Purely Organic Room-Temperature Phosphorescence Molecule for High-Performance Non-Doped Organic Light-Emitting Diodes.

Purely organic molecules with room-temperature phosphorescence (RTP) are potential luminescent materials with high exciton utilization for organic light-emitting diodes (OLEDs), but those exhibiting superb electroluminescence (EL) performances are rarely explored, mainly due to their long phosphorescence lifetimes. Herein, a robust purely organic RTP molecule, 3,6-bis(5-phenylindolo[3,2-a]carbazol-12(5H)-yl)-xanthen-9-one (3,2-PIC-XT), is developed. The neat film of 3,2-PIC-XT shows strong green RTP with a very short lifetime (2.9 µs) and a high photoluminescence quantum yield (72 %), and behaviors balanced bipolar charge transport. The RTP nature of 3,2-PIC-XT is validated by steady-state and transient absorption and emission spectroscopies, and the working mechanism is deciphered by theoretical simulation. Non-doped multilayer OLEDs using thin neat films of 3,2-PIC-XT furnish an outstanding external quantum efficiency (EQE) of 24.91 % with an extremely low roll-off (1.6 %) at 1000 cd m-2. High-performance non-doped top-emitting and tandem OLEDs are also achieved, providing remarkable EQEs of 24.53 % and 42.50 %, respectively. Delightfully, non-doped simplified OLEDs employing thick neat films of 3,2-PIC-XT are also realized, furnishing an excellent EQE of 17.79 % and greatly enhanced operational lifetime. The temperature-dependent and transient EL spectroscopies demonstrate the electrophosphorescence attribute of 3,2-PIC-XT. These non-doped OLEDs are the best devices based on purely organic RTP materials reported so far.

An Electroactive Pure Organic Room-Temperature Phosphorescence Polymer Based on a Donor-Oxygen-Acceptor Geometry.

An electroactive room-temperature phosphorescence (RTP) polymer has been demonstrated based on a characteristic donor-oxygen-acceptor geometry. Compared with the donor-acceptor reference, the inserted oxygen atom between donor and acceptor can not only decrease hole-electron orbital overlap to suppress the charge transfer fluorescence, but also strengthen spin-orbital coupling effect to facilitate the intersystem crossing and subsequent phosphorescence channels. As a result, a significant RTP is observed in solid states under photo excitation. Most noticeably, the corresponding polymer light-emitting diodes (PLEDs) reveal a dominant electrophosphorescence with a record-high external quantum efficiency of 9.7 %. The performance goes well beyond the 5 % theoretical limit for typical fluors, opening a new door to the development of pure organic RTP polymers towards efficient PLEDs.

Adamantane-based wide-bandgap host material: blue electrophosphorescence with high efficiency and very high brightness.

An adamantane-based host material, namely, 4-{3-[4-(9H-carbazol-9-yl)phenyl]adamantan-1-yl}benzonitrile (CzCN-Ad), was prepared by linking an electron-donating carbazole unit and an electron-accepting benzonitrile moiety through an adamantane bridge. In this approach, two functional groups were attached to tetrahedral points of adamantane to construct an "sp(3)" topological configuration. This design strategy endows the host material with a high triplet energy of 3.03 eV due to the disruption of intramolecular charge transfer. Although CzCN-Ad has a low molecular weight, the rigid nonconjugated adamantane bridge results in a glass transition temperature of 89 °C. These features make CzCN-Ad suitable for fabricating blue phosphorescent organic light-emitting diodes (PhOLEDs). The devices based on sky-blue phosphor bis[(4,6-difluorophenyl)pyridinato-N,C(2')](picolinato)iridium(III) (FIrpic) achieved a high maximum external quantum efficiency (EQE) of 24.1%, which is among the best results for blue PhOLEDs ever reported. Furthermore, blue PhOLEDs with bis(2,4-difluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(III) (FIr6) as dopant exhibited a maximum EQE of 14.2% and a maximum luminance of 34 262 cd m(-2). To the best of our knowledge, this is the highest luminance ever reported for FIr6-based PhOLEDs.

Triplet energies and excimer formation in meta- and para-linked carbazolebiphenyl matrix materials.

