contact of InGaN/GaN LEDs

Iridium-containing and Ni(4 nm)/Au(6 nm) films were evaporated separately on the n⁺-InGaN–GaN short-period-superlattice (SPS) structure of light-emitting diodes (LEDs). The collective deposition of iridium and other metals as an ohmic contact induces the formation of highly transparent IrO₂, which helps to enhance the light output and decrease the series resistance of LEDs. By comparing different metal films used as current spreading contact layer, Ir/Ni film annealed at 500 °C for 20 min in O₂ ambient renders devices with lowest turn-on voltage at 20 mA and highest luminous intensity. Moreover, we also analyzed films using atomic force microscopy (AFM) with an emphasis on studying how the surface quality of Ir/Ni and Ni/Au films influences the current spreading and luminosity of LEDs.     

Improved hole-transporting properties of Ir complex-doped organic layer for high-efficiency organic light-emitting diodes

We have investigated the hole-transporting properties of three different Ir complexes doped 4,4′,4″-tri (N-carbazolyl) triphenylamine (TCTA) using a series of hole-only devices. The improvement of hole-transporting ability was depended on the species of Ir complexes and their doping concentrations. We attributed the improved performance to their strong electron-accepting abilities or hole-transfer capabilities. Yellow organic light-emitting diodes (OLEDs) based on bis(2-phenylbenzothiazolato)(acetylacetonate)iridium bt₂Ir(acac) were fabricated by utilizing this method with optimized doping concentration. The best electroluminescent (EL) performance of maximum 83.6 lm/W was obtained for the yellowing-emitting OLED by doping of Firpic into TCTA hole transport layer, compared with the cases of doping of Ir(ppy)₃ into TCTA and doping of Ir(bpiq)₂acac into TCTA. Moreover, the turn-on voltage of device decreased to 2.2 V, which was corresponding to the optical band gap of the emitter.     

Photo-induced storage and mask-free arbitrary micro-patterning in solution-processable and simple-structured photochromic organic light-emitting diodes

A photochromic diarylethene-based compound BMTA, which undergoes a reversible conversion between ring- open and closed isomers by alternating UV and visible light illumination, has been designed and synthesized. By utilizing a mask-free Digital Micro-mirror Device (DMD) micro-lithography system, arbitrary micro-photopatterning in polymer films doped with BMTA can be easily obtained with UV light writing. This recorded photo information can easily be erased by further visible light irradiation. The reversible and rewritable optical storage is based on photo-switched intermolecular energy transfer between the emissive host and the ring-closed isomer c-BMTA. Furthermore, the solution-processable organic light-emitting devices (OLEDs) with the single emitting layer doped with BMTA were fabricated, which exhibit rewritable memory behavior with light control. The luminescence and current density decrease significantly upon UV light irradiation, and recover by further visible light illumination. This is because the hole trapping is much facilitated in closed-ring isomer based devices, due to elevated HOMO level of c-BMTA. Without incorporating any cross-linking layer, the maximum luminescence and current density on/off ratios of this solution-processable and simple-structured device are 1.9 × 10³ and 1.4 × 10², respectively. Arbitrary micro-photolithography of OLEDs by DMD system has also been demonstrated, which shows great prospects in large-scale production of high resolution OLED displays.     

Efficient solution-processed blue phosphorescent organic light-emitting diodes with halogen-free solvent to optimize the emissive layer morphology

Efficient solution-processed blue phosphorescent organic light-emitting diodes (OLEDs) featuring with halogen-free solvent processing are fabricated in this study. The organic molecule 3,6-bis(diphenylphosphoryl)-9-(4′-(diphenylphosphoryl) phenyl)-carbazole (TPCz) that possesses good solubility in halogen-free polar solvents is selected to serve as the host of blue phosphorescent iridium(III) [bis(4,6-difluorophenyl)-pyridinato-N,C²]-picolinate (FIrpic) dopant. The morphology of the TPCz:FIrpic emissive layer prepared with different polar solvents including chlorobenzene (CB), n-butanol (ButA) and isopropanol (IPA) and the effect on their electroluminescent performance have been investigated in detail. It is found that the more polar halogen-free solvent IPA restrains the FIrpic aggregation and renders a more densely packed emissive layer as compared to the CB-processed counterpart, which results in the enhanced electroluminescent performance. The luminous efficiency and power efficiency of the blue phosphorescent OLEDs prepared with CB are merely 5.7 cd/A and 3.3 lm/W, respectively. When using more polar halogen-free solvent IPA, the efficiencies are enhanced to 22.3 cd/A and 15.6 lm/W, about 2.9 and 3.7-time increment, respectively. This work provides an approach to fabricate efficient solution-processed phosphorescent OLEDs with environmental-friendly solvents, which is highly required in large-scale solution-processed manufacturing.     

