Rational Design of Charge‐Neutral,Near‐Infrared‐Emitting Osmium(II) Complexes and OLED Fabrication

A new series of charge neutral Os(II) isoquinolyl triazolate complexes ( 1 – 4 ) with both trans and cis arrangement of phosphine donors are synthesized, and their structural, electrochemical and photophysical properties are established. In sharp contrast to the cis‐arranged complexes 2 – 4 , the trans derivative 1 , which shows a planar arrangement of chromophoric N‐substituted chelates, offers the most effective extended π‐delocalization and hence the lowest excited state energy gap. These complexes exhibit phosphorescence with peak wavelengths ranging from 692–805 nm in degassed CH₂Cl₂ at room temperature. Near‐infrared (NIR)‐emitting electroluminescent devices employing 6 wt % of 1 (or 4 ) doped in Alq₃ host material are successfully fabricated. The devices incorporating 1 as NIR phosphor exhibit fairly intense emission with a peak wavelength at 814 nm. Forward radiant emittance reaches as high as 65.02 µW cm^?2, and a peak EQE of ～1.5% with devices employing Alq₃, TPBi and/or TAZ as electron‐transporting/exciton‐blocking layers. Upon switching to phosphor 4 , the electroluminescence blue shifts to 718 nm, while the maximum EQE and radiance increase to 2.7% and 93.26 (μW cm^?2) respectively. Their performances are optimized upon using TAZ as the electron transporting and exciton‐blocking material. The OLEDs characterized represent the only NIR‐emitting devices fabricated using charge‐neutral and volatile Os(II) phosphors via thermal vacuum deposition.     

High Efficiency White Organic Light‐Emitting Devices Incorporating Yellow Phosphorescent Platinum(II) Complex and Composite Blue Host

A new class of charge neutral, strongly luminescent cyclometalated platinum(II) complexes supported by dianionic tetradentate ligand are synthesized. One of these platinum(II) complexes, Y‐Pt , displays a high photoluminescence quantum yield of 86% and electroluminescence efficacy (η_power) of up to 52 lm W^?1, and is utilized as a yellow phosphorescent dopant in the fabrication of white organic light‐emitting devices (WOLEDs). WOLEDs based on conventional structures with yellow emission from Y‐Pt in combination with blue emission from bis(4,6‐difluorophenyl‐pyridinato‐N,C²′) (picolinate) iridium(III) (FIrpic) show a total η_power of up to 31 lm W^?1. A two‐fold increase in η_power by utilizing a modified WOLED structure comprising of a composite blue host is realized. With this modified device structure, the total η_power and driving voltage at a luminance of 1000 cd m^?2 can be improved to 61 lm W^?1 and 7.5 V (i.e., 10 V for control devices). The performance improvement is attributed to an effectively broaden exciton formation‐recombination zone and alleviation of localized exciton accumulation within the FIrpic‐doped composite host for reduced triplet‐triplet annihilation, yielding blue light‐emission with enhanced intensity. The modified device structure can also adopt a higher concentration of Y‐Pt towards its optimal value, leading to WOLEDs with high efficiency.     

Highly Efficient Electroluminescence from Green‐Light‐Emitting Electrochemical Cells Based on CuI Complexes

The complexes [Cu(dnbp)(DPEphos)]⁺(X^–) (dnbp and DPEphos are 2,9‐di‐n‐butyl‐1,10‐phenanthroline and bis[2‐(diphenylphosphino)phenyl]ether, respectively, and X^– is BF₄^–, ClO₄^–, or PF₆^–) can form high‐quality films with photoluminescence quantum yields of up to 71 ± 7 %. Their electroluminescent properties are studied using the device structure indium tin oxide (ITO)/complex/metal cathode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light‐emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre‐biasing at 25 V for 40 s, the devices turn on instantly, with a turn‐on voltage of ca. 2.9 V. A current efficiency of 56 cd A^–1 and an external quantum efficiency of 16 % are realized with Al as the cathode. Using a low‐work‐function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn‐on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m^–2 at 6 V and 4100 cd m^–2 at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.     