We present a spectroscopic investigation on the effect of changing the position where carbazole is attached to biphenyl in carbazolebiphenyl (CBP) on the triplet state energies and the propensity to excimer formation. For this, two CBP derivatives have been prepared with the carbazole moieties attached at the (para) 4- and 4(')-positions (pCBP) and at the (meta) 3- and 3(')-positions (mCBP) of the biphenyls. These compounds are compared to analogous mCDBP and pCDBP, i.e. two highly twisted carbazoledimethylbiphenyls, which have a high triplet energy at about 3.0 eV and tend to form triplet excimers in a neat film. This torsion in the structure is associated with localization of the excited state onto the carbazole moieties. We find that in mCBP and pCBP, excimer formation is prevented by localization of the triplet excited state onto the central moiety. As conjugation can continue from the central biphenyls into the nitrogen of the carbazole in the para-connected pCBP, emission involves mainly the benzidine. By contrast, the meta-linkage in mCBP limits conjugation to the central biphenyl. The associated shorter conjugation length is the reason for the higher triplet energy of 2.8 eV in mCBP compared with the 2.65 eV in pCBP.

Rationally investigating the influence of T1 location on electroluminescence performance of aryl amine modified phosphine oxide materials.

The correspondence between triplet location effect and host-localized triplet-triplet annihilation and triplet-polaron quenching effects was performed on the basis of a series of naphthyldiphenylamine (DPNA)-modified phosphine oxide hosts. The number and ratio of DPNA and diphenylphosphine oxide was adjusted to afford symmetrical and unsymmetrical molecular structures and different electronic environments. As designed, the first triplet (T1 ) states were successfully localized on the specific DPNA chromophores. Owing to the meso- and multi-insulating linkages, identical optical properties and comparable electrical performance was observed, including the same first singlet (S1 ) and T1 energy levels to support the similar singlet and triplet energy transfer and the close frontier molecular orbital energy levels. This established the basis of rational investigation on T1 location effect without interference from other optoelectronic factors.

Solution-processible brilliantly luminescent Eu(III) complexes with host-featured phosphine oxide ligands for monochromic red-light-emitting diodes.

A series of solution-processible electroluminescent (EL) Eu(3+) complexes were constructed with a self-host strategy, in which neutral ligands were employed as functionalized bidentate phosphine oxide (PO) ligands named DPEPOArn (DPEPO = bis(2-(diphenylphosphino)phenyl) ether oxide). The solubility of these complexes was dramatically improved owing to the increased ratios of organic components. This further enhanced the antenna effect of these ligands in both singlet and triplet energy-transfer processes to support high photoluminescent quantum yields (PLQYs) up to 86 % for their Eu(3+) complexes, which is outstanding among conjugated Eu(3+) complexes. Density function theory (DFT) simulations and electrochemical analysis further verified the contributions of DPEPOArn to the carrier injecting/transporting ability of the complexes. In this sense, these functionalized PO ligands served as hosts in optoelectronic processes, which rendered the self-host feature of their Eu(3+) complexes. With the enhanced electrical properties, the spin-coated single-layer organic light-emitting diodes (OLEDs) of these complexes achieved improved low driving voltages, such as onset voltages about 6 V, compared to their Eu(3+)-contained red-emitting polymeric analogues. [Eu(DBM)3DPEPODPNA2] (DBM = 1,3-diphenylpropane-1,3-dione, DPNA = diphenylnaphthylamine) with the most enhanced electrical properties and suitable frontier molecular orbital (FMO) and triplet state locations endowed its devices with the biggest maximum luminance of >90 cd m(-2) and the highest EL efficiencies. This work verified the potential of small molecular EL Eu(3+) complexes for solution-processed OLEDs through rational function integrations.

Molecular topology tuning of bipolar host materials composed of fluorene-bridged benzimidazole and carbazole for highly efficient electrophosphorescence.

