High color rendering index in phosphorescent white organic light-emitting diodes using a yellowish-green dopant with broad light emission

High color rendering index phosphorescent white organic light-emitting diodes (PHWOLEDs) were developed using a yellowish green dopant with broad light emission. A yellowish green phosphorescent dopant derived from difluorophenylquinoline ligand was synthesized and showed maximum emission peak at 550 nm and broad light emission with a full width at half maximum of 77 nm in addition to high quantum efficiency of 20.5%. The yellowish green dopant was used in PHWOLEDs to enhance the color rendering index and high color rendering index of 86.8 was obtained with a high quantum efficiency of 15.7%.     

Ideal host and guest system in phosphorescent OLEDs

Ideal host-guest system for emission in phosphorescent OLEDs with only 1% guest doping condition for efficient energy transfer have been demonstrated in the present investigation. Using a narrow band-gap fluorescent host material, bis(10-hydroxybenzo[h] quinolinato)beryllium complex (Bebq₂), and red dopant bis(2-phenylquinoline)(acetylacetonate)iridium (Ir(phq)₂acac), highly efficient red phosphorescent OLEDs (PHOLEDs) exhibiting excellent energy transfer characteristics with a doping concentration of 1% were developed. Fabricated PHOLEDs show a driving voltage of 3.7 V, maximum current and power efficiencies of 26.53 cd/A and 29.58 lm/W, and a maximum external quantum efficiency of 21%. Minimized electron or hole trapping at the phosphorescent guest molecules and efficient Förster and Dexter energy transfers from the Bebq₂ host singlet and triplet states to the emitting triplet of Ir(phq)₂acac guest appear to be the key mechanism for ideal phosphorescence emission.     

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.     

Efficient hole-transporter for phosphorescent organic light emitting diodes with a simple molecular structure

N,N-diphenyl-4-(quinolin-8-yl)aniline (SQTPA), which composes a triphenylamine group and a quinoline group, has been synthesized and employed as a hole-transporter in phosphorescent OLEDs. It has been proved that SQTPA has efficient hole-transport property with a hole-mobility of 3.60 × 10⁻⁵ cm²/V s at the electric field of 800 (V/cm)^1/2, which is higher than that of NPB (1.93 × 10⁻⁵ cm²/V s). Blue, orange and green phosphorescent OLEDs have been fabricated based on FIrpic, Ir(2-phq)₃, Ir(ppy)₃ with typical structures by using SQTPA as the hole-transporter. The SQTPA-based devices show maximum external quantum efficiencies and power efficiencies of 17.5%, 32.5 lm/W for blue, 12.3%, 20.5 lm/W for orange and 20.3%, 64.5 lm/W for green. The performances of SQTPA-based devices are much better than that of NPB-based phosphorescent OLEDs with similar structures. Thought of its very simple molecular structure and easy synthetic route, SQTPA should be an efficient hole-transporter for phosphorescent OLEDs.     

Highly efficient two component phosphorescent organic light-emitting diodes based on direct hole injection into dopant and gradient doping

A series of two component phosphorescent organic light-emitting diodes (PHOLEDs) combing the direct hole injection into dopant strategy with a gradient doping profile were demonstrated. The dopant, host, as well as molybdenum oxide (MoO₃)-modified indium tin oxide (ITO) anode were investigated. It is found that the devices ITO/MoO₃ (0 or 1 nm)/fac-tris(2-phenylpyridine)iridium [Ir(ppy)₃]:1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi) (30 → 0 wt%, 105 nm)/LiF (1 nm)/Al (100 nm) show maximum external quantum efficiency (EQE) over 20%, which are comparable to multi-layered PHOLEDs. Moreover, the systematic variation of the host from TPBi to 4,7-diphenyl-1,10-phenanthroline (Bphen), dopant from Ir(ppy)₃ to bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)], and anodes between ITO and ITO/MoO₃ indicates that balancing the charge as well as controlling the charge recombination zone play critical roles in the design of highly efficient two component PHOLEDs.     

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.     

