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).     

High-efficiency orange and white phosphorescent organic light-emitting diodes based on homojunction structure

We demonstrate high-efficiency orange and white phosphorescent organic light-emitting diodes based on homojunction structure. Excellent performance is realized by using step-graded p- and n-type doping structure in orange homojunction device. The resulting orange homojunction device exhibits a maximum current efficiency of 30.0 cd/A and low efficiency roll-off. The improvements are mainly attributed to the utilization of step-graded doped profile, which facilitates balanced charge carrier injection and transport. Moreover, one optimized white homojunction device based on two complementary colors shows a maximum efficiency of 15.4 cd/A, and superior color-stability in a wide range of luminance.     

Efficient single layer RGB phosphorescent organic light-emitting diodes

We report efficient single layer red, green, and blue (RGB) phosphorescent organic light-emitting diodes (OLEDs) using a “direct hole injection into and transport on triplet dopant” strategy. In particular, red dopant tris(1-phenylisoquinoline)iridium [Ir(piq)₃], green dopant tris(2-phenylpyridine)iridium [Ir(ppy)₃], and blue dopant bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium [FIrpic] were doped into an electron transporting 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi) host, respectively, to fabricate RGB single layer devices with indium tin oxide (ITO) anode and LiF/Al cathode. It is found that the maximum current efficiencies of the devices are 3.7, 34.5, and 6.8 cd/A, respectively. Moreover, by inserting a pure dopant buffer layer between the ITO anode and the emission layer, the efficiencies are improved to 4.9, 43.3, and 9.8 cd/A, respectively. It is worth noting that the current efficiency of the green simplified device was as high as 34.6 cd/A, even when the luminance was increased to 1000 cd/m² at an extremely low applied voltage of only 4.3 V. A simple accelerated aging test on the green device also shows the lifetime decay of the simplified device is better than that of a traditional multilayered one.     

Deep blue phosphorescent organic light-emitting diodes with excellent external quantum efficiency

Highly efficient deep blue phosphorescent organic light-emitting diodes (PHOLEDs) using two heteroleptic iridium compounds, (dfpypy)₂Ir(acac) and (dfpypy)₂Ir(dpm), as a dopant and 9-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazol-3-yl)diphenylphosphine oxide as a host material have been developed. The electroluminescent device of (dfpypy)₂Ir(dpm) at the doping level of 3 wt% shows the best performance with external quantum efficiency of 18.5–20.4% at the brightness of 100–1000 cd/m² and the color coordinate of (0.14, 0.18) at 1000 cd/m².     

Management of charge carriers and excitons for efficient and color-stable white phosphorescent organic light-emitting diodes with simplified structure

We have demonstrated color-stable and highly efficient simplified white phosphorescent organic light-emitting diodes. The key feature is the use of a novel approach to confine the distribution of charge carriers and excitons across the whole blue emission layer. The resulting two-color white device has the maximum power efficiency and current efficiency of 45.5 lm/W and 43.5 cd/A with a very low color shift over a wide range of luminance. By systematically investigating the working mechanisms, we found that the ambipolar charge carrier transport ability of co-host layer which ensures the distribution of excitons to form in the whole blue emission layer was the critical factors for constructing color-stable white devices. Our results show that simplified white devices based on two organic materials achieving excellent color stability are possible.     

Tailoring electronic structure of organic host for high-performance phosphorescent organic light-emitting diodes

We investigated highly efficient phosphorescent organic light-emitting diodes (PHOLEDs) based on three novel 1,3,5-triazine derivatives as the host materials and two kinds of iridium complexes as the guests, respectively. For comparison, the devices using a common phosphorescent host 4,4′-N,N′-dicarbazolebiphenyl (CBP) have also been fabricated. Results show that the devices using 9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole (PTC) and 4-(4,6-diphenoxy-1,3,5-triazin-2-yl)-N,N-diphenylaniline (POTA) as host have better performance than that of CBP. In comparison with the PHOLEDs based on CBP host, PTC- and POTA-based PHOLEDs show significantly lower driving voltages and higher power efficiencies. The high bipolar carrier mobility of the host is found to be critical to this kind of doping system, which would balance the injection of both carriers and improve efficiency.     

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.     

High quantum efficiency and color stability in white phosphorescent organic light-emitting diodes using carboline derivative as a host material

Highly efficient and color stable phosphorescent white organic light-emitting diodes were developed using a high triplet energy host material, 3,3′-bis(9H-pyrido[2,3-b]indol-9-yl)-1,1′-biphenyl (CbBPCb), derived from carboline. Two color phosphorescent white organic light-emitting diodes were fabricated by co-doping of blue and orange triplet emitters or double emitting layer structure of blue and orange emitting layers. High quantum efficiency above 20% and color stability were achieved in the white device by optimizing the doping concentration and emitting layer thickness.     

