Improved efficiency roll-off at high brightness in simplified phosphorescent organic light emitting diodes with a crossfading-host

We report a high efficiency and low efficiency roll-off green phosphorescent organic light emitting diode using both hole- and electron-transporting host materials in a crossfading profile. To eliminate the energy barrier and reduce the charge carrier accumulation, the host materials are used as transporting layers as well, which also simplifies the device fabrication. It is found out that the recombination zone of gradient doping host sample is not only wider but also extended at high current density, which contributes to the suppressed efficiency roll-off at high luminance. An external quantum efficiency of 21.0% at 1000 cd/m² is obtained, and maintains to 19.3% at 10,000 cd/m².     

Voltage independent white emission from all solution processed polymer light-emitting diode with dual emitting layers spaced by an alcohol soluble conjugated polymer as interlayer

Spatial control of recombination zone in multilayer white polymer light emitting diode (WPLED) is highly desirable for stable white-light emission. In this work, the utilization of 18-crown-6 (Cn6)-grafted polyfluorene (PFCn6) as an interlayer in between two emitting layers is demonstrated to control the recombination zones for the multilayer WPLED with β-phase and rubrene doped poly(9,9-di-n-octylfluorene) (PFO) as blue- and yellow-emitting layers, respectively. The device gives the maximum brightness of 15,695 cd/m² and maximum efficiency 5.43 cd/A, accompanying with voltage-independent electroluminescence spectrum having invariant Commission Internationale de L’Eclairage (CIE) coordinates of (0.32, 0.36). The performance with the luminance efficiency 5.43 cd/A and voltage independent white emission is the highest record among the reported multilayer WPLED.     

Silver grid transparent conducting electrodes for organic light emitting diodes

Polymer organic light emitting diodes (OLEDs) were fabricated using thin silver hexagonal grids replacing indium tin oxide (ITO) as the transparent conducting electrodes (TCE). Previous literature has assumed that thick metal grids (several hundred nanometres thick) with a lower sheet resistance (<10 Ω/□) and a similar light transmission (>80%) compared to thinner grids would lead to OLEDs with better performance than when thinner metal grid lines are used. This assumption is critically examined using OLEDs on various metal grids with different thicknesses and studying their performances. The experimental results show that a 20 nm thick silver grid TCE resulted in more efficient OLEDs with higher luminance (10 cd/A and 1460 cd/m² at 6.5 V) than a 111 nm thick silver grid TCE (5 cd/A and 159 cd/m² at 6.5 V). Furthermore, the 20 nm thick silver grid OLED has a higher luminous efficiency than the ITO OLED (6 cd/A and 1540 cd/m² at 6.5 V) at low voltages. The data shows that thinner metal grid TCEs (about 20 nm) make the most efficient OLEDs, contrary to previous expectations.     

Efficient nondoped organic light-emitting diodes with Cu complex emitter

In Cu^I complex based organic light emitting diodes (OLEDs) a host matrix is traditionally thought to be required to achieve high efficiency. Herein, it is found that the device ITO/MoO₃ (1 nm)/4,4′-N,N′-dicarbazole-biphenyl (CBP, 35 nm)/[Cu(μ-I)dppb]₂ (dppb = 1,2-bis[diphenylphosphino]benzene, 20 nm)/1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi, 65 nm)/LiF (1 nm)/Al (100 nm) with a vacuum thermal evaporated nondoped Cu^I complex emissive layer (EML) showed external quantum efficiency and current efficiency of 8.0% and 24.3 cd/A at a brightness of 100 cd/m², respectively, which are comparable to the maximum efficiencies reported in an optimized doped OLED with the same emitter, higher efficiency than the OLED with a [Cu(μ-I)dppb]₂:CBP EML, and much higher efficiencies than the nondoped OLED with a bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)] EML. A series of reference films and single carrier devices were fabricated and studied to understand the difference between Cu^I and Ir^III complex based nondoped OLEDs.     