Pyridoindole modified carbazole compounds as high triplet energy host materials of imidazole derived blue triplet emitters for high quantum efficiency

Carbazole compounds modified with a pyridoindole moiety were examined as thermally stable high triplet energy host materials for tris[1-(2,4-diisopropyldibenzo[b,d]furan-3-yl)-2-phenylimidazole] (Ir(dbi)₃) based blue phosphorescent organic light-emitting diodes. A well-known carbazole compound, N,N′-dicarbazolyl-3,5-benzene, was substituted with one or two pyridoindole moieties to develop the thermally stable host materials for Ir(dbi)₃ blue triplet emitters. Remarkably high glass transition temperature of 196 °C and thermal decomposition temperature of 486 °C in addition to high triplet energy of 2.89 eV were achieved by the pyridoindole modification. The pyridoindole modified carbazole compounds also delivered high quantum efficiency of 25.4% in the blue phosphorescent devices by doping Ir(dbi)₃.     

Highly efficient bluish green phosphorescent organic light-emitting diodes based on heteroleptic iridium(III) complexes with phenylpyridine main skeleton

A new series of heteroleptic iridium(III) complexes, bis(2-phenylpyridinato-N,C2′)iridium (2-(2′,4′-difluorophenyl)-4-methylpyridine), (ppy)₂Ir(dfpmpy) and bis(2-(2′,4′-difluorophenyl)-4-methylpyridinato-N,C2′)iridium (2-phenylpyridine) (dfpmpy)₂Ir(ppy), have been synthesized by using phenylpyridine as a main skeleton for bluish green phosphorescent organic light-emitting diodes (PhOLEDs). The Ir(III) complexes showed high thermal stability and high photoluminescent (PL) quantum yields of 95% ± 4% simultaneously. As a result, the PhOLEDs with the heteroleptic Ir(III) complexes showed excellent performances approaching 100% internal quantum efficiency with a very high external quantum efficiency (EQE) of ∼27%, a low turn-on voltage of 2.4 V, high power efficiency of ∼85 lm/W, and very low efficiency roll-off up to 20,000 cd/m².     

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.     

Functionalized terfluorene for solution-processed high efficiency blue fluorescence OLED and electrophosphorescent devices

A new multifunctional blue-emitting terfluorene derivative (TFDPA) featured with triphenylamine groups for hole-transportation and long alkyl chains for solution processability on the conjugation inert bridge centers was reported. TFDPA can give homogeneous thin film by solution process and exhibits high hole mobility (μ_h ≈ 10^?3 cm² V^?1 s^?1) and suitable HOMO for hole injection. Particularly, TFDPA performs efficient deep-blue emission with high quantum yield (～100% in solution, 43% in thin film) and suitable triplet energy (E_T = 2.28 eV), making solution-processed OLED devices of using TFDPA as blue emitter and as host for iridium-containing phosphorescent dopants feasible. The solution-processed nondoped blue OLED device gives saturated deep-blue electroluminescence [CIE = (0.17, 0.07)] with EQE of 2.7%. TFDPA-hosted electrophosphorescent devices performed with EQE of 6.5% for yellow [(Bt)₂Ir(acac)], 9.3% of orange [Ir(2–phq)₃], and 6.9% of red [(Mpq)₂Ir(acac)], respectively. In addition, with careful control on the doping concentration of [(Bt)₂Ir(acac)], a solution-processed fluorescence–phosphorescence hybrided two-color-based WOLED with EQE of 3.6% and CIE coordinate of (0.38, 0.33) was successfully achieved.     

A hybrid white organic light-emitting diode with stable color and reduced efficiency roll-off by using a bipolar charge carrier switch

A hybrid white organic light-emitting diode (WOLED) with an emission layer (EML) structure composed of red phosphorescent EML/green phosphorescent EML/spacer/blue fluorescent EML was demonstrated. This hybrid WOLED shows high efficiency, stable spectral emission and low efficiency roll-off at high luminance. We have attributed the significant improvement to the wide distribution of excitons and the effective control of charge carriers in EMLs by using mixed 4,4′,4″-tri(9-carbazoyl) triphenylamine (TCTA) and bis[2-(2-hydroxyphenyl)-pyridine] beryllium (Bepp₂) as the host of phosphorescent EMLs as well as the spacer. The bipolar mixed TCTA:Bepp_2, which was proved to be a charge carrier switch by regulating the distribution of charge carriers and then the exciton recombination zone, plays an important role in improving the efficiency, stabilizing the spectrum and reducing the efficiency roll-off at high luminous. The hybrid WOLED exhibits a current efficiency of 30.2 cd/A, a power efficiency of 32.0 lm/W and an external quantum efficiency of 13.4% at a luminance of 100 cd/m², and keeps a current efficiency of 30.8 cd/A, a power efficiency of 27.1 lm/W and an external quantum efficiency of 13.7% at a 1000 cd/m². The Commission Internationale de l’Eclairage (CIE) coordinates of (0.43, 0.43) and the color rendering index (CRI) of 89 remain nearly unchanged in the whole range of luminance.     