Archetype Cationic Iridium Complexes and Their Use in Solid‐State Light‐Emitting Electrochemical Cells

The archetype ionic transition‐metal complexes (iTMCs) [Ir(ppy)₂(bpy)][PF₆] and [Ir(ppy)₂(phen)][PF₆], where Hppy = 2‐phenylpyridine, bpy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline, are used as the primary active components in light‐emitting electrochemical cells (LECs). Solution and solid‐state photophysical properties are reported for both complexes and are interpreted with the help of density functional theory calculations. LEC devices based on these archetype complexes exhibit long turn‐on times (70 and 160 h, respectively) and low external quantum efficiencies (～2%) when the complex is used as a pure film. The long turn‐on times are attributed to the low mobility of the counterions. The performance of the devices dramatically improves when small amounts of ionic liquids (ILs) are added to the Ir‐iTMC: the turn‐on time improves drastically (from hours to minutes) and the device current and power efficiency increase by almost one order of magnitude. However, the improvement of the turn‐on time is unfortunately accompanied by a decrease in the stability of the device from 700 h to a few hours. After a careful study of the Ir‐iTMC:IL molar ratios, an optimum between turn‐on time and stability is found at a ratio of 4:1. The performance of the optimized devices using these rather simple complexes is among the best reported to date. This holds great promise for devices that use specially‐designed iTMCs and demonstrates the prospect for LECs as low‐cost light sources.     

Red Phosphorescent Iridium Complex Containing Carbazole‐Functionalized β‐Diketonate for Highly Efficient Nondoped Organic Light‐Emitting Diodes

A novel red phosphorescent iridium complex containing a carbazole‐functionalized β‐diketonate, Ir(DBQ)₂(CBDK) (bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐diketonate)) is designed, synthesized, and characterized. The electrophosphorescence properties of a nondoped device using the title complex as an emitter with a device configuration of indium tin oxide (ITO)/N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐diphenyl‐4,4′‐diamine (NPB; 20 nm)/iridium complex (20 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 5 nm)/tris(8‐hydroxyquinoline) (AlQ; 30 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) are examined. The results show that the nondoped device achieves a maximum lumen efficiency as high as 3.49 lm W^–1. To understand this excellent result observed, two reference complexes Ir(DBQ)₂(acac), where acac is the acetyl acetonate anion, and Ir(DBQ)₂(FBDK), [bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(9‐methyl‐fluoren‐9‐yl)‐6,6‐dimethylheptane‐3,5‐diketonate)], have also been synthesized, and as emitters they were examined under the same device configuration. The maximum lumen efficiency of the former compound is found to be 0.26 lm W^–1 while that for the latter is 0.37 lm W^–1, suggesting that the excellent performance of Ir(DBQ)₂(CBDK) can be attributed mainly to an improved hole‐transporting property that benefits the exciton transport. In addition, a bulky diketonate group separates the emitter centers from each other, which is also important for organic light‐emitting diodes.     

Highly efficient single-layer organic light-emitting devices using cationic iridium complex as host

Highly efficient single-layer organic light-emitting devices (OLEDs) based on blended cationic Ir complexes as emitting layer have been demonstrated using narrow band gap cationic Ir complex [Ir(Meppy)₂(pybm)](PF₆) (C1) as guest and wide band gap cationic Ir complex [Ir(dfppy)₂(tzpy-cn)](PF₆) (C2) as host. As compared with single cationic Ir complex emitting layer, these host–guest systems exhibit highly enhanced efficiencies, with maximum luminous efficiency of 25.7 cd/A, external quantum efficiency of 8.6%, which are nearly 3-folds of those of pure C1-based device. Compared with a multilayer host-free device containing C1 as emitting layer and TPBI as electron-transporting and hole-blocking layer, the above single-layer devices also show 2-folds enhancement efficiencies. The high efficiencies achieved in these host–guest systems are among the highest values reported for ionic Ir complexes-based solid-state light-emitting devices. In addition, a white-similar emission with CIE of (0.36, 0.47) has also been achieved with luminous efficiency of 4.2 cd/A as the C1 concentration is 0.1 wt.%. The results demonstrate that the ionic Ir complexes-based host–guest system provides a new approach to achieve highly efficient OLEDs upon single-layer device structure and solution-processing technique.     

