Investigation and optimization of each organic layer: A simple but effective approach towards achieving high-efficiency hybrid white organic light-emitting diodes

A highly efficient hybrid white organic light-emitting diode based on a simple structure has been successfully fabricated and characterized. By systematically investigating the influence of the emissive layer thickness, electron transporting layer thickness, spacer and hole transporting layer, the forward-viewing current efficiency and power efficiency of the resulting device without any out-coupling schemes or n-doping strategies can be as high as 59.4 cd/A and 58.4 lm/W, respectively. Besides, a Commission International de l’Eclairage of (0.412, 0.393) and a color rendering index of 60 are obtained at the current density of 11 mA/cm². Through the optimization and investigation, the origin of this unique device is explored comprehensively. Undoubtedly, such presented results will be beneficial to the design of both material and device architecture for ultra high-performance white organic light-emitting diodes.     

Color stable phosphorescent white organic light-emitting diodes with double emissive layer structure

In this paper, we report color stable phosphorescent white organic light-emitting diodes (OLEDs) based on a double emissive layer (EML) structure composed of blue and red/green phosphorescent units. Deep hole trapping situation of red and green dopants at the red/green EML could induce less voltage dependent white spectral characteristics by restricting the change of exciton generation zone. A wide band-gap host material, 2,6-bis(3-(carbazol-9-yl)phenyl)pyridine (26DCzPPy), was used for achieving such deep-trap generation. Fabricated phosphorescent white OLED shows a slight color coordinate change of (?0.002, +0.002) from 1000 cd/m² to 5000 cd/m² with power efficiency of 38.7 lm/W and current efficiency of 46.4 cd/A at 1000 cd/m². In addition, negligible color changes were observed by delaying red dopant saturation time using optimum red dopant concentration.     

Highly efficient green phosphorescent organic light emitting diodes with simple structure

A series of simple structures is investigated for realization of the highly efficient green phosphorescent organic light emitting diodes with relatively low voltage operation. All the devices were fabricated with mixed host system by using 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) and 1,3,5-tri(p-pyrid-3-yl-phenyl)benzene (TpPyPB) which were known to be hole and electron type host materials due to their great hole and electron mobilities [μ_h(TAPC): 1 × 10^?2 cm²/V s and μ_e(TpPyPB): 7.9 × 10^?3 cm²/V s] [1]. The optimized device with thin TAPC (5–10 nm) as an anode buffer layer showed relatively high current and power efficiency with low roll-off characteristic up to 10,000 cd/m². The performances of the devices; with buffer layer were compared to those of simple devices with single layer and three layers. Very interestingly, the double layer device with TAPC buffer layer showed better current and power efficiency behavior compared to that of three layer device with both hole and electron buffer layers (TAPC, TpPyPB, respectively).     

Synthesis and characterization of fluorene-based copolymers as electron-transporting materials for PLEDs

Owing to their low cost, easy processing, and the possibility of flexible fabrication, polymer light-emitting diodes (PLEDs) are emerging as an important class of materials. Despite promising characteristics, the relatively easy ionization of the well-known low-work-function cathodes such as Ca and Ba prevents the full usage of these materials. Herein, we report the syntheses of three alcohol-soluble conjugated polymers with different conjugation lengths and electron affinities as electron injection and transport materials for PLEDs: poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-tetrafluorobenzene] (PFOH-1), poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-thiophene] (PFOH-2), and poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-benzo-thiadiazole] (PFOH-3). For comparison, devices using Al, Ca, and Al cathodes were also fabricated. The device based on the Al cathode showed lower performance with a luminescence efficiency of 0.93 cd/A and a luminance of 248 cd/m²; that based on the low-work-function metal Ca as the cathode showed a near-threefold increase in luminescence efficiency at 2.51 cd/A and brightness at 856 cd/m² owing to greatly enhanced electron injection from the cathode; and the device employing the PFOH-3/Al cathode exhibited a luminescence efficiency of 2.35 cd/A and a brightness of 667 cd/m² at a current density of 35 mA/cm², which is comparable with the performance of the device with the Ca cathode.     