Efficient blue emitters based on 1,3,5-triazine for nondoped organic light emitting diode applications

Two novel efficient blue emitters (TTT-1, TTT-2) containing 1,3,5-triazine, thiophene and triphenylamine have been designed and synthesized. Organic light emitting diodes (OLEDs) using these new triazine derivatives as emissive layers, ITO/TAPC (60 nm)/TTT-1 (Device A) or TTT-2 (Device B) (40 nm)/TPBi (60 nm)/LiF (1 nm)/Al (100 nm), were fabricated and tested. The OLEDs exhibited good performances with low turn-on voltage of 3 V, maximum luminance of ca. 8990 cd/m² for TTT-1 and 15,980 cd/m² for TTT-2, and maximum luminance efficiency of 4.7 cd/A for TTT-1 and 4.0 cd/A for TTT-2, respectively.     

Efficient simplified orange and white phosphorescent organic light-emitting devices with reduced efficiency roll-off

Efficient orange phosphorescent organic light-emitting devices based on simplified structure with maximum efficiencies of 46.5 lm/W and 51.5 cd/A were reported. One device had extremely low efficiency roll-off with efficiencies of 50.6 cd/A, 45.0 cd/A and 39.2 cd/A at 1000 cd/m², 5000 cd/m² and 10,000 cd/m² respectively. The reduced efficiency roll-off was attributed to more balanced carrier injection and broader recombination zone. The designed simplified white device showed much lower efficiency roll-off than the control one based on multiple emitting layers. The efficiency of simplified white device was 40.8 cd/A at 1000 cd/m² with Commission Internationale de I’Eclairage coordinates of (0.39, 0.46).     

Color stable and low driving voltage white organic light-emitting diodes with low efficiency roll-off achieved by selective hole transport buffer layers

White organic light-emitting diodes (WOLEDs) showing high color stability, low operating voltage, high efficiency and low efficiency roll-off by adopting different hole transport buffer layers which also behaves as electron/exciton blocking layers (EBL) have been developed. The characteristics of WOLEDs based on blue–green and orange phosphors could be easily manipulated by hole transport buffer layer, which tailors charge carrier transportation and energy transfer. Our WOLEDs show low operating voltages, 100 cd/m² at 3.2 V, 1000 cd/m² at 3.7 V and 10000 cd/m² at 4.8 V, respectively, and achieve a current efficiency of 35.0 cd/A, a power efficiency of 29.0 lm/W at a brightness of 1000 cd/m², and a low efficiency roll-off 8.7% calculated from the maximum efficiency value to that of 5000 cd/m².     

Recent development of polyfluorene-based RGB materials for light emitting diodes

As a continuation of our presentation at IUMRS-2000 in Hong Kong, we report the latest development of polyfluorene-based Red, Green and Blue (RGB) materials for light emitting diodes at The Dow Chemical Company. A modified Suzuki coupling process is used to synthesize RGB fluorene-based homopolymers and copolymers. Optimization of reaction conditions has led to a highly efficient procedure to generate polymers with controlled molecular weight (Mw), ranging from 10,000 to above 500,000 depending on the requirements of the desired applications. The optical and electronic properties of the polymers are tailored through selective incorporation of different aromatic units into the fluorene copolymer systems. By using this methodology, a portfolio of fluorene-based polymers has been designed and synthesized, achieving emissive colors that cover the entire visible spectrum.The performance of fluorene-based polymers in light emitting devices has been optimized by modifying the polymer compositions so as to increase charge mobilities and to improve the carrier injection balance. As a result of these compositional changes, devices based on Dow's green emitters, using bi-layer structures on indium tin oxide substrates and evaporated metal cathodes, have demonstrated unprecedented high efficiencies at high brightness levels and long lifetime performance. A device comprised of a Dow green emitting polymer has a low turn-on voltage of 2.25 V and exhibits a peak efficiency of 10.5 Cd/A at 6600 Cd/m² at 4.85 V. These devices maintain an efficiency of greater than 10.0 Cd/A up to 50,000 Cd/m²and demonstrate very good stability as exemplified by a device half-life of greater than 1500-h starting from 1100 Cd/m². Similar outstanding progress with red and blue emitters has also been made and will be discussed.     

