Phosphorescent dye-doped hole transporting layer for organic light-emitting diodes

Hole transport materials are critical to the performance of organic light-emitting diodes (OLEDs). While 1,1-bis(di-4-tolylaminophenyl)cyclohexane (TAPC) with a high triplet energy is widely used for high efficiency phosphorescent OLEDs, devices using TAPC as a hole transport layer (HTL) have a short operating lifetime due to the build-up of trapped charges at the TAPC/emitting layer (EML) interface during device operation. In this work, to solve the operating stability problem, instead of using conventional HTLs, we use a(fac-tris(2-phenylpyridine)iridium (III))(Ir(ppy)₃) doped layer as an HTL to replace the conventional HTLs. Because of the hole injecting and transporting abilities of the phosphorescent dye, holes can be directly injected into the emitting layer without an injection barrier. OLEDs based on a phosphorescent dye-doped HTL show significant improvement in operational stability without loss of efficiency.     

Enhanced efficiency and brightness in organic light- emitting devices with MoO3 as hole-injection layer

The organic light-emitting devices (OLEDs) using 4,4’,4’’-tris{N-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) and MoO3 or 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-tetrachloride (TAPC) and MoO3 as the hole-injection layer (HIL) were fabricated. MoO3 can be expected to be a good injection layer material and thus enhance the emission performance of OLED. The highest occupied molecular (HOMO) of MoO3 is between those of m-MTDATA or TAPC and N,N’-bis-(1-naphthyl)-N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB), which reduces the hole-injection barrier and improves the luminance of the OLEDs. The current efficiency is improved compared with that of the device without the MoO3 layer. The highest luminous efficiency of the device with 2-nm-thick MoO3 as HIL is achieved as 5.27 cd/A at 10 V, which is nearly 1.2 times larger than that of the device without it. Moreover, the highest current efficiency and power efficiency of the device with the structure indium-tin oxide (ITO)/TAPC (40 nm)/MoO3 (2 nm)/TcTa:Ir(ppy)3 (10%, 10 nm)/ tris-(8-hydroxyquinoline) aluminium (Alq) (60 nm)/LiF (1 nm)/Al are achieved as 37.15 cd/A and 41.23 lm/W at 3.2 V and 2.8 V, respectively.     

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.     

High performance top-emitting organic light-emitting diodes with copper iodide-doped hole injection layer

Efficient top-emitting organic light-emitting diodes were fabricated using copper iodide (CuI) doped 1,4-bis[N-(1-naphthyl)-N′-phenylamino]-4,4′-diamine (NPB) as a hole injection layer and Ir(ppy)₃ doped CBP as the emitting layer. CuI doped NPB layer functions as an efficient p-doped hole injection layer and significantly improves hole injection from a silver bottom electrode. The top-emitting device shows high current efficiency of 69 cd/A with Lambertian emission pattern. The enhanced hole injection is originated from the formation of the charge transfer complex between CuI and NPB.     

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.     

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.     

利用Ir(ppy)_3敏化CzHQZn提高OLED的性能

用CzHQZn作为受主,利用磷光敏化的方法制备了有机电致黄光和白光器件。黄光器件采用Ir(ppy)3掺杂4,4-N,N′-=咔唑基联苯(CBP),敏化新的黄光材料CzHQZn作为发光层,当发光层厚度为18nm时器件性能最好,最大发光效率为3.26cd/A(at10V),最大发光亮度为17560cd/m2(at10V);白光器件采用多发光层结构,结合ADN的蓝光复合发光,同时加入了电子阻挡层(NPBX)和空穴阻挡层(BCP),获得的白光器件最大发光效率为2.94cd/A(at8V),最大亮度为11089cd/m2(at13V)。     

Carbazole-bridged triphenylamine-bipyridine bipolar hosts for high-efficiency low roll-off multi-color PhOLEDs