All-small-molecule efficient white organic light-emitting diodes by multi-layer blade coating

Blue and white small-molecule organic light-emitting diodes are fabricated by multi-layer blade coating on hot plate at 80 °C with hot wind. Uniform multi-layer structures are made without dissolution due to rapid drying. Only small molecules originally developed for vacuum deposition are used. For hole transport layer of, 4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA), electron transport layer of 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TBPI), emissive layer host of, 6-bis(3-(9H-carbazol-9-yl)phenyl)pyridine (26DCzPPy), triplet emitters of bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III) (FIrpic), and cathode of LiF/Al, the peak current efficiency for blue emission is 25.1 cd/A (10.8% and 9.3 lm/W). Orange emitter iridium(III)bis (4-(4-t-butylphenyl) thieno[3,2-c]pyridinato-N,C2′)acetylacetonate (PO-01-TB) is added to obtain white emission with CIE coordinate of (0.39, 0.46) [1]. The current efficiency is 34.2 cd/A (11.6% and 12 lm/W) at maximum, 32.4 cd/A at 1000 cd/m², and 31 cd/A at 10,000 cd/m².     

Tandem white organic light-emitting device using non-modified Ag layer as cathode and interconnecting layer

Tandem white organic light-emitting device (WOLED) using non-modified Ag film as cathode and interconnecting layer is demonstrated. Effective electron injection is achieved when Ag is deposited on 4,7-diphenyl-1,10-phenanthroline electron transporting layer without any modified layer. Single OLED with Ag cathode shows comparable performance to that of device with Mg:Ag cathode. Such tandem WOLED exhibits low driving voltage, high power efficiency (15.1 lm/W at 1000 cd/m²) and low efficiency roll-off. The working mechanisms of single and tandem devices were discussed in detail. These results could provide a simple method to fabricate high performance tandem white OLED.     

Enabling high-efficiency organic light-emitting diodes with a cross-linkable electron confining hole transporting material

Wet-process enables flexible, large area-size organic devices to be fabricated cost-effectively via roll-to-roll manufacturing. However, wet-processed devices often show comparatively poor performance due to the lack of solution-process feasible functional materials that exhibit robust mechanical properties. We demonstrate here a cross-linkable material, 3,6-bis(4-vinylphenyl)-9-ethylcarbazole (VPEC), to facilitate the injection of hole and meanwhile effectively confine electron to realize, for examples, high efficiency organic light-emitting diodes, especially at high luminance. The VPEC shows a hole mobility of 1 × 10⁻⁴ cm² V⁻¹ s⁻¹ and a triplet energy of 2.88 eV. Most importantly, the VPEC not only works for devices containing low band-gap red or green emitters, but also for the counterpart with high band-gap blue emitter. With the electron confining hole transporting material, the power efficiency of a studied red device, at 1,000 cd m⁻² for example, is increased from 8.5 to 13.5 lm W⁻¹, an increment of 59%, and the maximum luminance enhanced from 13,000 to 19,000 cd m⁻², an increment of 46%. For a high triplet energy blue emitter containing device, it is increased from 6.9 to 8.9 lm W⁻¹, an increment of 29%, and the maximum luminance enhanced from 9,000 to 11,000 cd m⁻², an increment of 22%.     

p-Doped p-phenylenediamine-substituted fluorenes for organic electroluminescent devices

Two novel p-phenylenediamine-substituted fluorenes have been designed and synthesized. Their applications as hole injection materials in organic electroluminescent devices were investigated. These materials show a high glass transition temperature and a good hole-transporting ability. It has been demonstrated that the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) doped p-phenylene-diamine-substituted fluorenes, in which F4-TCNQ acts as p-type dopant, are highly conducting with a good hole-transporting property. The organic light emitting devices (OLEDs) utilizing these F4-TCNQ-doped materials as a hole injection layer were fabricated and investigated. The pure Alq₃-based OLED device shows a current efficiency of 5.2 cd/A at the current density of 20 mA/cm² and the operation lifetime is 1500 h with driving voltage increasing only about 0.7 mV/h. The device performance and stability of this hole injection material meet the benchmarks for the commercial requirements for OLED materials.     

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).     

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.     

High-efficiency and multi-function blue fluorescent material for organic electroluminescent devices

We demonstrate one high-efficiency blue fluorescent material, N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine, with an emissive peak of 472 nm and the hole-transporting property speculated from different devices. It can function either as the single emissive layer or as the dye doped in N,N′-dicarbazolyl-4-4′-biphenyl (CBP). The former shows a maximum current efficiency and luminance of 7.06 cd/A (0.04 mA/cm²) and 16 930 cd/m², in contrast to 11.5 cd/A (4.35 mA/cm²) and 25 690 cd/m² for the latter. The better performance of the latter can be attributed to the bipolar carrier transport property of CBP and the hole-blocking and electron-transporting characteristic of 4,7-diphenyl-1,10-phenanthroline (BPhen), which resulting in a good balance of holes and electrons. Moreover, the Commission Internationale De L’Eclairage coordinates of the latter change slightly from (0.162, 0.3) to (0.148, 0.268) upon increasing the voltage from 3 V to 14 V.     