Efficient non-doped blue light emitting diodes based on novel carbazole-substituted anthracene derivatives

In this study, we synthesized three anthracene derivatives featuring carbazole moieties as side groups - 2-tert-butyl-9,10-bis[4-(9-carbazolyl)phenyl]anthracene (Cz⁹PhAnt), 2-tert-butyl-9,10-bis{4-[3,6-di-tert-butyl-(9-carbazolyl)]phenyl}anthracene (tCz⁹PhAnt), and 2-tert-butyl-9,10-bis{4′-[3,6-di-tert-butyl-(9-carbazolyl)]biphenyl-4-yl}anthracene (tCz⁹Ph₂Ant) - for use in blue organic light emitting devices (OLEDs). The anthracene derivatives presenting rigid and bulky tert-butyl-substituted carbazole units possessed high glass-transition temperatures (220 °C). Moreover, the three anthracene derivatives exhibited strong blue emissions in solution, with high quantum efficiencies (91%). We studied the electroluminescence (EL) properties of non-doped OLEDs incorporating these anthracene derivatives, with and without a hole-transporting layer (HTL). OLEDs incorporating an HTL provided superior EL performance than did those lacking the HTL. The highest brightness (6821 cd/m²) was that for the tCz⁹PhAnt-based device; the greatest current efficiency (2.1 cd/A) was that for the tCz⁹Ph₂Ant-based device. The devices based on these carbazole-substituted anthracene derivatives also exhibited high color purity.     

Achieving above 30% external quantum efficiency for inverted phosphorescence organic light-emitting diodes based on ultrathin emitting layer

High efficiency inverted phosphorescence organic light-emitting diodes (PhOLEDs) based on ultrathin undoped and doped emitting layer (EML) have been developed. Compared to conventional device, the inverted PhOLED with 0.5 nm undoped EML exhibits significantly larger external quantum efficiency (EQE), due to effective energy transfer from the excited host to the emitter. According to the atomic force microscopy image of EML, the 0.5 nm emitter sandwiched by two hosts can be considered as the emitter doped in two hosts. The inverted device with intentionally doped ultrathin EML (1.5 nm) exhibits the maximum EQE of 31.1%, which is attributed to optimized charge balance and preferred horizontal orientation of emitter. However, such inverted device has large efficiency roll-off at high brightness because of triplet–triplet annihilation process within the ultrathin EML. This can be improved by broadening the doped EML. The inverted device with 10.5 nm doped EML has about EQE of 20 % at 10,000 cd/m². It is expected that our inverted PhOLED will promote development of high efficiency active-matrix organic light-emitting diodes based on the n-type Indium Gallium Zinc Oxide thin film transistor.     

Efficient fluorescent white organic light-emitting devices based on a ultrathin 5,6,11,12-tetraphenylnaphthacene layer

White organic light-emitting devices (OLEDs) were fabricated using a ultrathin layer 5,6,11,12-tetraphenylnaphthacene as the yellow light-emitting layer and p-bis(p-N,N-diphenyl-aminostyryl)benzene (DSA-ph) doped in 2-methyl-9,10-di(2-naphthyl)anthracene (MADN) matrix as the blue light-emitting layer. The thickness of rubrene ultrathin layer will seriously affect the device performance, and the device with 1 nm rubrene achieves the best performance, with the maximum luminance of 33,152 cd/m² at 11 V and the maximum current efficiency of 8.69 cd/A at 7 V.     

High efficiency green phosphorescent organic light-emitting diodes with a low roll-off at high brightness

Highly efficient green phosphorescent organic light-emitting diodes (PHOLEDs) with low efficiency roll-off at high brightness have been demonstrated with a novel iridium complex. The host material 1,3-bis(carbazol-9-yl)benzene (mCP) with high triplet energy is also used as the hole transporting layer to avoid carrier accumulation near the exciton formation interface and reduce exciton quenching. It provides a new approach for easily fabricating PHOLED with high triplet energy emitter. Moreover, the hole blocking layer is extended into the light emitting layer to form a co-host, realizing better control of the carrier balance and broader recombination zone. As a consequence, a maximum external quantum efficiency of 20.8% and current efficiency of 72.9 cd/A have been achieved, and maintain to 17.4% and 60.7 cd/A even at 10,000 cd/m², respectively.     

