Peter I. Djurovich

Endothermic energy transfer: A mechanism for generating very efficient high-energy phosphorescent emission in organic materials

Intermolecular energy transfer processes typically involve an exothermic transfer of energy from a donor site to a molecule with a substantially lower-energy excited state (trap). Here, we demonstrate that an endothermic energy transfer from a molecular organic host (donor) to an organometallic phosphor (trap) can lead to highly efficient blue electroluminescence. This demonstration of endothermic transfer employs iridium(III)bis(4,6-di-fluorophenyl)-pyridinato-N,C2′)picolinate as the phosphor. Due to the comparable energy of the phosphor triplet state relative to that of the 4,4′-N,N′-dicarbazole-biphenyl conductive host molecule into which it is doped, the rapid exothermic transfer of energy from phosphor to host, and subsequent slow endothermic transfer from host back to phosphor, is clearly observed. Using this unique triplet energy transfer process, we force emission from the higher-energy, blue triplet state of the phosphor (peak wavelength of 470 nm), obtaining a very high maximum organic light-emi...

Deep blue phosphorescent organic light-emitting diodes with very high brightness and efficiency.

The combination of both very high brightness and deep blue emission from phosphorescent organic light-emitting diodes (PHOLED) is required for both display and lighting applications, yet so far has not been reported. A source of this difficulty is the absence of electron/exciton blocking layers (EBL) that are compatible with the high triplet energy of the deep blue dopant and the high frontier orbital energies of hosts needed to transport charge. Here, we show that N-heterocyclic carbene (NHC) Ir(III) complexes can serve as both deep blue emitters and efficient hole-conducting EBLs. The NHC EBLs enable very high brightness (>7,800 cd m(-2)) operation, while achieving deep blue emission with colour coordinates of [0.16, 0.09], suitable for most demanding display applications. We find that both the facial and the meridional isomers of the dopant have high efficiencies that arise from the unusual properties of the NHC ligand-that is, the complexes possess a strong metal-ligand bond that destabilizes the non-radiative metal-centred ligand-field states. Our results represent an advance in blue-emitting PHOLED architectures and materials combinations that meet the requirements of many critical illumination applications.

Saturated deep blue organic electrophosphorescence using a fluorine-free emitter

We demonstrate saturated, deep blue organic electrophosphorescence using the facial- and meridianal- isomers of the fluorine-free emitter tris(phenyl-methyl-benzimidazolyl)iridium(III)(f-Ir(pmb)3 and m-Ir(pmb)3, respectively) doped into the wide energy gap host, p-bis(triphenylsilyly)benzene (UGH2). The highest energy electrophosphorescent transition occurs at a wavelength of λ=389nm for the fac- isomer and λ=395nm for the mer- isomer. The emission chromaticity is characterized by Commission Internationale de l’Eclairage coordinates of (x=0.17,y=0.06) for both isomers. Peak quantum and power efficiencies of (2.6±0.3)% and (0.5±0.1)lm∕W and (5.8±0.6)% and (1.7±0.2)lm∕W are obtained using f-Ir(pmb)3 andm-Ir(pmb)3 respectively. This work represents a departure from previously explored, fluorinated blue phosphors, and demonstrates an efficient deep blue/near ultraviolet electrophosphorescent device.

A codeposition route to CuI-pyridine coordination complexes for organic light-emitting diodes.

We demonstrate a new approach for utilizing CuI coordination complexes as emissive layers in organic light-emitting diodes that involves in situ codeposition of CuI and 3,5-bis(carbazol-9-yl)pyridine (mCPy). With a simple three-layer device structure, pure green electroluminescence at 530 nm from a Cu(I) complex was observed. A maximum luminance and external quantum efficiency (EQE) of 9700 cd/m(2) and 4.4%, respectively, were achieved. The luminescent species was identified as [CuI(mCPy)(2)](2) on the basis of photophysical studies of model complexes and X-ray absorption spectroscopy.