Novel Heteroleptic CuI Complexes with Tunable Emission Color for Efficient Phosphorescent Light‐Emitting Diodes

A series of orange‐red to red phosphorescent heteroleptic Cu^I complexes (the first ligand: 2,2′‐biquinoline (bq), 4,4′‐diphenyl‐2,2′‐biquinoline (dpbq) or 3,3′‐methylen‐4,4′‐diphenyl‐2,2′‐biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2‐(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline‐type ligands, complexes [Cu(mdpbq)(PPh₃)₂](BF₄) and [Cu(mdpbq)(DPEphos)](BF₄) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N‐(4‐(carbazol‐9‐yl)phenyl)‐3,6‐bis(carbazol‐9‐yl) carbazole (TCCz), phosphorescent organic light‐emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF₄) exhibits the best device performance. With the device structure of ITO/PEDOT/TCCz:[Cu(mdpbq)(DPEphos)](BF₄) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A^–1 with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu^I complexes with red emission.     

Blue‐Emitting Cationic Iridium Complexes with 2‐(1H‐Pyrazol‐1‐yl)pyridine as the Ancillary Ligand for Efficient Light‐Emitting Electrochemical Cells

Two blue‐emitting cationic iridium complexes with 2‐(1H‐pyrazol‐1‐yl)pyridine (pzpy) as the ancillary ligands, namely, [Ir(ppy)₂(pzpy)]PF₆ and [Ir(dfppy)₂(pzpy)]PF₆ (ppy is 2‐phenylpyridine, dfppy is 2‐(2,4‐difluorophenyl) pyridine, and PF₆^? is hexafluorophosphate), have been prepared, and their photophysical and electrochemical properties have been investigated. In CH₃CN solutions, [Ir(ppy)₂(pzpy)]PF₆ emits blue‐green light (475 nm), which is blue‐shifted by more than 100 nm with respect to the typical cationic iridium complex [Ir(ppy)₂(dtb‐bpy)]PF₆ (dtb‐bpy is 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine); [Ir(dfppy)₂(pzpy)]PF₆ with fluorine‐substituted cyclometalated ligands shows further blue‐shifted light emission (451 nm). Quantum chemical calculations reveal that the emissions are mainly from the ligand‐centered ³π–π* states of the cyclometalated ligands (ppy or dfppy). Light‐emitting electrochemical cells (LECs) based on [Ir(ppy)₂(pzpy)]PF₆ gave green‐blue electroluminescence (486 nm) and had a relatively high efficiency of 4.3 cd A^?1 when an ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate was added into the light‐emitting layer. LECs based on [Ir(dfppy)₂(pzpy)]PF₆ gave blue electroluminescence (460 nm) with CIE (Commission Internationale de L'Eclairage) coordinates of (0.20, 0.28), which is the bluest light emission for iTMCs‐based LECs reported so far. Our work suggests that using diimine ancillary ligands involving electron‐donating nitrogen atoms (like pzpy) is an efficient strategy to turn the light emission of cationic iridium complexes to the blue region.     

Efficient Blue Phosphorescent OLEDs with Improved Stability and Color Purity through Judicious Triplet Exciton Management

Highly efficient and stable blue phosphorescent organic light‐emitting diodes are achieved by employing a step‐wise graded doping of platinum(II) 9‐(pyridin‐2‐yl)‐2‐(9‐(pyridin‐2‐yl)‐9H‐carbazol‐2‐yloxy)‐9H‐carbazole (PtNON) in a device setting. A device employing PtNON demonstrates a high peak external quantum efficiency (EQE) of 17.4% with an estimated LT₇₀ lifetime of over 1330 h at a brightness of 1000 cd m^?2. PtNON is then investigated as a “triplet sensitizer” in an alternating donor–acceptor doped emissive layer to further improve the device emission color purity by carefully managing an efficient Förster resonant energy transfer from PtNON to 2,5,8,11‐tetra‐tert‐butylperylene as a selected acceptor material. Thus, such OLED devices demonstrate an EQE of 16.9% with color coordinates of (0.16, 0.25) and an estimated luminance (LT₇₀) lifetime of 628 h at a high brightness of 1000 cd m^?2.     

Facile Synthesis of Highly Efficient Lepidine‐Based Phosphorescent Iridium(III) Complexes for Yellow and White Organic Light‐Emitting Diodes

