Bright and Efficient,Non‐Doped,Phosphorescent Organic Red‐Light‐Emitting Diodes

Ir^(III) metal complexes with formula [(nazo)₂Ir(Fppz)] ( 1 ), [(nazo)₂Ir(Bppz)] ( 2 ), and [(nazo)₂Ir(Fptz)] ( 3 ) [(nazo)H = 4‐phenyl quinazoline, (Fppz)H = 3‐trifluoromethyl‐5‐(2‐pyridyl) pyrazole, (Bppz)H = 3‐t‐butyl‐5‐(2‐pyridyl) pyrazole, and (Fptz)H = 3‐trifluoromethyl‐5‐(2‐pyridyl) triazole] were synthesized, among which the exact configuration of 1 was confirmed using single‐crystal X‐ray diffraction analysis. These complexes exhibited bright red phosphorescence with relatively short lifetimes of 0.4–1.05 μs in both solution and the solid‐state at room temperature. Non‐doped organic light‐emitting diodes (OLEDs) were fabricated using complexes 1 and 2 in the absence of a host matrix. Saturated red electroluminescence was observed at λ_max = 626 nm (host‐emitter complex 1 ) and 652 nm (host‐emitter complex 2 ), which corresponds to coordinates (0.66,0.34) and (0.69,0.31), respectively, on the 1931 Commission Internationale de l'Eclairage (CIE) chromaticity diagram. The non‐doped devices employing complex 1 showed electroluminance as high as 5780 cd m^–2, an external quantum efficiency of 5.5 % at 8 V, and a current density of 20 mA cm^–2. The short phosphorescence lifetime of 1 in the solid state, coupled with its modest π–π stacking interactions, appear to be the determining factors for its unusual success as a non‐doped host‐emitter.     

Amorphous Diphenylaminofluorene‐Functionalized Iridium Complexes for High‐Efficiency Electrophosphorescent Light‐Emitting Diodes

Two new phosphorescent iridium(III ) cyclometalated complexes, [Ir(DPA‐Flpy)₃] ( 1 ) and [Ir(DPA‐Flpy)₂(acac)] ( 2 ) ((DPA‐Flpy)H = (9,9‐diethyl‐7‐pyridinylfluoren‐2‐yl)diphenylamine, Hacac = acetylacetone), have been synthesized and characterized. The incorporation of electron‐donating diphenylamino groups to the fluorene skeleton is found to increase the highest occupied molecular orbital (HOMO) levels and add hole‐transporting ability to the phosphorescent center. Both complexes are highly amorphous and morphologically stable solids and undergo glass transitions at 160 and 153 °C, respectively. These iridium phosphors emit bright yellow to orange light at room temperature with relatively short lifetimes (< 1 μs) in both solution and the solid state. Organic light‐emitting diodes (OLEDs) fabricated using 1 and 2 as phosphorescent dopant emitters constructed with a multilayer configuration show very high efficiencies. The homoleptic iridium complex 1 is shown to be a more efficient electrophosphor than the heteroleptic congener 2 . Efficient electrophosphorescence with a maximum external quantum efficiency close to 10 % ph/el (photons per electron), corresponding to a luminance efficiency of ～ 30 cd A^–1 and a power efficiency of ～ 21 lm W^–1, is obtained by using 5 wt.‐% 1 as the guest dopant.     

Platinum Binuclear Complexes as Phosphorescent Dopants for Monochromatic and White Organic Light‐Emitting Diodes