Phosphorescence versus Thermally Activated Delayed Fluorescence. Controlling Singlet–Triplet Splitting in Brightly Emitting and Sublimable Cu(I) Compounds

Photophysical properties of two highly emissive three-coordinate Cu(I) complexes, (IPr)Cu(py2-BMe2) (1) and (Bzl-3,5Me)Cu(py2-BMe2) (2), with two different N-heterocyclic (NHC) ligands were investigated in detail (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; Bzl-3,5Me = 1,3-bis(3,5-dimethylphenyl)-1H-benzo[d]imidazol-2-ylidene; py2-BMe2 = di(2-pyridyl)dimethylborate). The compounds exhibit remarkably high emission quantum yields of more than 70% in the powder phase. Despite similar chemical structures of both complexes, only compound 1 exhibits thermally activated delayed blue fluorescence (TADF), whereas compound 2 shows a pure, yellow phosphorescence. This behavior is related to the torsion angles between the two ligands. Changing this angle has a huge impact on the energy splitting between the first excited singlet state S1 and triplet state T1 and therefore on the TADF properties. In addition, it was found that, in both compounds, spin-orbit coupling (SOC) is particularly effective compared to other Cu(I) complexes. This is reflected in short emission decay times of the triplet states of only 34 μs (1) and 21 μs (2), respectively, as well as in the zero-field splittings of the triplet states amounting to 4 cm(-1) (0.5 meV) for 1 and 5 cm(-1) (0.6 meV) for 2. Accordingly, at ambient temperature, compound 1 exhibits two radiative decay paths which are thermally equilibrated: one via the S1 state as TADF path (62%) and one via the T1 state as phosphorescence path (38%). Thus, if this material is applied in an organic light-emitting diode, the generated excitons are harvested mainly in the singlet state, but to a significant portion also in the triplet state. This novel mechanism based on two separate radiative decay paths reduces the overall emission decay time distinctly.

Cyclometalated Ir complexes in polymer organic light-emitting devices

Several new iridium based cyclometalated complexes were investigated as phosphorescent dopants for molecularly doped polymeric organic light-emitting diodes. Specifically, the complexes used in this study were iridium (III) bis(2-phenylpyridinato-N,C2′) (acetylacetonate) [ppy], iridium (III) bis(7,8-benzoquinolinato-N,C3′) (acetylacetonate) [bzq], iridium (III) bis(2-phenylbenzothiazolato-N,C2′) (acetylacetonate) [bt], iridium (III) bis(2-(2′-naphthyl)benzothiazolato-N,C2′) (acetylacetonate) [bsn] and iridium (III) bis(2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C3′) (acetylacetonate) [btp]. Single layer devices of doped polyvinylcarbazole: 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole give maximum external quantum efficiencies that varied from 3.5% for the ppy dopant to 0.4% for the btp dopant. Several different device heterostructure architectures were explored, and the best quantum efficiency of the devices reached 4.2% for the heterostructures.

Molecularly doped polymer light emitting diodes utilizing phosphorescent Pt(II) and Ir(III) dopants