Highly efficient lepidine‐based phosphorescent iridium(III) complexes with pentane‐2,4‐dione or triazolpyridine as ancillary ligands have been designed and prepared by a newly developed facile synthetic route. Fluorine atoms and trifluoromethyl groups have been introduced into the different positions of ligand, and their influence on the photophysical properties of complexes has been investigated in detail. All the triazolpyridine‐based complexes display the blueshifted dual‐peak emission compared to the pentane‐2,4‐dione‐based ones with a broad single‐peak emission. The complexes show emission with broad full width at half maximum (FWHM) over 100 nm, and the emissions are ranges from greenish–yellow to orange region with the absolute quantum efficiency (Φ_PL) of 0.21–0.92 in solution, i.e., Φ_PL = 0.92 ( 18 ), which is the highest value among the reported neutral yellow iridium(III) complexes. Furthermore, high‐performance yellow and complementary‐color‐based white organic light‐emitting diodes (OLEDs) have been fabricated. The FWHMs of the yellow, greenish–yellow OLEDs are in the range of 94–102 nm, which are among the highest values of the reported yellow or greenish–yellow‐emitting devices without excimer emission. The maximum external quantum efficiency of monochrome OLEDs can reach 24.1%, which is also the highest value among the reported yellow or greenish–yellow devices. The color rendering indexes of blue and complementary yellow‐based white OLED is as high as 78.     

Efficient and Long Lived Green Light‐Emitting Electrochemical Cells

The combination of high efficiencies and long lifetime in a single light‐emitting electrochemical cell (LEC) device remain a major problem in LEC technology, preventing its application in commercial lighting devices. Three green light‐emitting cationic iridium‐based complexes of the general composition [Ir(C^{^}N)₂(N^{^}N)][PF₆] with 4‐Fppy (2‐(4‐fluorophenyl)pyridinato) as the cyclometalating C^{^}N ligand and 1,10‐phenanthroline ( 1 ), 4,7‐diphenyl‐1,10‐phenanthroline (bathophenanthroline, bphen, 2 ), and 2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (bathocuprione, dmbphen, 3 ) as ancillary N^{^}N ligands are synthesized and characterized. Computational studies are carried out in order to compare the electronic structure of the three ionic transition metal complexes (iTMCs) and provide insights into their potential as LEC emitter materials. LECs are then fabricated with complexes 1 – 3 . Driven under a pulsed current, they display a high luminance and current and power efficiencies. As the LEC based on complex 2 displays the overall best device performance, including the longest lifetime of 474 h, it is selected for subsequent driving conditions optimization. An extraordinary power efficiency of 25 lm W^?1 and current efficiency of 30 cd A^?1 are achieved under optimized operation conditions with reduced current density, resulting in a long device lifetime of 720 h. Altogether, ligand design in iTMCs and optimization of the device driving conditions leads to a significant improvement in LEC performance.     

Unveiling the Role of Dopant Polarity in the Recombination and Performance of Organic Light‐Emitting Diodes

The recombination of charges is an important process in organic photonic devices, because the process influences the device characteristics such as the driving voltage, efficiency, and lifetime. Here, by using various homoleptic and heteroleptic Ir complexes as dopants, it is reported that the stationary dipole moment (μ₀) of the dopant rather than the trap depth (ΔE_t ) is a major factor determining the recombination mechanism in dye‐doped organic light‐emitting diodes (OLEDs). Dopants with large μ₀ (e.g., homoleptic Ir(III) dyes) induce large charge trapping on them, resulting in high driving voltage and trap‐assisted recombination‐dominated emission. On the other hand, dyes with small μ₀ (e.g., heteroleptic Ir(III) dyes) show Langevin recombination‐dominated emission characteristics with much less charge trapping on them no matter what ΔE_t is, leading to lower driving voltage and higher efficiencies. This finding will be useful in any organic photonic devices such as phosphorescent or thermally assisted delayed fluorescent dye sensitized fluorescent OLEDs where trapping and recombination mechanisms play key roles.     

Scrutinizing Design Principles toward Efficient,Long‐Term Stable Green Light‐Emitting Electrochemical Cells