Efficient blue‐, green‐, and red‐light‐emitting organic diodes are fabricated using binuclear platinum complexes as phosphorescent dopants. The series of complexes used here have pyrazolate bridging ligands and the general formula C^∧NPt(μ‐pz)₂PtC^∧N (where C^∧N = 2‐(4′,6′‐difluorophenyl)pyridinato‐N,C^2′, pz = pyrazole ( 1 ), 3‐methyl‐5‐tert‐butylpyrazole ( 2 ), and 3,5‐bis(tert‐butyl)pyrazole ( 3 )). The Pt–Pt distance in the complexes, which decreases in the order 1 > 2 > 3 , solely determines the electroluminescence color of the organic light‐emitting diodes (OLEDs). Blue OLEDs fabricated using 8 % 1 doped into a 3,5‐bis(N‐carbazolyl)benzene (mCP) host have a quantum efficiency of 4.3 % at 120 Cd m^–2, a brightness of 3900 Cd m^–2 at 12 V, and Commission Internationale de L'Eclairage (CIE) coordinates of (0.11, 0.24). Green and red OLEDs fabricated with 2 and 3 , respectively, also give high quantum efficiencies (～ 6.7 %), with CIE coordinates of (0.31, 0.63) and (0.59, 0.46), respectively. The current‐density–voltage characteristics of devices made using dopants 2 and 3 indicate that hole trapping is enhanced by short Pt–Pt distances (< 3.1 Å). Blue electrophosphorescence is achieved by taking advantage of the binuclear molecular geometry in order to suppress dopant intermolecular interactions. No evidence of low‐energy emission from aggregate states is observed in OLEDs made with 50 % 1 doped into mCP. OLEDs made using 100 % 1 as an emissive layer display red luminescence, which is believed to originate from distorted complexes with compressed Pt–Pt separations located in defect sites within the neat film. White OLEDs are fabricated using 1 and 3 in three different device architectures, either with one or two dopants in dual emissive layers or both dopants in a single emissive layer. All the white OLEDs have high quantum efficiency (～ 5 %) and brightness (～ 600 Cd m^–2 at 10 V).     

Solution‐Processible Multi‐component Cyclometalated Iridium Phosphors for High‐Efficiency Orange‐Emitting OLEDs and Their Potential Use as White Light Sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole‐transporting carbazole and fluorene‐based 2‐phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the π‐conjugation through incorporation of electron‐pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest occupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium‐based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo‐ and electroluminescence properties of these phosphorescent carbazolylfluorene‐functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light‐emitting diodes (OLEDs) using these complexes as the solution‐processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole‐transporting layer. These orange‐emitting devices can produce a maximum current efficiency of ～ 30 cd A^–1 corresponding to an external quantum efficiency of ～ 10 % ph/el (photons per electron) and a power efficiency of ～ 14 lm W^–1. The homoleptic iridium phosphors generally outperform the heteroleptic counterparts in device performance. The potential of exploiting these orange phosphor dyes in the realization of white OLEDs is also discussed.     

Highly Efficient Green‐Emitting Phosphorescent Iridium Dendrimers Based on Carbazole Dendrons

Green‐emitting iridium dendrimers with rigid hole‐transporting carbazole dendrons are designed, synthesized, and investigated. With second‐generation dendrons, the photoluminescence quantum yield of the dendrimers is up to 87 % in solution and 45 % in a film. High‐quality films of the dendrimers are fabricated by spin‐coating, producing highly efficient, non‐doped electrophosphorescent organic light‐emitting diodes (OLEDs). With a device structure of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonic acid)/neat dendrimer/1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene/LiF/Al, a maximum external quantum efficiency (EQE) of 10.3 % and a maximum luminous efficiency of 34.7 cd A^–1 are realized. By doping the dendrimers into a carbazole‐based host, the maximum EQE can be further increased to 16.6 %. The integration of rigid hole‐transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution‐processable dendrimers for OLED applications.     

A Light‐Blue Phosphorescent Dendrimer for Efficient Solution‐Processed Light‐Emitting Diodes

We describe the preparation of a dendrimer that is solution‐processible and contains 2‐ethylhexyloxy surface groups, biphenyl‐based dendrons, and a fac‐tris[2‐(2,4‐difluorophenyl)pyridyl]iridium(III ) core. The homoleptic complex is highly luminescent and the color of emission is similar to the heteroleptic iridium(III ) complex, bis[2‐(2,4‐difluorophenyl)pyridyl]picolinate iridium(III ) (FIrpic). To avoid the change in emission color that would arise from attaching a conjugated dendron to the ligand, the conjugation between the dendron and the ligand is decoupled by separating them with an ethane linkage. Bilayer devices containing a light‐emitting layer comprised of a 30 wt.‐% blend of the dendrimer in 1,3‐bis(N‐carbazolyl)benzene (mCP) and a 1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene electron‐transport layer have external quantum and power efficiencies, respectively, of 10.4 % and 11 lm W^–1 at 100 cd m^–2 and 6.4 V. These efficiencies are higher than those reported for more complex device structures prepared via evaporation that contain FIrpic blended with mCP as the emitting layer, showing the advantage of using a dendritic structure to control processing and intermolecular interactions. The external quantum efficiency of 10.4 % corresponds to the maximum achievable efficiency based on the photoluminescence quantum yield of the emissive film and the standard out‐coupling of light from the device.     