Abstract The use of molecular phosphorescent dyes in polymer-based organic light emitting diodes (OLED) of different architectures was investigated by incorporating several phosphorescent dopants into poly( N -vinylcarbazole) (PVK)-based single layer and single heterostructure light emitting diodes (LEDs). In particular, cis -bis[2-(2-thienyl)pyridine-N,C 3 ] platinum(II) (Pt(thpy) 2 ) and platinum(II) 2,8,12,17-tetraethyl-3,7,13,18-tetramethyl porphyrin (PtOX), and an Ir(III) compound, fac -tris[2-(4 ′ ,5 ′ -difluorophenyl)pyridine-C ′2 ,N] iridium(III) (FIrppy) were used. The maximum external quantum efficiency of phosphorescent devices exceeds 0.6% for the two Pt dopants and reaches ≈1.8% for FIrppy. An overall increase in LED efficiency compared to similar devices based on fluorescence is attributed to the fact that phosphorescent dopants allow both singlet and triplet excitons to be involved in emission. In addition to finding an energetically suitable dopant, such parameters as dopant concentration and organic layer thickness influence the performance of the LEDs. Introduction of an electron injecting layer of tris(8-hydroxyquinoline) aluminum(III) causes an increase of quantum efficiency of up to 1.8–2.8%. The second order quenching process present in these OLEDs, which is prevalent at high current densities, is most likely not due to T–T annihilation of excitons trapped at dopant sites in these OLEDs. T–T annihilation in the PVK matrix or trapped charge-triplet annihilation are more likely explanations for the decrease.

Singlet and Triplet Excitation Management in a Bichromophoric Near-Infrared-Phosphorescent BODIPY-Benzoporphyrin Platinum Complex

Multichromophoric arrays provide one strategy for assembling molecules with intense absorptions across the visible spectrum but are generally focused on systems that efficiently produce and manipulate singlet excitations and therefore are burdened by the restrictions of (a) unidirectional energy transfer and (b) limited tunability of the lowest molecular excited state. In contrast, we present here a multichromophoric array based on four boron dipyrrins (BODIPY) bound to a platinum benzoporphyrin scaffold that exhibits intense panchromatic absorption and efficiently generates triplets. The spectral complementarity of the BODIPY and porphryin units allows the direct observation of fast bidirectional singlet and triplet energy transfer processes (k(ST)((1)BDP→(1)Por) = 7.8 × 10(11) s(-1), k(TT)((3)Por→(3)BDP) = 1.0 × 10(10) s(-1), k(TT)((3)BDP→(3)Por) = 1.6 × 10(10) s(-1)), leading to a long-lived equilibrated [(3)BDP][Por]⇌[BDP][(3)Por] state. This equilibrated state contains approximately isoenergetic porphyrin and BODIPY triplets and exhibits efficient near-infrared phosphorescence (λ(em) = 772 nm, Φ = 0.26). Taken together, these studies show that appropriately designed triplet-utilizing arrays may overcome fundamental limitations typically associated with core-shell chromophores by tunable redistribution of energy from the core back onto the antennae.

Efficient dipyrrin-centered phosphorescence at room temperature from bis-cyclometalated iridium(III) dipyrrinato complexes.

A series of seven dipyrrin-based bis-cyclometalated Ir(III) complexes have been synthesized and characterized. All complexes display a single, irreversible oxidation wave and at least one reversible reduction wave. The electrochemical properties were found to be dominated by dipyrrin centered processes. The complexes were found to display room temperature luminescence with emission maxima ranging from 658 to 685 nm. Through systematic variation of the cyclometalating ligand and the meso substituent of the dipyrrin moiety, it was found that the observed room temperature emission was due to phosphorescence from a dipyrrin-centered triplet state with quantum efficiencies up to 11.5%. Bis-cyclometalated Ir(III) dipyrrin based organic light emitting diodes (OLEDs) display emission at 682 nm with maximum external quantum efficiencies up to 1.0%.

Ultraviolet electroluminescence and blue-green phosphorescence using an organic diphosphine oxide charge transporting layer

We report electroluminescence at 338nm from a simple bilayer organic light-emitting device (OLED) made using 4,4′-bis(diphenylphosphine oxide) biphenyl (PO1). In an OLED geometry, the material is preferentially electron transporting. Doping the PO1 layer with iridium(III)bis(4,6-(di-fluorophenyl)-pyridinato-N,C2′)picolinate (FIrpic) gives rise to electrophosphorescence with a peak external quantum efficiency of 7.8% at 0.09mA∕cm2 and 5.9% at 13mA∕cm2. The latter current density is obtained at 6.3V applied forward bias.