Enhancing the efficiency and lifetime of light emitting electrochemical cells (LEC) is the most important challenge on the way to energy efficient lighting devices of the future. To avail this, emissive Ir(III) complexes with fluoro‐substituted cyclometallated ligands and electron donating groups (methyl and tert ‐butyl)‐substituted diimine ancillary (N^{^}N) ligands and their associated LEC devices are studied. Four different complexes of general composition [Ir(4ppy)₂(N^{^}N)][PF₆] (4Fppy = 2‐(4‐fluorophenyl)pyridine) with the N^{^}N ligand being either 2,2′‐bipyridine ( 1 ), 4.4′‐dimethyl‐2,2′‐bipyridine ( 2 ), 5.5′‐dimethyl‐2,2′‐bipyridine ( 3 ), or 4.4′‐di‐tert ‐butyl‐2,2′‐bipyridine ( 4 ) are synthesized and characterized. All complexes emit in the green region of light with emission maxima of 529–547 nm and photoluminescence quantum yields in the range of 50.6%–59.9%. LECs for electroluminescence studies are fabricated based on these complexes. The LEC based on ( 1 ) driven under pulsed current mode demonstrated the best performance, reaching a maximum luminance of 1605 cd m^?2 resulting in 16 cd A^?1 and 8.6 lm W^?1 for current and power efficiency, respectively, and device lifetime of 668 h. Compared to this, LECs based on ( 3 ) and ( 4 ) perform lower, with luminance and lifetime of 1314 cd m^?2, 45.7 h and 1193 cd m^?2, 54.9 h, respectively. Interestingly, in contrast to common belief, the fluorine content of the Ir‐iTMCs does not adversely affect the LEC performance, but rather electron donating substituents on the N^{^}N ligands are found to dramatically reduce both performance and stability of the green LECs. In light of this, design concepts for green light emitting electrochemical devices have to be reconsidered.     

Solution‐Processed Thermally Activated Delayed Fluorescent OLED with High EQE as 31% Using High Triplet Energy Crosslinkable Hole Transport Materials

Solution‐processed organic light‐emitting diodes (OLEDs) with thermally activated delayed fluorescent (TADF) material as emitter have attracted much attention because of their low cost and high performance. However, exciton quench at the interface between the hole injection layer, poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), and emitting layer (EML) in devices can lead to low device performance. Here, a novel high triplet energy (2.89 eV) and crosslinkable hole‐transporting material grafted with oxetane groups, N,N‐bis(4‐(6‐((3‐ethyloxetan‐3‐yl)methoxy)hexyloxy)phenyl)‐3,5‐di(9H‐carbazol‐9‐yl)benzenamine (Oxe‐DCDPA)), as crosslinked hole transport layer (HTL) into the interface of PEDOT:PSS layer and EML is proposed for prevention of exciton quenching, and among the reported devices with single HTL in solution‐processed TADF‐OLED, the highest external quantum efficiency (EQE)/luminous efficiency (η_L) of 26.1%/94.8 cd A^?1 and 24.0%/74.0 cd A^?1 are achieved for green emission (DACT‐II as emitter) and bluish‐green emission (DMAC‐TRZ as emitter), respectively. Further improvement, using double HTLs, composed of N,N′‐bis(4‐(6‐((3‐ethyloxetan‐3‐yl)methoxy))‐hexylphenyl)‐N,N′‐diphenyl‐4,4′‐diamine with high hole mobility and Oxe‐DCDPA with high triplet energy, leads to the highest EQE/η_L of 30.8%/111.9 cd A^?1 and 27.2%/83.8 cd A^?1 for green emission and bluish‐green emission, respectively. These two devices show the high maximum brightness of 81 100 and 70 000 cd m^?2, respectively.     

Pure‐Red Dye for Organic Electroluminescent Devices: Bis‐Condensed DCM Derivatives

In this paper, the bis‐condensed 4‐(dicyanomethylene)‐2‐methyl‐6‐[p‐(dimethylamino)styryl]‐4H‐pyran ( DCM) derivatives are introduced as a new class of red dye for organic light‐emitting devices (OLEDs). They showed more red‐shifted emission than the mono‐substituted DCM derivatives and the emission maxima increased as the electron‐donating ability of the aromatic donor group increased. On the basis of these results, red light‐emitting devices were fabricated with bis‐condensed DCM derivatives as red dopants. For a device of configuration ITO/TPD/Alq₃ + DADB (5.2 wt.‐%)/Alq₃/Al (where ITO is indium tin oxide, TPD is N,N′‐diphenyl‐N,N′‐bis(3‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine, Alq₃ is tris(8‐hydroxyquinoline) aluminum, and DADB is [2,6‐bis[2‐[5‐(dibutylamino)phenyl]vinyl]‐4H‐pyran‐4‐ylidene]propanedinitrile), pure red emission was observed with Commission Internationale de l’Eclairage (CIE 1931) coordinates of (0.658, 0.337) at 25 mA/cm².     