High Performance Polymer Electrophosphorescent Devices with tert‐Butyl Group Modified Iridium Complexes as Emitters

The synthesis and photophysical study of two novel tert‐butyl modified cyclometalated iridium(III) complexes, i.e., bis(4‐tert‐butyl‐2‐phenylbenzothiozolato‐N,C^2′) iridium(III)(acetylacetonate) [(tbt)₂Ir(acac)] and bis(4‐tert‐butyl‐1‐phenyl‐1H‐benzimidazolato‐N,C^2′) iridium(III)(acetylacetonate) [(tpbi)₂Ir(acac)], are reported, their molecular structures were characterized by ¹³C NMR, ¹H NMR, ESI‐MS, FT‐IR, and elementary analysis. Compared with their prototypes without tert‐butyl substituents [(bt)₂Ir(acac) and (pbi)₂Ir(acac)], (tbt)₂Ir(acac) and (tpbi)₂Ir(acac) both have shortened phosphorescent lifetimes[(tbt)₂Ir(acac) versus (bt)₂Ir(acac), 1.1 μs:1.8 μs; (pbi)₂Ir(acac) versus (tpbi)₂Ir(acac), 0.8 μs:1.82 μs]. Moreover, (tbt)₂Ir(acac) has much more improved phototoluminescence quantum efficiencies in CH₂Cl₂ solution, [(tbt)₂Ir(acac), 0.51; (bt)₂Ir(acac), 0.26]. Employing them as dopants, high performance double‐layer PLEDs were fabricated. The (tbt)₂Ir(acac)‐based and (tpbi)₂Ir(acac)‐based PLEDs have the maximum external quantum efficiencies of 8.71 % and 10.25 %, respectively, and high EL quantum efficiencies of 5.92 % and 7.21 % can be achieved under high driven current density of 100 mA cm^–2. PLEDs fabricated with both the two phosphors have much broadened EL spectra with FWHM of > 110 nm, which afford the feasibility to be used as dopants in white LEDs, and the best doping concentrations of the two complexes in fabrication of PLEDs were optimized.     

Novel Heteroleptic CuI Complexes with Tunable Emission Color for Efficient Phosphorescent Light‐Emitting Diodes

A series of orange‐red to red phosphorescent heteroleptic Cu^I complexes (the first ligand: 2,2′‐biquinoline (bq), 4,4′‐diphenyl‐2,2′‐biquinoline (dpbq) or 3,3′‐methylen‐4,4′‐diphenyl‐2,2′‐biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2‐(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline‐type ligands, complexes [Cu(mdpbq)(PPh₃)₂](BF₄) and [Cu(mdpbq)(DPEphos)](BF₄) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N‐(4‐(carbazol‐9‐yl)phenyl)‐3,6‐bis(carbazol‐9‐yl) carbazole (TCCz), phosphorescent organic light‐emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF₄) exhibits the best device performance. With the device structure of ITO/PEDOT/TCCz:[Cu(mdpbq)(DPEphos)](BF₄) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A^–1 with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu^I complexes with red emission.     

Highly Efficient Non‐Doped Blue Organic Light‐Emitting Diodes Based on Fluorene Derivatives with High Thermal Stability

A new series of blue‐light‐emitting fluorene derivatives have been synthesized and characterized. The fluorene derivatives have high fluorescence yields, good thermal stability, and high glass‐transition temperatures in the range 145–193 °C. Organic light‐emitting diodes (OLEDs) fabricated using the fluorene derivatives as the host emitter show high efficiency (up to 5.3 cd A^–1 and 3.0 lm W^–1) and bright blue‐light emission (Commission Internationale de L'Eclairage (CIE) coordinates of x = 0.16, y = 0.22). The performance of the non‐doped fluorene‐based devices is among the best fluorescent blue‐light‐emitting OLEDs. The good performance of the present blue OLEDs is considered to derive from: 1) appropriate energy levels of the fluorene derivatives for good carrier injection; 2) good carrier‐transporting properties; and 3) high fluorescence efficiency of the fluorene derivatives. These merits are discussed in terms of the molecular structures.     