Transient electroluminescence in heavy metal complex-based phosphorescent organic light-emitting diodes

In phosphorescent organic light-emitting diodes (PHOLEDs), both the rise time and decay time decrease with increasing amplitude of the applied voltage pulse. The rise time τ_r of the transient electroluminescence (TEL) increases linearly with increasing value of the ratio of voltage V to the current j, that is, with V/j. Using the equations for the dynamics of charge carriers an expression is derived for the rise time τ_r of the TEL in OLEDs. It is shown that τ_r should increase with increasing values of the ratio (V/j), dielectric constant ε, and area of cross-section of the emission layer, however, it should decrease with the thickness of emission layer. For higher values of the applied voltage nonlinearity occurs in the τ_r versus V/j plot because the increase in mobility of carriers at high electric field causes increase in the current flowing through the OLEDs. In fact, the rise time of TEL is related to the product of capacitance and effective resistance of the OLED. Considering the rate of generation and decay of radiative triplet excitons in the emission layer, an expression is derived for the decay time of TEL in PHOLEDs and it is shown that, for higher values of the time-constant of OLED, the decay time should be equal to the time-constant, however, for lower values of the time-constant, the decay time should be equal to the lifetime of radiative triplet excitons in the emission layer. A good agreement is found between the theoretical and experimental results.     

Synthesis,characterization of the phenylquinoline-based on iridium(III) complexes for solution processable phosphorescent organic light-emitting diodes

A new series of highly efficient Ir(III) complexes, (DPQ)₂Ir(pic-N-O), (F₄PPQ)₂Ir(pic-N-O), (FPQ)₂Ir(pic-N-O), and (CPQ)₂Ir(pic-N-O) were synthesized for phosphorescent organic light-emitting diodes (PhOLEDs), and their photophysical, electrochemical, and electroluminescent (EL) properties were investigated. The Ir(III) complexes, including picolinic acid N-oxide (pic-N-O) ancillary ligand, are comprised with the various main ligands such as 2,4-diphenylquinoline (DPQ), 4-phenyl-2-(2,3,4,5-tetrafluorophenyl)quinoline (F₄PPQ), 2-(9,9-diethyl-9H-fluoren-2-yl)-4-phenylquinoline (FPQ) and 9-ethyl-3-(4-phenylquinolin-2-yl)-9H-carbazole. Remarkably, high performance PhOLEDs using a solution-processable (DPQ)₂Ir(pic-N-O) doped CBP host emission layer were fabricated to give a high luminance efficiency (LE) of 26.9 cd/A, equivalent to an external quantum efficiency (EQE) of 14.2%.The calculated HOMO–LUMO energy gaps for (DPQ)₂Ir(pic-N-O), (F₄PPQ)₂Ir(pic-N-O), (FPQ)₂Ir(pic-N-O) and (CPQ)₂Ir(pic-N-O) were in good agreement with the experimental results.     

High triplet,bipolar polymeric hosts for highly efficient solution-processed blue phosphorescent polymer light-emitting diodes

Two polymeric hosts PCzTPP and PCzTPPO with twisted geometrical configurations for blue phosphorescent polymer light-emitting diodes (PhPLEDs) were designed and synthesized by incorporating electron-accepting carbazole units with electron-donating TPP/TPPO groups. This molecular design endows PCzTPP and PCzTPPO with high glass transition temperatures of 204 °C and 215 °C, high triplet energies of 2.72 eV and bipolar features. In addition, the HOMO and LUMO of these polymers matched well with the HOMO of the hole-transport layer and the Fermi level of cathode compared with PVK, which facilitated the injection of holes and electrons. PCzTPP- and PCzTPPO-based single-emissive-layer blue PhPLEDs were fabricated with simplified device configuration by solution process using FIrpic as a dopant. These devices exhibited lower turn on voltages (<8 V) than PVK-based devices (12 V). The maximum luminances of PCzTPP- and PCzTPPO-based devices were twofold and threefold that of PVK-based devices, and the maximum current efficiencies were nearly threefold and ninefold, respectively. Moreover, PCzTPPO-based solution processed blue PhPLEDs with improved configuration showed maximum current efficiency and external quantum efficiency of 14.5 cd/A and 6.6%, respectively.     