Efficient iridium(III) based, true-blue emitting phosphorescent OLEDS employing both double emission and double buffer layers

New device architectures and efficient iridium based phosphors were simultaneously developed for fabrication of true-blue phosphorescent organic light-emitting devices (OLEDs). To fully explore the potential of these true-blue-emitting phosphors, we employed a device architecture that incorporates both double-emitting layers (one with hole-transport and the second with electron-transport materials) and double buffer layers for efficient exciton confinement. In addition, the parent, true-blue emitting heteroleptic Ir^III complex Ir1 was synthesized by incorporating one 4,6-difluorophenyl-2-pyridyl cyclometalate (dfppy) together with two 3-(trifluoromethyl)-5-pyridyl pyrazolates (fppz), while others derivatives Ir2–Ir4 were prepared by addition of alkyl substituent at the pyridyl sites. Electrophosphorescence with efficiencies up to 13.7% photon/electron and 20.4 cd/A, and with adequate CIE_x,y color coordinates of (0.157, 0.189) were successfully achieved.     

异质结堆叠发光层红色磷光有机发光二极管

本文采用主客体交错结构的发光层,即发光层是 由多组主体材料CBP和客体材料Ir(piq)₂(acac)异质结堆叠构成的。为了改善器件的性能 ,分别优化 了单主体层和单客体层的厚度。研 究表明,单主体层厚度为3~4 nm,单客体层厚度为0.3 nm时,器件能够获得的最大电流效率为3.92 cd/A,色纯度 和发光稳 定性俱佳,1mA工作电流下的CIE色坐标为(0.669,0.308),当工作电流从0.1 mA变化 到1mA,色度坐标的变化值(Δ(x,y)) 仅为(0.004,0.002)。所采用的 主客体交错发光层的制备方法,工艺简单,且因为能分别调整主客体层的厚度而改善因客体 分子聚集或因长程偶极子间相互作用对发光效率的影响,为非掺杂磷光有机发光二极管的制 备提供了思路。     

Heteroleptic iridium (III) complexes with three different ligands: Unusual triplet emitters for light-emitting electrochemical cells

Two cationic iridium (III) complexes [Ir(dfppy)(tpy)(bpy)](PF₆) and [Ir(dfppy)(tpy)(phen)](PF₆) bearing three different ligands were tested as triplet emitters for Light-Emitting Electrochemical Cells (LECs). These two phosphorescent materials only constitute the third and fourth examples of triple heteroleptic cationic iridium complexes to be tested in electroluminescent devices. LECs fabricated with this almost unknown class of iridium complex furnished green-emitting devices. Parallel to investigations devoted to electroluminescent properties, photophysical and electrochemical properties of the two new complexes were examined. Density functional theory calculations were also performed to provide insight into the electronic structure of the two emitters.     

Efficient hole-transporter for phosphorescent organic light emitting diodes with a simple molecular structure

N,N-diphenyl-4-(quinolin-8-yl)aniline (SQTPA), which composes a triphenylamine group and a quinoline group, has been synthesized and employed as a hole-transporter in phosphorescent OLEDs. It has been proved that SQTPA has efficient hole-transport property with a hole-mobility of 3.60 × 10⁻⁵ cm²/V s at the electric field of 800 (V/cm)^1/2, which is higher than that of NPB (1.93 × 10⁻⁵ cm²/V s). Blue, orange and green phosphorescent OLEDs have been fabricated based on FIrpic, Ir(2-phq)₃, Ir(ppy)₃ with typical structures by using SQTPA as the hole-transporter. The SQTPA-based devices show maximum external quantum efficiencies and power efficiencies of 17.5%, 32.5 lm/W for blue, 12.3%, 20.5 lm/W for orange and 20.3%, 64.5 lm/W for green. The performances of SQTPA-based devices are much better than that of NPB-based phosphorescent OLEDs with similar structures. Thought of its very simple molecular structure and easy synthetic route, SQTPA should be an efficient hole-transporter for phosphorescent OLEDs.     

Functionalized terfluorene for solution-processed high efficiency blue fluorescence OLED and electrophosphorescent devices

A new multifunctional blue-emitting terfluorene derivative (TFDPA) featured with triphenylamine groups for hole-transportation and long alkyl chains for solution processability on the conjugation inert bridge centers was reported. TFDPA can give homogeneous thin film by solution process and exhibits high hole mobility (μ_h ≈ 10^?3 cm² V^?1 s^?1) and suitable HOMO for hole injection. Particularly, TFDPA performs efficient deep-blue emission with high quantum yield (～100% in solution, 43% in thin film) and suitable triplet energy (E_T = 2.28 eV), making solution-processed OLED devices of using TFDPA as blue emitter and as host for iridium-containing phosphorescent dopants feasible. The solution-processed nondoped blue OLED device gives saturated deep-blue electroluminescence [CIE = (0.17, 0.07)] with EQE of 2.7%. TFDPA-hosted electrophosphorescent devices performed with EQE of 6.5% for yellow [(Bt)₂Ir(acac)], 9.3% of orange [Ir(2–phq)₃], and 6.9% of red [(Mpq)₂Ir(acac)], respectively. In addition, with careful control on the doping concentration of [(Bt)₂Ir(acac)], a solution-processed fluorescence–phosphorescence hybrided two-color-based WOLED with EQE of 3.6% and CIE coordinate of (0.38, 0.33) was successfully achieved.