High-efficiency fluorescent white organic light-emitting device with double emissive layers

The authors demonstrate a fluorescent white organic light-emitting device (WOLED) with double emissive layers. The yellow and blue dyes, 5,6,11,12-tetraphenylnaphthacene and N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine, are doping into the same conductive host material, N,N′-dicarbazolyl-4-4′-biphenyl). The maximum luminance and power efficiency of the WOLED are 14.6 cd/A and 9.5 lm/W at 0.01 mA/cm², with the maximum brightness of 20 100 cd/m² at 17.8 V. The Commission International de L’Éclairage coordinates change slightly from (0.27, 0.37) to (0.28, 0.36), as the applied voltage increases from 6 V to 16 V. The high efficiencies can be attributed to the balance between holes and electrons.     

Efficient solution-processed green and white phosphorescence organic light-emitting diodes based on bipolar host materials

Four carbazole-based bipolar host materials are utilized for solution-processed phosphorescent organic light-emitting diodes (PhOLEDs). These bipolar materials consist of an electron-donor unit (carbazole) linking to a fluorene unit bearing various electron-acceptor units (oxadiazole, cyano, and benzimidazole) via a saturated carbon, giving sufficiently high triplet energies due to the lack of direct electronic coupling between the donor and acceptor(s). The resulting physical properties and bipolar characteristics render the realization of efficient solution-processed green and white OLEDs feasible. The best green light-emitting device based on bipolar host CzFCBI incorporating a stepwise hole-injection/transporting system exhibit a low drive voltage, a maximum external quantum efficiency of 14.0%, a current efficiency of 49.0 cd/A, and a power efficacy of 55.0 lm/W. Moreover, the CzFOXa-based two-component (blue–orange) white light-emitting device shows a warmish-white emission with a maximum external quantum efficiency of 6.9% and stable chromaticity coordinates at different luminance levels and yield a high color rendering index (CRI) reaching 76 at a luminance of 1000 cd/m².     

Cadmium-free quantum dots based violet light-emitting diodes: High-efficiency and brightness via optimization of organic hole transport layers

Bright and efficient violet quantum dot (QD) based light-emitting diodes (QD-LEDs) with heavy-metal-free ZnSe/ZnS have been demonstrated by choosing different hole transport layers, including poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB), and poly-N-vinylcarbazole (PVK). Violet QD-LEDs with maximum luminance of about 930 cd/m², the maximum current efficiency of 0.18 cd/A, and the peak EQE of 1.02% when poly-TPD was used as HTL. Higher brightness and low turn-on voltage (3.8 V) violet QD-LEDs could be fabricated when TFB was used as hole transport material. Although the maximum luminance could reach up to 2691 cd/m², the devices exhibited only low current efficiency (∼0.51 cd/A) and EQE (∼2.88%). If PVK is used as hole transport material, highly efficient violet QD-LEDs can be fabricated with lower maximum luminance and higher turn-on voltages compared with counterpart using TFB. Therefore, TFB and PVK mixture in a certain proportion has been used as HTL, turn-on voltage, brightness, and efficiency all have been improved greatly. The QD-LEDs is fabricated with 7.39% of EQE and 2856 cd/m² of maximum brightness with narrow FWHM less than 21 nm. These results represent significant improvements in the performance of heavy-metal-free violet QD-LEDs in terms of efficiency, brightness, and color purity.     

Fluorene-based cathode interlayer polymers for high performance solution processed organic optoelectronic devices