N∧C∧N‐Coordinated Platinum(II) Complexes as Phosphorescent Emitters in High‐Performance Organic Light‐Emitting Devices

A series of terdentate cyclometallated Pt^II complexes with remarkable luminescence properties are used as new phosphorescence‐emitting dopants in a blended host matrix as the emitting layer, resulting in very high electroluminescence efficiencies. Because of the high phosphorescence quantum yields of these Pt complexes and the efficient energy transfer from both singlet and triplet excited states of the host to the emitting guest, external electroluminescence quantum efficiencies as high as 4–16 % photons per carrier and luminous efficiencies of 15–40 cd A^–1 are achieved. Moreover, these high efficiency values were maintained over a four‐decade current intensity span with no significant roll‐off. Tuning of the electroluminescence spectra from the yellow to the green‐bluish region of the chromaticity diagram is obtained simply by changing the substituents at the central 5‐position of the cyclometallating ligand.     

Highly Branched Phosphorescent Dendrimers for Efficient Solution‐Processed Organic Light‐Emitting Diodes

Intermolecular interactions play a crucial role in the performance of organic light‐emitting diodes (OLEDs). Here we report the photophysical and electroluminescence properties of a fac‐tris(2‐phenylpyridyl)iridium(III ) cored dendrimer in which highly branched biphenyl dendrons are used to control the intermolecular interactions. The presence of fluorene surface groups improves the solubility and enhances the efficiency of photoluminescence, especially in the solid state. The emission peak of the dendrimer is around 530 nm with a PL quantum yield of 76 % in solution and 25 % in a film. The photophysical properties of this dendrimer are compared with a similar dendrimer with the same structure but without the fluorene surface groups. Dendrimer LEDs (DLEDs) are prepared using each dendrimer as a phosphorescent emitter blended in a 4,4′‐bis(N‐carbazolyl)biphenyl host. Device performance is improved significantly by the incorporation of an electron‐transporting layer of 1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene. A peak external quantum efficiency of 10 % (38 Cd A^–1) for the dendrimer without surface groups and 13 % (49.8 Cd A^–1) for the dendrimer with fluorene surface groups is achieved in the bilayer LEDs.     

White‐Light‐Emitting Diodes Based on Iridium Complexes via Efficient Energy Transfer from a Conjugated Polymer

Efficient white‐light‐emitting diodes (WLEDs) have been developed using a polyfluorene‐type blue‐emitting conjugated polymer doped with green and red phosphorescent dyes. The emission spectrum of the conjugated polymer, which has a very high luminescent efficiency, shows a large spectral overlap with the absorbance of green and red iridium complexes. Also, efficient energy transfer from the conjugated polymer to the iridium complexes is observed. Poly(N‐vinyl carbazole) is used to improve the miscibility between conjugated polymer and iridium complexes because of their poor chemical compatibility and phase separation. A white emission spectrum is easily obtained by varying the contents of the three materials and controlling the phase morphology. Moreover, these WLEDs show a voltage‐independent electroluminescence owing to the threshold and driving voltage of the three materials being similar as a result of energy transfer.     

Red Phosphorescent Iridium Complex Containing Carbazole‐Functionalized β‐Diketonate for Highly Efficient Nondoped Organic Light‐Emitting Diodes

A novel red phosphorescent iridium complex containing a carbazole‐functionalized β‐diketonate, Ir(DBQ)₂(CBDK) (bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(carbazol‐9‐yl)‐5,5‐dimethylhexane‐2,4‐diketonate)) is designed, synthesized, and characterized. The electrophosphorescence properties of a nondoped device using the title complex as an emitter with a device configuration of indium tin oxide (ITO)/N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐diphenyl‐4,4′‐diamine (NPB; 20 nm)/iridium complex (20 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 5 nm)/tris(8‐hydroxyquinoline) (AlQ; 30 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) are examined. The results show that the nondoped device achieves a maximum lumen efficiency as high as 3.49 lm W^–1. To understand this excellent result observed, two reference complexes Ir(DBQ)₂(acac), where acac is the acetyl acetonate anion, and Ir(DBQ)₂(FBDK), [bis(dibenzo[f,h]quinoxalinato‐N,C²) iridium (1‐(9‐methyl‐fluoren‐9‐yl)‐6,6‐dimethylheptane‐3,5‐diketonate)], have also been synthesized, and as emitters they were examined under the same device configuration. The maximum lumen efficiency of the former compound is found to be 0.26 lm W^–1 while that for the latter is 0.37 lm W^–1, suggesting that the excellent performance of Ir(DBQ)₂(CBDK) can be attributed mainly to an improved hole‐transporting property that benefits the exciton transport. In addition, a bulky diketonate group separates the emitter centers from each other, which is also important for organic light‐emitting diodes.     