Three new bipolar molecules composed of carbazole, triarylamine, and bipyridine were synthesized and utilized as host materials in multi-color phosphorescent OLEDs (PhOLEDs). These carbazole-based materials comprise a hole-transport triarylamine at C3 and an electron-transport 2,4′- or 4,4′-bipyridine at N9. The different bipyridine isomers and linking topology of the bipyridine with respect to carbazole N9 not only allows fine-tuning of physical properties but also imparts conformational change which subsequently affects molecular packing and carrier transport properties in the solid state. PhOLEDs were fabricated using green [(ppy)₂Ir(acac)], yellow [(bt)₂Ir(acac)], and red [(mpq)₂Ir(acac)] as doped emitters, which showed low driving voltage, high external quantum efficiency (EQE), and extremely low efficiency roll-off. Among these new bipolar materials, the 2Cz-44Bpy-hosted device doping with 10% (ppy)₂Ir(acac) as green emitting layer showed a high EQE of 22% (79.8 cd A⁻¹) and power efficiency (PE) of 102.5 lm W⁻¹ at a practical brightness of 100 cd m⁻². In addition, the device showed limited efficiency roll-off (21.6% EQE) and low driving voltage (2.8 V) at a practical brightness of 1000 cd m⁻².     

Inducing the trap-site in an emitting-layer for an organic upconversion device exhibiting high current-gain ratio and low turn-on voltage

We report a fabrication method of controlling the doped concentration of phosphorescent dye to induce the trap-site in an emitting layer (EML) for an efficient near-infrared (NIR) organic upconversion device (OUD). Such an OUD was used as a device configuration of ITO/mixed layer of chloroaluminum phthalocyanine and C₆₀/1,1-bis(di-4-tolylaminophenyl) cyclohexane/4,4′ -Bis(N-carbazolyl)-1,1′ -biphenyl doped with fac-tris (2-phenylpyridine) iridium (III) [Ir(ppy)₃]/4,7-diphenyl-l,10-phenanthroline/CS₂CO₃/Ag to provide a green emission under NIR illumination. Our optimized OUD with a high Ir(ppy)₃ doped concentration of ∼13 wt% exhibited a higher electroluminescent efficiency in the display unit and was suitable for inducing a large amount of trap-sites in the EML, which effectively blocked the hole and electron carrier in the EML. To induce the trap-site in the EML by the doping process, we used a hole- and electron-only device to examine the OUD with a lower dark current density. As a result, an optimal OUD with a current gain as high as 21,300 (defined as the light current density divided by dark current density) at a driving voltage of 3 V was successfully achieved.     

Investigating Morphology and Stability of Fac‐tris (2‐phenylpyridyl)iridium(III) Films for OLEDs

Stable film morphology is critical for long‐term high performance organic light‐emitting diodes (OLEDs). Neutron reflectometry (NR) is used to study the out‐of‐plane structure of blended thin films and multilayer structures comprising evaporated small molecules. It is found that as‐prepared blended films of fac‐tris(2‐phenylpyridyl)iridium(III) [Ir(ppy)₃] in 4,4′‐bis(N‐carbazolyl)biphenyl (CBP) are uniformly mixed, but the occurrence of phase separation upon thermal annealing is dependent on the blend ratio. Films comprised of the ratio of 6 wt% of Ir(ppy)₃ in CBP typically used in OLEDs are found to phase separate with moderate heating while a higher weight percent mixture (12 wt%) is found to be stable. Furthermore, it is found that thermal annealing of a multilayer film comprised of typical layers found in efficient devices ([tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA)/Ir(ppy)₃:CBP/bathocuproine (BCP)]) causes the BCP layer to become mixed with the emissive blend layer, whereas the TCTA interface remains unchanged. This significant structural change causes no appreciable difference in the photo­luminescence of the stack although such a change would have a dramatic effect on the charge transport through the device, leading to changes in performance. These results demonstrate the effect of thermal stress on the delicate interplay between the chemical composition and morphology of OLED films.     

基于FHQZn发光的新结构有机黄光器件

利用一种新型材料(E)-2-(2-(9H-fluoren-2-yl)vinyl)quinolato-Zinc(FHQZn)制备了一种新结构的黄光OLED,器件的结构为:indium-tinoxide(ITO)/4,4′,4″-{N,-(2-naphthyl)-N-phenylamino}-triphenylamine(2T-NATA)(15nm)/FHQZn(xnm)/4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl(DPVBi)(20nm)/2,2′,2″-(1,3,5-phenylene)tris(1-phenyl-1H-benzimidazole-(TPBi):6%factris(2-phenylpyridine)iridium(Ir(ppy)3)(45nm)/LiF(0.5nm)/Al,FHQZn作空穴传输层和黄色发光层,DPVBi作空穴阻挡层,TPBi中掺杂Ir(ppy)3作电子传输层;研究了发光层FHQZn的厚度对该器件的发光性能的影响。当FHQZn厚度x=25时,得到了效率和亮度最大的黄光器件,最大电流效率为1.31cd/A(at13V),最大亮度为5705cd/m2(at14V),此时色坐标为(0.4,0.5516)。     