A hydrophilic polyfluorene-based conjugated polyelectrolyte (CPE) Poly[9,9-bis(4′-(6″-(diethanolamino)hexyloxy) phenyl)fluorene], PPFN-OH (Scheme 1) has been synthesized and utilized as cathode interlayer for both polymer light emitting diodes (PLEDs) and solar cells (PSCs). For comparison, another CPE namely Poly[9,9-bis(6′-(diethanolamino)hexyl)fluorene] (PFN-OH) has also been investigated. They comprise the same polyfluorene backbone structures with, respectively, diethanolaminohexyl (PFN-OH) and diethanolaminohexoxyphenyl (PPFN-OH) substituents attached to the C9 carbon of the fluorene repeat unit. In comparison to reference devices with more reactive Ca/Al cathodes, utilizing these CPEs as interlayers allowed an Al cathode to be used for blue light emission PLEDs, yielding 51% and 92% enhancement of maximum luminous efficiency (LE) for PFN-OH and PPFN-OH, respectively. The PLEDs with PPFN-OH showed both higher maximum LE and maximum luminance (L) (LE = 2.53 cd/A at 6.2 V, L = 9917 cd/m² at 8.3 V) than devices with PFN-OH (2.00 cd/A at 4.1 V, 3237 cd/m² at 7.2 V). The PPFN-OH PLEDs also showed no significant roll-off in efficiency with increasing current density up to 400 mA/cm², indicating excellent electron injection ability and stability for this interlayer. The insertion of alkoxy-phenyl groups at the C9-position in PPFN-OH is clearly advantageous. This simple modification significantly improves the CPE cathode interlayer performance. Parallel investigations of the electron extraction properties of PPFN-OH in inverted architecture PSCs with PCDTBT:PC₇₀BM bulk heterojunction active layers demonstrated a power conversion efficiency enhancement of ∼19% (from 4.99% to 5.95%) for indium tin oxide cathode devices compared with reference devices using Ca/Al cathodes. These results confirm PPFN-OH to be a promising interlayer material for high performance solution processed organic optoelectronic devices.     

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.     

Carrier transport of inverted quantum dot LED with PEIE polymer

An inverted-type quantum-dot light-emitting-diode (QD LED), employing low-work function organic material polyethylenimine ethoxylated (PEIE) as electron injection layer, was fabricated by all solution processing method, excluding anode electrode. From transmission electron microscopy (TEM) and scanning electron microscopy (SEM) studies, it was confirmed that CdSe@ZnS QDs with 7 nm size were uniformly distributed as a monolayer on PEIE layer. In this inverted QD LED, two kinds of hybrid organic materials, [poly (9,9-di-n-octyl-fluorene-alt-benzothiadiazolo)(F8BT) + poly(N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine (poly-TPD)] and [4,4′-N,N′-dicarbazole-biphenyl (CBP) + poly-TPD], were adopted as hole transport layer having high highest occupied molecular orbital (HOMO) level for improving hole transport ability. At a low-operating voltage of 8 V, the device emits orange and red spectral radiation with high brightness up to 2450 and 1420 cd/m², and luminance efficacy of 1.4 cd/A and 0.89 cd/A, respectively, at 7 V applied bias. Also, the carrier transport mechanisms for the QD LEDs are described by using several models to fit the experimental I–V data.     

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.     

Flexible top-emitting warm-white organic light-emitting diodes with highly luminous performances and extremely stable chromaticity

The flexible top-emitting white organic light-emitting diode (FTEWOLED) with a very high efficiency but a significant color alteration is achieved with a blue/red/blue sandwiched tri-emission-layer. The voltage-dependent recombination region alternation and the emission mechanism are systematically investigated through a delta-doping method and the time-resolved transient photoluminescence lifetime measurement. By locating the main exciton recombination region at the 4,4′,4″-Tris(carbazol-9-yl)-triphenylamine (TCTA) and 9,9-spirobifluoren-2-yl-diphenyl-phosphine oxide (SPPO1) interface, replacing the carrier-trapping red dopant guest with an orange guest that utilizes energy transfer mechanism, and using a P–I–N structure together with the FIrpic blue guest dopant to balance the electron and hole carriers, an extremely color stable and a very high efficient FTEWOLED is fabricated, with the resulting high current and power efficiencies of 22.7 cd/A and 14.27 lm/W, and a warm white illumination with a small chromaticity variation of (−0.0087, +0.0015) over a broad luminance range of more than four orders of magnitude. In addition, the performances can be further improved to 23,340 cd/m², 24.49 cd/A and 15.39 lm/W with a slight concentration alteration of the orange emitter.     

Small polymeric nano-dot enhanced pure-white organic light-emitting diode

Marked efficiency improvement of a spin-coated phosphorescent pure-white organic light-emitting diode was obtained by incorporating a novel small polymeric nano-dot (PND) in the hole-transporting layer. The resultant device efficiency strongly depended on the concentration and size of the PND used. The resultant power efficiency at 100 cd/m², for example, was increased from 6.8 to 23.7 lm/W, an increase of 350%, as 14 wt% PND of 8 nm in size was employed. The improvement may be attributed to a better carrier-injection balance resulted from hole trapping on the PND.