Extremely Low Operating Voltage Green Phosphorescent Organic Light‐Emitting Devices

Organic light‐emitting devices (OLEDs) are expected to be adopted as the next generation of general lighting because they are more efficient than fluorescent tubes and are mercury‐free. The theoretical limit of operating voltage is generally believed to be equal to the energy gap, which corresponds to the energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) for the emitter molecule divided by the electron charge (e). Here, green OLEDs operating below a theoretical limit of the energy gap (E_g) voltage with high external quantum efficiency over 20% are demonstrated using fac‐tris(2‐phenylpyridine)iridium(III) with a peak emission wavelength of 523 nm, which is equivalent to a photon energy of 2.38 eV. An optimized OLED operates clearly below the theoretical limit of the E_g voltage at 2.38 V showing 100 cd m^?2 at 2.25 V and 5000 cd m^?2 at 2.95 V without any light outcoupling enhancement techniques.     

Candle Light‐Style Organic Light‐Emitting Diodes

In response to the call for a physiologically‐friendly light at night that shows low color temperature, a candle light‐style organic light emitting diode (OLED) is developed with a color temperature as low as 1900 K, a color rendering index (CRI) as high as 93, and an efficacy at least two times that of incandescent bulbs. In addition, the device has a 80% resemblance in luminance spectrum to that of a candle. Most importantly, the sensationally warm candle light‐style emission is driven by electricity in lieu of the energy‐wasting and greenhouse gas emitting hydrocarbon‐burning candles invented 5000 years ago. This candle light‐style OLED may serve as a safe measure for illumination at night. Moreover, it has a high color rendering index with a decent efficiency.     

Enhancement of External Quantum Efficiency of Red Phosphorescent Organic Light‐Emitting Devices with Facially Encumbered and Bulky PtII Porphyrin Complexes

An enhancement in the external quantum efficiency (QE) of red phosphorescent organic light‐emitting devices (OLEDs) by using facially encumbered and bulky meso‐aryl substituted Pt^II porphyrin complexes is demonstrated. The maximum external QEs of phosphorescent OLEDs doped with the facially non‐encumbered Pt^II porphyrin complex 1 [5,15‐bis[4‐(4,4‐dimethyl‐2,6‐dioxacyclohexyl)phenyl]‐2,8,12,18‐tetrahexyl‐3,7,13,17‐tetramethylporphyrin platinum(II )], the facially encumbered Pt^II porphyrin complex 2 [5,15‐bis(2,6‐dimethoxyphenyl)‐2,8,12,18‐tetrahexyl‐3,7,13,17‐tetramethylporphyrinato platinum(II )], the Pt^II porphyrin complex 3 that bears bulkier 3,5‐di‐tert‐butylphenyl substituents [5,15‐bis(3,5‐di‐t‐butylphenyl)‐2,8,12,18‐tetrahexyl‐3,7,13,17‐tetramethylporphyrin platinum(II )], and the “doubly‐decamethylene‐strapped” Pt^II porphyrin complex 4 were 1, 4.2, 7.3, and 8.2 %, respectively. The trend of increasing QE values in the order of 1 < 2 < 3 < 4 may be related to facial encumbrance and steric bulkiness of meso‐aryl substituted Pt^II porphyrin complexes. Especially, in the case of the Pt^II porphyrin 4 , it is considered that the “double straps” play an important role in restricting rotational freedom of the meso‐aryl substituents. The triplet excited‐state lifetimes for Pt^II porphyrins 1 – 4 in OLEDs at an injection current density of 0.55 mA cm^–2 were 80, 103, 140, and 152 μs, respectively. We believe that the trend of increasing triplet lifetime in going from 1 to 4 is correlated with suppressing non‐radiative decay.     

Chain‐Length Dependence of Singlet and Triplet Exciton Formation Rates in Organic Light‐Emitting Diodes

The operation and efficiencies of molecular or polymer organic light‐emitting diodes depend on the nature of the excited species that are formed. The lowest singlet and triplet excitons display different characteristics that impact on the quantum yields achievable in the devices. Here, by performing correlated quantum‐chemical calculations that account for both the electronic couplings and energetics of the charge‐recombination process from a pair of positive and negative polarons into singlet and triplet excitons, we show that the formation rates for singlet over triplet excitons vary with chain length and favor singlet excitons in longer chains. Thus, in polymer devices, the resulting singlet/triplet fraction can significantly exceed the spin‐statistical limit.