White organic light emitting devices with a color conversion layer

A white organic light emitting device (WOLED) combining the blue organic light emitting device with a red color conversion layer (CCL) is reported, which includes a fluorescent material N-(4-((E)-2-(6-((E)-4-(diphenylamino) styryl)naphtha len-2-yl)vinyl) phenyl)-N-phenylbenzenamine (N-BDAVBi) doped into 4,4′-N,N′-dicarbazole-biphenyl (CBP) as the blue light emitting layer, and the poly (2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene (MEH-PPV) as a red CCL. By optimizing the concentration of MEH-PPV in the CCL, a good white light emission is obtained, which shows that the stable CIE coordinates of (0.33, 0.34) will have a slight change when the driving voltage is increased from 6 to 11 V. The maximum brightness and current efficiency of the optimized device are 11294 cd/m² and 6.4 cd/A, respectively.     

A new spiro[fluorene-9,9′-xanthene]-based host material possessing no conventional hole- and electron-transporting units for efficient and low voltage blue PHOLED via simple two-step synthesis

A new spiro[fluorene-9,9′-xanthene]-based host material SFX-PF without possessing conventional hole- and electron-transporting units has been developed, via very simple two-step synthesis, for efficient and low voltage blue phosphorescent organic light-emitting device (PHOLED). The blue device exhibited a low turn-on voltage of 2.8 V, and high maximum current efficiency, power efficiency, and external quantum efficiency up to 29.3 cd/A, 28.9 lm/W, and 14.7%, respectively. At the luminance level of 1000 cd/m², the driving voltages are still lower than 4.0 V with 12.9% roll-off of the external quantum efficiency. Based on our previous studies, these investigations provide the clues that SFX could be a new building block for designing blue phosphorescent host materials.     

High efficiency and non-color-changing orange organic light emitting diodes with red and green emitting layers

We report a high performance orange organic light-emitting diode (OLED) where red and green phosphorescent dyes are doped in an exciplex forming co-host as separate red and green emitting layers (EMLs). The OLED shows a maximum external quantum efficiency (EQE) of 22.8%, a low roll-off of efficiency with an EQE of 19.6% at 10,000 cd/m², and good orange color with a CIE coordinate of (0.442, 0.529) and no color change from 1000 to 10,000 cd/m². The exciplex forming co-host system distributes the recombination zone all over the EMLs and reduces the triplet exciton quenching processes.     

Stacked inverted top-emitting green electrophosphorescent organic light-emitting diodes on glass and flexible glass substrates

Stacked inverted top-emitting green electrophosphorescent organic light-emitting diodes (OLEDs) are demonstrated on glass and flexible glass substrates. A single-unit OLED is shown to have a current efficacy of 46.8 cd/A at a luminance of 1215 cd/m². When two of these OLEDs are stacked, the double-unit OLED exhibits a current efficacy more than twice that of the single-unit OLED, with a current efficacy of 97.8 cd/A at a luminance of 1119 cd/m². With the addition of an optical outcoupling layer of N,N′-Di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl)-4,4′-diamine (α-NPD) on top of the semitransparent gold anode, the double-unit stacked OLED achieves a maximum current efficacy of 205 cd/A at a luminance of 103 cd/m², maintaining a high current efficacy of 200 cd/A at a luminance of 1011 cd/m². These stacked inverted OLED combine the advantages of inverted OLEDs with the benefits of having a stacked architecture.     

Small molecule interlayer for solution processed phosphorescent organic light emitting device

Using a 4,4′,4′′-tris(N-carbazolyl)-triphenylamine (TCTA) small molecule interlayer, we have fabricated efficient green phosphorescent organic light emitting devices by solution process. Significantly a low driving voltage of 3.0 V to reach a luminance of 1000 cd/m² is reported in this device. The maximum current and power efficiency values of 27.2 cd/A and 17.8 lm/W with TCTA interlayer (thickness 30 nm) and 33.7 cd/A and 19.6 lm/W with 40 nm thick interlayer are demonstrated, respectively. Results reveal a way to fabricate the phosphorescent organic light emitting device using TCTA small molecule interlayer by solution process, promising for efficient and simple manufacturing.     