High morphology stability and ambipolar transporting host for use in blue phosphorescent single-layer organic light-emitting diodes

The authors report a small molecule host of 2,7-bis(diphenylphosphoryl)-9-[4-(N,N-diphenylamino)phenyl]-9-phenylfluorene (POAPF) doped with 8 wt% iridium(III)-bis[(4,6-difluorophenyl)pyridinato-N,C^2′]picolinate (FIrpic) for use in efficient and single-layer blue phosphorescent organic light-emitting diodes (PHOLEDs) exhibiting a maximum external quantum efficiency of ∼20.3% at brightness of 100 cd/m². The high performance of such single layer PHOLEDs is attributed to the POAPF host’s high morphological stability, suitable triplet energy level, and equal charge carrier mobilities of hole and electron to form the broad carrier recombination zone in the emitting layer, thus reducing the triplet-triplet annihilation and resulting in a slight efficiency roll off of 0.5% from the brightness of 1 and 1000 cd/m². This work also systematically investigated the arrangement of the POAPF:FIrpic recombination zone for optimizing the performance of the single layer PHOLED.     

Highly efficient phosphorescent organic light-emitting diodes using a beryllium metal–chelate complex as electron-transporting host material

A classical fluorescent metal–chelate complex bis(2-(2-hydroxyphenyl)-pyridine)beryllium (Bepp₂) has been used as an efficient electron-transporting host material to construct highly efficient phosphorescent organic light-emitting diodes (PHOLEDs) with an orange-emitting phosphorescent guest bis(7,8-benzoquinolinato) iridium (III) (N,N′-diisopropyl-benzamidine) ((bzq)₂Ir(dipba)). Due to the well-matched energy levels of Bepp₂ with the corresponding hole-/electron- transporting (HT/ET) materials and the high-efficiency and complete energy transfer of this host–guest system, the Bepp₂-based PHOLEDs exhibit rather low driving voltage (2.8 V) and high peak EL efficiencies of over 70 cd A⁻¹ for luminous efficiency, 55 lm W⁻¹ for power efficiency, and 23% for external quantum efficiency, a performance significantly better than that using CBP as the host.     

Charge conduction study of phosphorescent iridium compounds for organic light-emitting diodes application

The charge conduction properties of a series of iridium-based compounds for phosphorescent organic light-emitting diodes (OLEDs) have been investigated by thin-film transistor (TFT) technique. These compounds include four homoleptic compounds: Ir(ppy)₃, Ir(piq)₃, Ir(Tpa-py)₃, Ir(Cz-py)₃, and two heteroleptic compounds Ir(Cz-py)₂(acac) and FIrpic. Ir(ppy)₃, Ir(piq)₃ and FIrpic are commercially available compounds, while Ir(Tpa-py)₃, Ir(Cz-py)₃ and Ir(Cz-py)₂(acac) are specially designed to test their conductivities with respect to the commercial compounds. In neat films, with the exception of FIrpic, all Ir-compounds possess significant hole transporting capabilities, with hole mobilities in the range of about 5 × 10⁻⁶–2 × 10⁻⁵ cm² V⁻¹ s⁻¹. FIrpic, however, is non-conducting as revealed by TFT measurements. We further investigate how Ir-compounds modify carrier transport as dopants when they are doped into a phosphorescent host material CBP. The commercial compounds are chosen for the investigation. Small amounts of Ir(ppy)₃ and Ir(piq)₃ (<10%) behave as hole traps when they are doped into CBP. The hole conduction of the doped CBP films can be reduced by as much as 4 orders of magnitude. Percolating conduction of Ir-compounds occurs when the doping concentrations of the Ir-compounds exceed 10%, and the hole mobilities gradually increase as their values reach those of the neat Ir films. In contrast to Ir(ppy)₃ and Ir(piq)₃, FIrpic does not participate in hole conduction when it is doped into CBP. The hole mobility decreases monotonically as the concentration of FIrpic increases due to the increase of the average charge hopping distance in CBP.     

Synthesis and characterization of blue-emitting Ir(III) complexes with multi-functional ancillary ligands for solution-processed phosphorescent organic light-emitting diodes

A series of Ir(III) complexes, (dfpmpy)₂Ir(pic), (dfpmpy)₂Ir(EO₂-pic), (dfpmpy)₂Ir(pic-N-O), and (dfpmpy)₂Ir(EO₂-pic-N-O), containing 2-(2,4-difluorophenyl)-4-methylpyridine (dfpmpy) based main ligand with varying ancillary ligands such as picolinic acid (pic), 4-(2-ethoxyethoxy)picolinic acid (EO₂-pic), picolinic acid N-oxide (pic-N-O), and 4-(2-ethoxyethoxy)picolinic acid N-oxide (EO₂-pic-N-O), respectively were successfully synthesized for highly efficient blue phosphorescent organic light-emitting diodes (PhOLEDs). The photophysical, electrochemical, and electroluminescent (EL) properties were systematically correlated. The solubilizing 2-ethoxyethanol (EO₂-) group was attached to the ancillary ligand through tandem reaction. All of the Ir(III) complexes show high thermal stability and good photoluminescence quantum yields (Ф_pl) in film state. Solution-processed PhOLEDs were fabricated using these Ir(III) complexes as dopants and achieved a maximum external quantum efficiency (EQE) of 10.9% and current efficiency of 21.15 cd/A for (dfpmpy)₂Ir(EO₂-pic). All the Ir(III) complexes emitted blue light with color purity at the Commission Internationale de L’Eclairage (CIE) coordinates of (0.15, 0.31).     