New hole blocking material for green-emitting phosphorescent organic electroluminescent devices

The new amorphous molecular material, 2,5-bis(4-triphenylsilanyl-phenyl)-[1,3,4]oxadiazole, that functions as good hole blocker as well as electron transporting layer in the phosphorescent devices. The obtained material forms homogeneous and stable amorphous film. The new synthesized showed the reversible cathodic reduction for hole blocking material and the low reduction potential for electron transporting material in organic electroluminescent (EL) devices. The fabricated devices exhibited high performance with high current efficiency and power efficiency of 45 cd/A and 17.7 lm/W in 10 mA/cm², which is superior to the result of the device using BAlq (current efficiency: 31.5 cd/A and power efficiency: 13.5 lm/W in 10 mA/cm²) as well-known hole blocker. The ITO/DNTPD/α-NPD/6% Ir(ppy)₃ doped CBP/2,5-bis(4-triphenylsilanyl-phenyl)-[1,3,4]oxadiazole as both hole blocking and electron transporting layer/Al device showed efficiency of 45 cd/A and maximum brightness of 3000 cd/m² in 10 mA/cm².     

Electrical and optical characteristics of phosphorescent organic light-emitting device with thin-codoped layer insertion

In this paper, we demonstrated the changes of electrical and optical characteristics of a phosphorescent organic light-emitting device (OLED) with tris(phenylpyridine)iridium Ir(ppy)₃ thin layer (4 nm) slightly codoped (1%) inside the emitting layer (EML) close to the cathode side. Such a thin layer helped for electron injection and transport from the electron transporting layer into the EML, which reduced the driving voltage (0.40 V at 100 mA/cm²). Electroluminescence (EL) spectral shift at different driving voltage was observed in our blue OLED with [(4,6-di-fluoropheny)-pyridinato-N,C^2′]picolinate (FIrpic) emitter, which came from the recombination zone shift. With the incorporation of thin-codoped Ir(ppy)₃, such EL spectral shift was almost undetectable (color coordinate shift (0.000, 0.001) from 100 to 10,000 cd/m²), due to the compensation of Ir(ppy)₃ emission at low driving voltage. Such a methodology can be applied to a white OLED which stabilized the EL spectrum and the color coordinates ((0.012, 0.002) from 100 to 10,000 cd/m²).     

Green and blue–green light-emitting electrochemical cells based on cationic iridium complexes with 2-(4-ethyl-2-pyridyl)-1H-imidazole ancillary ligand

The ionic iridium complexes, [Ir(ppy)₂(EP-Imid)]PF₆ (Complex 1) and [Ir(dfppy)₂(EP-Imid)]PF₆ (Complex 2) are used as the light-emitting material for the fabrication of light-emitting electrochemical cells (LECs). These complexes have been synthesized, employing 2-(4-ethyl-2-pyridyl)-1H-imidazole (EP-Imid) as the ancillary ligand, 2-phenylpyridine (ppy) and 2-(2,4-difluorophenyl)pyridine (dfppy) as the cyclometalated ligands, which were characterized by various spectroscopic, photophysical and electrochemical methods. The photoluminescence (PL) emission spectra in acetonitrile solution show blue–green and blue light emission for Complexes 1 and 2 respectively. However, LECs incorporating these complexes resulted in green (522 nm) light emission for Complex 1 with the Commission Internationale de L’Eclairage (CIE) coordinates of (0.33, 0.56) and blue–green (500 nm) light emission for Complex 2 with the CIE coordinates of (0.24, 0.44). Using Complex 1, a maximum luminance of 1191 cd m⁻² and current efficiency of 1.0 cd A⁻¹ are obtained while that of Complex 2 are 741 cd m⁻² and 0.88 cd A⁻¹ respectively.     