Two new molecules, CzFCBI and CzFNBI, have been tailor-made to serve as bipolar host materials to realize high-efficiency electrophosphorescent devices. The molecular design is configured with carbazole as the hole-transporting block and N-phenylbenzimidazole as the electron-transporting block hybridized through the saturated bridge center (C9) and meta-conjugation site (C3) of fluorene, respectively. With structural topology tuning of the connecting manner between N-phenylbenzimidazole and the fluorene core, the resulting physical properties can be subtly modulated. Bipolar host CzFCBI with a C connectivity between phenylbenzimidazole and the fluorene bridge exhibited extended π conjugation; therefore, a low triplet energy of 2.52 eV was observed, which is insufficient to confine blue phosphorescence. However, the monochromatic devices indicate that the matched energy-level alignment allows CzFCBI to outperform its N-connected counterpart CzFNBI while employing other long-wavelength-emitting phosphorescent guests. In contrast, the high triplet energy (2.72 eV) of CzFNBI imparted by the N connectivity ensures its utilization as a universal bipolar host for blue-to-red phosphors. With a common device configuration, CzFNBI has been utilized to achieve highly efficient and low-roll-off devices with external quantum efficiency as high as 14 % blue, 17.8 % green, 16.6 % yellowish-green, 19.5 % yellow, and 18.6 % red. In addition, by combining yellowish-green with a sky-blue emitter and a red emitter, a CzFNBI-hosted single-emitting-layer all-phosphor three-color-based white electrophosphorescent device was successfully achieved with high efficiencies (18.4 %, 36.3 cd A(-1) , 28.3 lm W(-1) ) and highly stable chromaticity (CIE x=0.43-0.46 and CIE y=0.43) at an applied voltage of 8 to 12 V, and a high color-rendering index of 91.6.

Modulating the optoelectronic properties of large, conjugated, high-energy gap, quaternary phosphine oxide hosts: impact of the triplet-excited-state location.

The purposeful modulation of the optoelectronic properties was realised on the basis of a series of the large, conjugated, phosphine oxide hosts 9,9-bis-{4'-[2-(diphenylphosphinoyl)phenoxy]biphenyl-4-yl}-9H-fluorene (DDPESPOF), 9,9-bis-{3'-(diphenylphosphinoyl)-4'-[2-(diphenylphosphinoyl)phenoxy]biphenyl-4-yl}-9H-fluorene (DDPEPOF), 9-[4'-(9-{4'-[2-(diphenylphosphoryl)phenoxy]biphenyl-4-yl}-9H-fluoren-9-yl)biphenyl-4-yl]-9H-carbazole (DPESPOFPhCz) and 9-[4'-(9-{3'-(diphenylphosphoryl)-4'-[2-(diphenylphosphoryl)phenoxy]biphenyl-4-yl}-9H-fluoren-9-yl)biphenyl-4-yl]-9H-carbazole (DPEPOFPhCz). The last two are quaternary with fluorenyls as linking bridges, diphenylphosphine oxide (DPPO) moieties as electron acceptors and diphenylethers and carbazolyls as two different kinds of electron donors. Owing to the fine-organised molecular structures and the mixed indirect and multi-insulating linkages, all of these hosts achieve the same first triplet energy levels (T1) of 2.86 eV for exothermic energy transfer to phosphorescent dopants. The first singlet energy levels (S1) and the carrier injection/transportation ability of the hosts were accurately modulated, so that DPESPOFPhCz and DPEPOFPhCz revealed extremely similar optoelectronic properties. However, the T1 state of the former is localised on fluorenyl, whereas the carbazolyl mainly contributes to the T1 state of the latter. A lower driving voltages and much higher efficiencies of the devices based on DPESPOFPhCz indicated that the chromophore-localised T1 state can suppress the quenching effects through realising independent contributions from the different functional groups to the optoelectronic properties and the embedding and protecting effect on the T1 states by peripheral carrier transporting groups.

Silicon-based material with spiro-annulated fluorene/triphenylamine as host and exciton-blocking layer for blue electrophosphorescent devices.

A novel silicon-based compound, 10-phenyl-2'-(triphenylsilyl)-10H-spiro[acridine-9,9'-fluorene] (SSTF), with spiro structure has been designed, synthesized, and characterized. Its thermal, electronic absorption, and photoluminescence properties were studied. Its energy levels make it suitable as a host material or exciton-blocking material in blue phosphorescent organic light-emitting diodes (PhOLEDs). Accordingly, blue-emitting devices with iridium(III) bis[(4,6-difluorophenyl)-pyridinato-N,C(2)']picolinate (FIrpic) as phosphorescent dopant have been fabricated and show high efficiency with low roll-off. In particular, 44.0 cd A(-1) (41.3 lm W(-1)) at 100 cd m(-2) and 41.9 cd A(-1) (32.9 lm W(-1)) at 1000 cd m(-2) were achieved when SSTF was used as host material; 28.1 lm W(-1) at 100 cd m(-2) and 20.6 lm W(-1) at 1000 cd m(-2) were achieved when SSTF was used as exciton-blocking layer. All of the results are superior to those of the reference devices and show the potential applicability and versatility of SSTF in blue PhOLEDs.