Orange and Red Organic Light‐Emitting Devices Employing Neutral Ru(II) Emitters: Rational Design and Prospects for Color Tuning

A new series of charge‐neutral Ru(II ) pyridyl and isoquinoline pyrazolate complexes, [Ru(bppz)₂(PPh₂Me)₂] (bbpz: 3‐tert‐butyl‐5‐pyridyl pyrazolate) ( 1 ), [Ru(fppz)₂(PPh₂Me)₂] (fppz: 3‐trifluoromethyl‐5‐pyridyl pyrazolate) ( 2 ), [Ru(ibpz)₂(PPhMe₂)₂] (ibpz: 3‐tert‐butyl‐5‐(1‐isoquinolyl) pyrazolate) ( 3 ), [Ru(ibpz)₂(PPh₂Me)₂] ( 4 ), [Ru(ifpz)₂(PPh₂Me)₂] (ifpz: 3‐trifluoromethyl‐5‐(1‐isoquinolyl) pyrazolate) ( 5 ), [Ru(ibpz)₂(dpp?)] (dpp? represents cis‐1,2‐bis‐(diphenylphosphino)ethene) ( 6 ), and [Ru(ifpz)₂(dpp?)] ( 7 ), have been synthesized, and their structural, electrochemical, and photophysical properties have been characterized. A comprehensive time‐dependant density functional theory (TDDFT) approach has been used to assign the observed electronic transitions to specific frontier orbital configurations. A multilayer organic light‐emitting device (OLED) using 24 wt % of 5 as the dopant emitter in a 4,4′‐N,N′‐dicarbazolyl‐1,1′‐biphenyl (CBP) host with 4,4′‐bis[N‐(1‐naphthyl)‐N‐phenylamino]biphenyl (NPB) as the hole‐transport layer exhibits saturated red emission with an external quantum efficiency (EQE) of 5.10 %, luminous efficiency of 5.74 cd A^–1, and power efficiency of 2.62 lm W^–1. The incorporation of a thin layer of poly(styrene sulfonate)‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT) between indium tin oxide (ITO) and NPB gave anoptimized device with an EQE of 7.03 %, luminous efficiency of 8.02 cd A^–1, and power efficiency of 2.74 lm W^–1 at 20 mA cm^–2. These values represent a breakthrough in the field of OLEDs using less expensive Ru(II ) metal complexes. The nonionic nature of the complexes as well as their high emission quantum efficiencies and short radiative lifetimes are believed to be the key factors enabling this unprecedented achievement. The prospects for color tuning based on Ru(II ) complexes are also discussed in light of some theoretical calculations.     

Efficient Light‐Emitting Electrochemical Cells (LECs) Based on Ionic Iridium(III) Complexes with 1,3,4‐Oxadiazole Ligands

Eight new iridium(III) complexes 1‐8 , with 1,3,4‐oxadiazole (OXD) derivatives as the cyclometalated C^N ligand and/or the ancillary N^N ligands are synthesized and their electrochemical, photophysical, and solid‐state light‐emitting electrochemical cell (LEC) properties are investigated. Complexes 1 , 2 , 7 and 8 are additionally characterized by single crystal X‐ray diffraction. LECs based on complexes 1‐8 are fabricated with a structure indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/cationic iridium complex:ionic liquid/Al. LECs of complexes 1 – 6 with OXD derivatives as the cyclometalated ligands and as the ancillary ligand show yellow luminescence (λ_max = 552–564 nm). LECs of complexes 7 and 8 with cyclometalated C^N phenylpyridine ligands and an ancillary N^N OXD ligand show red emission (λ_max 616–624 nm). Using complex 7 external quantum efficiency (EQE) values of >10% are obtained for devices (210 nm emission layer) at 3.5 V. For thinner devices (70 nm) high brightness is achieved: red emission for 7 (8528 cd m^?2 at 10 V) and yellow emission for 1 (3125 cd m^?2 at 14 V).     

Cover Picture: An Organic Light‐Emitting Diode with Field‐Effect Electron Transport (Adv. Funct. Mater. 1/2008)