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.     

Spirobifluorene/sulfone hybrid: Highly efficient solution-processable material for UV–violet electrofluorescence,blue and green phosphorescent OLEDs

A high efficient UV–violet emission type material bis[4-(9,9′-spirobifluorene-2-yl)phenyl] sulfone (SF-DPSO) has been synthesized by incorporating electron deficient sulfone and morphologically stable spirobifluorene into one molecule. The steric and bulky compound SF-DPSO exhibits an excellent solid state photoluminescence quantum yield (Φ_PL = 92%), high glass transition temperature (T_g = 211 °C) and high triplet energy (E_T = 2.85 eV). In addition, the uniform amorphous thin film could be formed by spin-coating from its solution. These promising physical properties of the material made it suitable for using as UV–violet emitter in non-doped device and appropriate host in phosphorescent OLEDs. With SF-DPSO as an emitter, the non-doped solution processed device achieved an efficient UV–violet emission with the EL peak around 400 nm. By using SF-DPSO as a host, solution processed blue and green phosphorescent organic light emitting diodes showed a high luminous efficiency of 13.7 and 30.2 cd A⁻¹, respectively.     

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).     

Spiro-fused N-phenylcarbazole-based host materials for blue phosphorescent organic light-emitting diodes

Two host materials, SFCA and SFCC, consist of a diphenylamine or carbazole unit linking to spiro-fused phenyl carbazole (SFC) backbone, were designed and synthesized. By choosing the meta linkage way between diphenylamine/carbazole units and SFC ring, higher triplet energies could be easily achieved for the two new materials, which mean that they could be used as effective host material for popular blue phosphorescent material Iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C^2′] picolinate (FIrpic, E_T = 2.65). Besides that, the steric SFC structure could guarantee their good thermal stabilities. Their thermal, photophysical and electroluminescent properties were systematically investigated. The blue phosphorescent OLEDs with the two materials as hosts and FIrpic as a dopant exhibited excellent performance with maximum current efficiencies of 33.9 and 40.8 cd/A, respectively.     

Novel dibenzothiophene based host materials incorporating spirobifluorene for high-efficiency white phosphorescent organic light-emitting diodes

Two host materials, DBTSF2 and DBTSF4, were designed and synthesized, incorporating dibenzothiophene (DBT) and spirobifluorene (SF) blocks. Their thermal, electrochemical and photo-physical properties were fully characterized. DBTSF4, which adopted an ortho-linkage between DBT and SF moieties, showed a significantly higher T₁ energy of 2.82 eV as compared to its para-linkage analogue DBTSF2 (2.49 eV). Their applications as host for green, blue and white phosphorescent organic light-emitting diodes (PHOLEDs) were explored. The DBTSF4 based blue PHOLED has a highest current efficiency of 23.5 cd A^?1. And using DBTSF4 as a single host, two-color based white PHOLEDs were achieved from cold white emission with CIE coordinate of (0.31, 0.43) to yellowish warm white emission (0.44, 0.49) with maximum current efficiencies varying from 35.8 to 52.3 cd A^?1 and maximum external quantum efficiencies from 13.1% to 16.9% respectively. The white PHOLED devices also showed a low efficiency roll-off even at 10,000 cd m^?2.     

High external quantum efficiency in yellow and white phosphorescent organic light-emitting diodes using an indoloacridinefluorene type host material

High efficiency yellow phosphorescent organic light-emitting diodes were developed using spiro[fluorene-9,8′-indolo[3,2,1-de]acridine]-2,7-dicarbonitrile (ACDCN) as the host material for yellow emitting iridium(III) bis(4-phenylthieno[3,2-c]pyridinato-N,C²′)acetylacetonate (PO-01). The ACDCN host showed bipolar charge transport properties and efficient energy transfer to PO-01 dopant. Maximum external quantum efficiency of 25.7% and external quantum efficiency of 21.9% at 1000 cd/m² were obtained using ACDCN as the host material. In addition, high external quantum efficiency of 20.9% was achieved in the two color white phosphorescent organic light-emitting diodes with the PO-01 and iridium(III) bis[(4,6-difluorophenyl)-pyridinato-N,C²]picolinate doped ACDCN emitting layer.