Solution-based nanostructure to reduce waveguide and surface plasmon losses in organic light-emitting diodes

Organic light-emitting diodes (OLEDs) typically have low out-coupling efficiency. In this paper, a solution-based nanoparticle layer is presented as a nanostructure to enhance the out-coupling efficiency of OLEDs. Silica nanoparticles (NPs) are randomly distributed on indium tin oxide by spin-coating a silica NP solution. By further spin-coating poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) as a hole injection layer, a randomly corrugated PEDOT:PSS layer is fabricated. A nanostructured OLED having the corrugated PEDOT:PSS layer above the NP layer shows enhanced external quantum efficiency and power efficiency because the trapped light of the waveguide and surface plasmon modes is extracted by Bragg diffraction. The nanostructured OLED shows no angular dependence due to the broad periodicities of the corrugation. The simply fabricated and cost-effective silica NP layer nanostructure, which does not require a lithography step, has potential to enhance the efficiency of both white OLED displays and lighting.     

Solution‐Processible Carbazole Dendrimers as Host Materials for Highly Efficient Phosphorescent Organic Light‐Emitting Diodes

A group of dendrimers with oligo‐carbazole dendrons appended at 4,4′‐ positions of biphenyl core are synthesized for use as host materials for solution‐processible phosphorescent organic light‐emitting diodes (PHOLEDs). In comparison with the traditional small molecular host 4,4′‐N,N′‐dicarbazolebiphenyl (CBP), the dendritic conformation affords these materials extra merits including amorphous nature with extremely high glass transition temperatures (ca. 376 °C) and solution‐processibility, but inherent the identical triplet energies (2.60–2.62 eV). In comparison with the widely‐used polymeric host polyvinylcarbazole (PVK), these dendrimers possess much higher HOMO levels (–5.61 to –5.42 eV) that facilitate efficient hole injection and are favorable for high power efficiency in OLEDs. The agreeable properties and the solution‐processibility of these dendrimers makes it possible to fabricate highly efficient PHOLEDs by spin coating with the dendimers as phosphorescent hosts. The green PHOLED containing Ir(ppy)₃ (Hppy = 2‐phenyl‐pyridine) dopant exhibits high peak efficiencies of 38.71 cd A^?1 and 15.69 lm W^?1, which far exceed those of the control device with the PVK host (27.70 cd A^?1 and 9.6 lm W^?1) and are among the best results for solution‐processed green PHOLEDs ever reported. The versatility of these dendrimer hosts can be spread to orange PHOLEDs and high efficiencies of 32.22 cd A^?1 and 20.23 lm W^?1 are obtained, among the best ever reported for solution‐processed orange PHOLEDs.     

A high thermal stability terpyridine derivative as the electron transporter for long-lived green phosphorescent OLED

A new terpyridine-based compound of 2,2′,7,7′-tetra([2,2':6′,2″-terpyridin]-4′-yl)-9,9′-spirobi[fluorene] (4oTPSF) was designed and synthesized as the electron transporter in organic light-emitting diodes (OLEDs). 4oTPSF exhibited excellent thermal stability with high glass transition temperature (T_g) of 250 °C and melting temperature (T_m) of 460 °C during the thermal measurement. The excellent thermal stability is attributed to the molecular structure, that the steric effect of rigid twisted spirobiflourene and the connected terpyridine (TPY) resulted in a decrease of the intermolecular π-stacking interaction. The studies on electrical characteristics of electron-only devices revealed that 4oTPSF showed high electron-transporting capability, as good as the conventional electron-transporting material (ETM) 1,3,5-tris(N-phenylbenzimid-azol-2-yl-benzene (TPBi). A series of green phosphorescent OLEDs (PhOLEDs) based on bis(2-phenylpyridine)iridium(III)(2,2,6,6-tetramethylheptane-3,5-diketonate) (Ir(ppy)₂tmd) or tris[2-(p-tolyl)pyridine]iridium(III) (Ir(mppy)₃) as emitter and 4oTPSF as ETM displayed a turn-on voltage of 2.23 V and a maximum power efficiency of 97.8 l m/W and a half-life (T₅₀) of 101, 5680 and 319 390 h at an initial luminance of 10 000, 1000 and 100 cd/m², respectively. The lifetime of 4oTPSF-based device was twice more than the lifetime of TPBi-based device.     