Control of Host-Matrix Morphology Enables Efficient Deep-Blue Organic Light-Emitting Devices.

Mixing a sterically bulky, electron-transporting host material into a conventional single host-guest emissive layer is demonstrated to suppress phase separation of the host matrix while increasing the efficiency and operational lifetime of deep-blue phosphorescent organic light-emitting diodes (PHOLEDs) with chromaticity coordinates of (0.14, 0.15). The bulky host enables homogenous mixing of the molecules comprising the emissive layer while suppressing single host aggregation; a significant loss channel of nonradiative recombination. By controlling the amorphous phase of the host-matrix morphology, the mixed-host device achieves a significant reduction in nonradiative exciton decay, resulting in 120 ± 6% increase in external quantum efficiency relative to an analogous, single-host device. In contrast to single host PHOLEDs where electrons are transported by the host and holes by the dopants, both charge carriers are conducted by the mixed host, reducing the probability of exciton annihilation, thereby doubling of the deep-blue PHOLED operational lifetime. These findings demonstrate that the host matrix morphology affects almost every aspect of PHOLED performance.

Solution-processable carbazole-based conjugated dendritic hosts for power-efficient blue-electrophosphorescent devices.

A novel class of hosts suitable for solution processing has been developed based on a conjugated dendritic scaffold. By increasing the dendron generation, the highest occupied molecular orbital (HOMO) energy level can be tuned to facilitate hole injection, while the triplet energy remains at a high level, sufficient to host high-energy-triplet emitters. A power-efficient blue-electrophosphorescent device based on H2 is presented.

In Search of Deeper Blues: Trans-N-Heterocyclic Carbene Platinum Phenylacetylide as a Dopant for Phosphorescent OLEDs.

A trans-N-heterocyclic carbene (NHC) platinum(II) acetylide complex bearing phenyl acetylene ligands (NPtPE1) has been synthesized via the Hagihara reaction in 64% yield. The complex features spectrally narrow deep blue emission with a phosphorescence quantum yield (0.30) and lifetime (∼10 µs) in the solid state. The modest quantum yield and lifetime make NPtPE1 a candidate for incorporation into an organic light emitting diode (OLED). Prototype devices exhibited a maximum EQE of 8% with CIE (0.20,0.20). To the best of our knowledge, this is the first example of a platinum(II) acetylide bearing NHC ligands to be incorporated into an OLED.

Novel Emitting System Based on a Multifunctional Bipolar Phosphor: An Effective Approach for Highly Efficient Warm-White Light-Emitting Devices with High Color-Rendering Index at High Luminance.

A three-color warm-white organic light-emitting diode employing an efficient phosphor-phosphor type host-guest emitting system achieves efficiencies of 27.3% for external quantum efficiency and 74.5 lm W(-1) for power efficiency at a luminance of 1000 cd m(-2) , which maintained the high levels of 24.3% and 45.8 lm W(-1) at 10 000 cd m(-2) , with a stable color-rendering index of 86-87.

Highly efficient multifluorenyl host materials with unsymmetrical molecular configurations and localized triplet States for green and red phosphorescent devices.

Highly efficient green and red electro-phosphorescence is achieved in devices with the host material DPESPODEF3. The multiple fluorenyl moieties of the host material are arranged such that it has an unsymmetrical molecular configuration, and its triplet-state location is tuned such that it has independent energy (ET) and charge transfer (CT) channels. As a result, DPESPODEF3 can suppress triplet-triplet annihilation and triplet-polaron quenching. In the resulting green and red phosphorescent devices, impressive external quantum efficiencies of ca. 20% and 16% and power efficiencies of ca. 75 and 20 lm W(-1) , respectively, are observed.