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

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

A rational molecular design on choosing suitable spacer for better host materials in highly efficient blue and white phosphorescent organic light-emitting diodes

A series of host materials, 3,3′-linked carbazole-based molecules have been designed with phenyl and biphenyl spacers. Their optical and electrical properties can be fine-tuning by the spacers. Their HOMO energy levels depend on HOMO distributions within the range of −5.64 to −5.96 eV. On the other hand, the three compounds have similar LUMO energy levels and triplet energies. Their thermal, photophysical, electrochemical and carrier mobilities properties were also systematically investigated. The relationship between the molecular structures and optoelectronic properties are discussed. A blue PHOLED device incorporating PBCz achieved a maximum external quantum efficiency, current efficiency, and power efficiency of 19.5%, 45.5 cd/A and 43.8 lm/W, respectively. Moreover a two-color, all-phosphor and single-emitting-layer WOLED hosted by PBCz was also achieved with a maximum external quantum efficiency, current efficiency and power efficiency of 24.6%, 76.3 cd/A and 69.4 lm/W respectively. Furthermore, we also utilized this versatile host for three-component RGB white PHOLEDs and show excellent performance. For example, combination of PBCz with FIrpic, Ir(ppy)₂(acac) and Ir(MDQ)₂(acac) in the active layer, the resulting WOLEDs showed three evenly separated peaks and gave a high efficiency of 49.2 cd/A. The efficient PHOLEDs demonstrated that the versatile host PBCz has great potential for applications in the solid-state lighting.     

High efficiency phosphorescent white organic light-emitting diodes with an ultra-thin red and green co-doped layer and dual blue emitting layers

Phosphorescent white organic light emitting diodes (WOLEDs) with a multi-layer emissive structure comprising two separate blue layers and an ultra-thin red and green co-doped layer sandwiched in between have been studied. With proper host and dopant compositions and optimized layer thicknesses, high-performance WOLEDs having a power efficiency over 40 lm/W at 1000 cd/m² with a low efficiency roll-off have been produced. Through a systematic investigation of the exciton confinement and various pathways for energy transfer among the hosts and dopants, we have found that both the ultra-thin co-doped layer and two blue emitting layers play a vital role in achieving high device efficiency and controllable white emission.     

Efficient,color-stable flexible white top-emitting organic light-emitting diodes

Flexible white top-emitting organic light-emitting diodes (WTEOLEDs) with red and blue phosphorescent dual-emitting layers were fabricated onto polyethylene terephthalate (PET) substrates. By inserting a 2-nm thin tris(phenypyrazole)iridium between the red and the blue emitters as an electron/exciton blocking layer, significant improvements on luminous efficiency and color stability were observed, reaching 9.9 cd/A (3.74 lm/W) and a small chromaticity change of (0.019, 0.011) in a wide luminance range of 80–5160 cd/m². The origin on color stability was explored by analyzing the electroluminescent spectra, the time-resolved transient photoluminescence decay lifetimes of phosphors, and the tunneling phenomenon. In addition, mechanical bending lifetimes in WTEOLEDs with spin-coated     

Unmodified small-molecule organic light-emitting diodes by blade coating

Blade coating with substrate heating and hot wind is demonstrated to be a general platform for multi-layer deposition of unmodified small-molecule organic semiconductors. Most unmodified small molecules, originally designed for vacuum evaporation, can be blade coated while the solubility is above 0.5 wt.%. High uniformity is achieved for scale over 5 cm. Orange devices by evaporation and blade coating are compared with 4,4′-bis(carbazol-9-yl)biphenyl (CBP) as the host, iridium(III) bis(4-(4-t-butylphenyl)thieno[3,2-c]pyridinato-N,C²′)acetylacetonate (PO-01-TB) as the emitter. The efficiency difference is within 10%. When 2,6-bis(3-(9H-carbazol-9-yl)phenyl)pyridine (26DCzPPy) is used as the host, the current efficiencies are 40 cd/A for orange, 32 cd/A for green, and 20 cd/A for blue. The optimized organic light-emitting diodes (OLED) structure developed for vacuum deposition can therefore be exactly copied by the low cost blade coating method in solution.