Crosslinkable TAPC‐Based Hole‐Transport Materials for Solution‐Processed Organic Light‐Emitting Diodes with Reduced Efficiency Roll‐Off

1‐Bis[4‐[N,N‐di(4‐tolyl)amino]phenyl]‐cyclohexane (TAPC) has been widely used in xerography and organic light‐emitting diodes (OLEDs), but derivatives are little known. Here, a new series of solution‐processable, crosslinkable hole conductors based on TAPC with varying highest occupied molecular orbital (HOMO) energies from ?5.23 eV to ?5.69 eV is implemented in blue phosphorescent OLEDs. Their superior perfomance compared with the well‐known N4,N4,N4′,N4′‐tetraphenylbiphenyl‐4,4′‐diamine (TPDs) analogues regarding hole‐injection and mobility, electron and exciton blocking capabilities, efficiency, and efficiency roll‐off is demonstrated. Overall, the TAPC‐based devices feature higher luminous and power efficiency over a broader range of brightness levels and reduced efficiency roll off. A systematic broadening of the emission zone is observed as the hole‐injection barrier between the anode and the hole‐transporting layer increased.     

Fourfold power efficiency improvement in organic light-emitting devices using an embedded nanocomposite scattering layer

It has been demonstrated that internal extraction structures (IES) can be introduced in OLEDs to decrease the ratio of the waveguide mode and simultaneously increase the ratios of the substrate and radiation modes. In this study, titanium oxide (TiO₂) nanoparticles (NPs) combined with transparent photoresist (TPR) were utilized to form an embedded nanocomposite scattering layer between the indium-tin-oxide (ITO) and glass substrate, leading to a significant boost in the out-coupling efficiency of the OLEDs. Inside the nanocomposite scattering layer, NPs of different sizes served distinct functions. The 250 nm-TiO₂ particles were used to induce scattering and diminish the light reflection back to the ITO layer. On the other hand, the refractive index of the TPR can be increased by increasing the concentration of the 25 nm-TiO₂, which reduced the difference in the refractive index between the ITO and TPR and thus multiplied the amount of light entering into the scattering layer. By employing nanocomposite substrate with mixed dual-sized NPs, we obtained power efficiencies of the blue phosphorescent OLEDs that were about 4.3 times higher than that of the control device at the high luminance of 5 × 10³ cd/m².     

(t-bt)2Ir(acac)超薄层厚度对有机电致发光器件性能的影响

以新型铱配合物黄光磷光染料bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2']iridium(acetylacetonate)[(tbt)2Ir(acac)]为超薄层,制备了结构为indium tin oxide(ITO)/N,N'-bis(naphthalen-1-yl)-N...     

Hybrid intermediate connector for tandem OLEDs with the combination of MoO3-based interlayer and p-type doping

We report on a high-quality hybrid intermediate connector (IC) used in tandem organic light-emitting diodes (OLEDs), which is composed of an ultrathin MoO₃ interlayer sandwiched between a n-type Cs₂CO₃-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) layer and a p-type MoO₃-doped N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB) layer. The charge generation characteristics for light emission in tandem OLEDs have been identified by studying the interfaces and the corresponding devices. The hybrid IC structure exhibits superior charge generation capability, and its interfacial electronic structures are beneficial to the generation and injection of electrons and holes into bottom and top emission units, respectively. Compared to the organic-TMO bilayer and doped p–n junction structures, the hybrid IC structure combining MoO₃-based interlayer and p-type doping can effectively decrease the driving voltage and improve the current efficiency of tandem devices due to the increased bulk heterojunction-like charge generation interfaces. Our results indicate that the TMO-based hybrid IC structure can be a good structure in the fabrication of high-efficiency tandem OLEDs.     

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.