The cover shows an organic light‐emitting diode with remote metallic cathode, reported by Sarah Schols and co‐workers on p. 136. The metallic cathode is displaced from the light‐emission zone by one to several micrometers. The injected electrons accumulate at an organic heterojunction and are transported to the light‐emission zone by field‐effect. The achieved charge‐carrier mobility and in combination with reduced optical absorption losses because of the remoteness of the cathode may lead to applications as waveguide OLEDs and possibly a laser structure. (The result was obtained in the EU‐funded project “OLAS” IST‐ FP6‐015034.) We describe an organic light‐emitting diode (OLED) using field‐effect to transport electrons. The device is a hybrid between a diode and a field‐effect transistor. Compared to conventional OLEDs, the metallic cathode is displaced by one to several micrometers from the light‐emitting zone. This micrometer‐sized distance can be bridged by electrons with enhanced field‐effect mobility. The device is fabricated using poly(triarylamine) (PTAA) as the hole‐transport material, tris(8‐hydroxyquinoline) aluminum (Alq₃) doped with 4‐(dicyanomethylene)‐2‐methyl‐6‐(julolindin‐4‐yl‐vinyl)‐4H‐pyran (DCM₂) as the active light‐emitting layer, and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C₁₃H₂₇), as the electron‐transport material. The obtained external quantum efficiencies are as high as for conventional OLEDs comprising the same materials. The quantum efficiencies of the new devices are remarkably independent of the current, up to current densities of more than 10 A cm^–2. In addition, the absence of a metallic cathode covering the light‐emission zone permits top‐emission and could reduce optical absorption losses in waveguide structures. These properties may be useful in the future for the fabrication of solid‐state high‐brightness organic light sources.     

High‐Purity‐Blue and High‐Efficiency Electroluminescent Devices Based on Anthracene

Novel blue‐light‐emitting materials, 9,10‐bis(1,2‐diphenyl styryl)anthracene (BDSA) and 9,10‐bis(4′‐triphenylsilylphenyl)anthracene (BTSA), which are composed of an anthracene molecule as the main unit and a rigid and bulky 1,2‐diphenylstyryl or triphenylsilylphenyl side unit, have been designed and synthesized. Theoretical calculations on the three‐dimensional structures of BDSA and BTSA show that they have a non‐coplanar structure and inhibited intermolecular interactions, resulting in a high luminescence efficiency and good color purity. By incorporating these new, non‐doped, blue‐light‐emitting materials into a multilayer device structure, it is possible to achieve luminance efficiencies of 1.43 lm W^–1 (3.0 cd A^–1 at 6.6 V) for BDSA and 0.61 lm W^–1 (1.3 cd A^–1 at 6.7 V) for BTSA at 10 mA cm^–2. The electroluminescence spectrum of the indium tin oxide (ITO)/copper phthalocyanine (CuPc)/1,4‐bis[(1‐naphthylphenyl)‐amino]biphenyl (α‐NPD)/BDSA/tris(9‐hydroxyquinolinato)aluminum (Alq₃)/LiF/Al device shows a narrow emission band with a full width at half maximum (FWHM) of 55 nm and a λ_max = 453 nm. The FWHM of the ITO/CuPc/α‐NPD/BTSA/Alq₃/LiF/Al device is 53 nm, with a λ_max = 436 nm. Regarding color, the devices showed highly pure blue emission ((x,y) = (0.15,0.09) for BTSA, (x,y) = (0.14,0.10) for BDSA) at 10 mA cm^–2 in Commission Internationale de l'Eclairage (CIE) chromaticity coordinates.     

Highly Efficient Red Phosphorescent OLEDs based on Non‐Conjugated Silicon‐Cored Spirobifluorene Derivative Doped with Ir‐Complexes

A novel host material containing silicon‐cored spirobifluorene derivative (SBP‐TS‐PSB), is designed, synthesized, and characterized for red phosphorescent organic light‐emitting diodes (OLEDs). The SBP‐TS‐PSB has excellent thermal and morphological stabilities and exhibits high electroluminescence (EL) efficiency as a host for the red phosphorescent OLEDs. The electrophosphorescence properties of the devices using SBP‐TS‐PSB as the host and red phosphorescent iridium (III) complexes as the emitter are investigated and these devices exhibit higher EL performances compared with the reference devices with 4,4′‐N,N′‐dicarbazole‐biphenyl (CBP) as a host material; for example, a (piq)₂Ir(acac)‐doped SBP‐TS‐PSB device shows maximum external quantum efficiency of η_ext = 14.6%, power efficiency of 10.3 lm W^?1 and Commission International de L'Eclairage color coordinates (0.68, 0.32) at J = 1.5 mA cm^?2, while the device with the CBP host shows maximum η_ext = 12.1%. These high performances can be mainly explained by efficient triplet energy transfer from the host to the guests and improved charge balance attributable to the bipolar characteristics of the spirobifluorene group.