High-efficiency low color temperature organic light emitting diodes with solution-processed emissive layer

Low color temperature (CT) lighting provides a warm and comfortable atmosphere and shows mild effect on melatonin suppression. A high-efficiency low CT organic light emitting diode can be easily fabricated by spin coating a single white emission layer. The resultant white device shows an external quantum efficiency (EQE) of 22.8% (34.9 lm/W) with CT 2860 K at 100 cd/m², while is shown 18.8% (24.5 lm/W) at 1000 cd/m². The high efficiency may be attributed to the use of electroluminescence efficient materials and the ambipolar-transport host. Besides, proper device architecture design enables excitons to form on the host and allows effective energy transfer from host to guest or from high triplet guest to low counterparts. By decreasing the doping concentration of blue dye in the white emission layer, the device exhibited an orange emission with a CT of 2280 K. An EQE improvement was observed for the device, whose EQE was 27.4% (38.8 lm/W) at 100 cd/m² and 20.4% (24.6 lm/W) at 1000 cd/m².     

Multifunctional Fluorene‐Based Oligomers with Novel Spiro‐Annulated Triarylamine: Efficient,Stable Deep‐Blue Electroluminescence,Good Hole Injection,and Transporting Materials with Very High Tg

A series of fluorene‐based oligomers with novel spiro‐annulated triarylamine structures, namely DFSTPA, TFSTPA, and TFSDTC, are synthesized by a Suzuki cross‐coupling reaction. The spiro‐configuration molecular structures lead to very high glass transition temperatures (197–253 °C) and weak intermolecular interactions, and consequently the structures retain good morphological stability and high fluorescence quantum efficiencies(0.69–0.98). This molecular design simultaneously solves the spectral stability problems and hole‐injection and transport issues for fluorene‐based blue‐light‐emitting materials. Simple double‐layer electroluminescence (EL) devices with a configuration of ITO/TFSTPA (device A) or TFSDTC (device B)/ TPBI/LiF/Al, where TFSTPA and TFSDTC serve as hole‐transporting blue‐light‐emitting materials, show a deep‐blue emission with a peak around 432 nm, and CIE coordinates of (0.17, 0.12) for TFSTPA and (0.16, 0.07) for TFSDTC, respectively, which are very close to the National Television System Committee (NTSC) standard for blue (0.15, 0.07). The maximum current efficiency/external quantum efficiencies are 1.63 cd A^?1/1.6% for device A and 1.91 cd A^?1/2.7% for device B, respectively. In addition, a device with the structure ITO/DFSTPA/Alq₃/LiF/Al, where DFSTPA acts as both the hole‐injection and ‐transporting material, is shown to achieve a good performance, with a maximum luminance of 14 047 cd m^?2, and a maximum current efficiency of 5.56 cd A^?1. These values are significantly higher than those of devices based on commonly usedN,N′‐di(1‐naphthyl)‐N,N′‐diphenyl‐[1,1′‐biphenyl]‐4,4′‐diamine (NPB) as the hole‐transporting layer (11 738 cd m^?2 and 3.97 cd A^?1) under identical device conditions.     

Enhancing the efficiency of simplified red phosphorescent organic light emitting diodes by exciton harvesting

High efficiency red phosphorescent organic light emitting diode (PHOLED) employing co-doped green emitting molecule bis(2-phenylpyridine)(acetylacetonate)iridium(III) [Ir(ppy)₂(acac)] and red emitting molecule bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) [Ir(MDQ)₂(acac)] into 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host in a simplified wide-bandgap platform is demonstrated. The green molecule is shown to function as an exciton harvester that traps carriers to form excitons that are then efficiently transferred to the Ir(MDQ)₂(acac) by triplet-to-triplet Dexter energy transfer, thereby significantly enhancing red emission. In particular, a maximum current efficiency of 37.0 cd/A and external quantum efficiency (EQE) of 24.8% have been achieved without additional out-coupling enhancements. Moreover, a low efficiency roll-off with the EQE remaining as high as 20.8% at a high luminance of 5000 cd/m² is observed.