Benzobisoxazole cruciforms: a tunable, cross-conjugated platform for the generation of deep blue OLED materials

Four new cross-conjugated small molecules based on a central benzo[1,2-d:4,5-d′]bisoxazole moiety possessing semi-independently tunable HOMO and LUMO levels were synthesized and the properties of these materials were evaluated experimentally and theoretically. The molecules were thermally stable with 5% weight loss occurring well above 350 °C. The cruciforms all exhibited blue emission in solution ranging from 433–450 nm. Host–guest OLEDs fabricated from various concentrations of these materials using the small molecule host 4,4′-bis(9-carbazolyl)-biphenyl (CBP) exhibited deep blue-emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.15 ≤ x ≤ 0.17, 0.05 ≤ y ≤ 0.11), and maximum luminance efficiencies as high as ∼2 cd A−1. These results demonstrate the potential of benzobisoxazole cruciforms as emitters for developing high-performance deep blue OLEDs.We would like to thank Dr Sarah Cady, Dr Kamel Harrata and Mr Steven Veysey of Iowa State University (ISU) Chemical Instrumentation Facility for compound analysis. We thank Eeshita Manna for technical assistance. We also thank the National Science Foundation (CHE-1413173) for financial support of this work. RK and JS were partially supported by Basic Energy Sciences, Division of Materials Science and Engineering, USDOE. Ames Laboratory is operated by Iowa State University for the US Department of Energy (USDOE) under Contract No. DE-AC 02-07CH11358. Computational resources were provided in part by the MERCURY consortium (http://mercuryconsortium.org/) under NSF grants CHE-0116435, CHE-0521063, CHE-0849677, and CHE-1229354. (CHE-1413173 - National Science Foundation; Basic Energy Sciences, Division of Materials Science and Engineering, USDOE; DE-AC 02-07CH11358 - Iowa State University for the US Department of Energy (USDOE); CHE-0116435 - MERCURY consortium under NSF; CHE-0521063 - MERCURY consortium under NSF; CHE-0849677 - MERCURY consortium under NSF; CHE-1229354 - MERCURY consortium under NSF)http://pubs.rsc.org/en/Content/ArticleLanding/2016/TC/C5TC03622D#!divAbstractPublished versio

Low efficiency roll-off phosphorescent organic light-emitting devices using thermally activated delayed fluorescence hosts materials based 1, 2, 4-triazole acceptor

The host in phosphrescent organic light emitting devices (PhOLEDs), showing the thermally activated delayed fluorescence (TADF) charateristic, can effectively overcome the efficiency roll-off. Herein, six bipolar compounds with donor-π-acceptor (D-π-A) and D-π-A-π-D structures have been synthesized using 1,2,4-triazole derivative (TAZ) as an acceptor and phenothiazine (PTZ), phenoxazine (PXZ), and 9, 9-dimethylacridane (DMAC) as donors. The molecular structures were confirmed by 1H NMR, 13C NMR and X-ray single-crystal diffractions. The large steric hindrance endows these molecules with typical TADF features, including the small singlet-triplet energy splitting (Delta E-ST) of 0.08–0.30 eV and completely spatially separate highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO) electron densities. The PhOLEDs hosted by these novel TADF materials display excellent performances with low efficiency roll-off

Soft lithography microlens fabrication and array for enhanced light extraction from organic light emitting diodes (OLEDs)

Provided are microlens arrays for use on the substrate of OLEDs to extract more light that is trapped in waveguided modes inside the devices and methods of manufacturing same. Light extraction with microlens arrays is not limited to the light emitting area, but is also efficient in extracting light from the whole microlens patterned area where waveguiding occurs. Large microlens array, compared to the size of the light emitting area, extract more light and result in over 100% enhancement. Such a microlens array is not limited to (O)LEDs of specific emission, configuration, pixel size, or pixel shape. It is suitable for all colors, including white, for microcavity OLEDs, and OLEDs fabricated directly on the (modified) microlens array

Red-green-blue Emission From Tris(5-aryl-8-quinolinolate)al(iii) Complexes

A simple yet effective strategy for synthesis of 5-aryl-8-quinolinolate-based electroluminophores with tunable emission wavelengths is presented. Two different pathways for the attachment of electron-donating or electron-withdrawing aryl groups to the 5-position of the quinolinolate ligand via Suzuki coupling were developed. A successful tuning in the emission color was achieved: the emission wavelength was found to correlate with the Hammett constant of the respective substituents, providing a powerful strategy for prediction of the optical properties of new electroluminophores

Soft holographic interference lithography microlens for enhanced organic light emitting diode light extraction

Very uniform 2 μm-pitch square microlens arrays (μLAs), embossed on the blank glass side of an indium-tin-oxide (ITO)-coated 1.1 mm-thick glass, are used to enhance light extraction from organic light-emitting diodes (OLEDs) by ~100%, significantly higher than enhancements reported previously. The array design and size relative to the OLED pixel size appear to be responsible for this enhancement. The arrays are fabricated by very economical soft lithography imprinting of a polydimethylsiloxane (PDMS) mold (itself obtained from a Ni master stamp that is generated from holographic interference lithography of a photoresist) on a UV-curable polyurethane drop placed on the glass. Green and blue OLEDs are then fabricated on the ITO to complete the device. When the μLA is ~15 × 15 mm2, i.e., much larger than the ~3 × 3 mm2 OLED pixel, the electroluminescence (EL) in the forward direction is enhanced by ~100%. Similarly, a 19 × 25 mm2μLA enhances the EL extracted from a 3 × 3 array of 2 × 2 mm2 OLED pixels by 96%. Simulations that include the effects of absorption in the organic and ITO layers are in accordance with the experimental results and indicate that a thinner 0.7 mm thick glass would yield a ~140% enhancement

Comparative analysis of magnetic resonance in the polaron pair recombination and the triplet exciton-polaron quenching models

We present a comparative theoretical study of magnetic resonance within the polaron pair recombination (PPR) and the triplet exciton-polaron quenching (TPQ) models. Both models have been invoked to interpret the photoluminescence detected magnetic resonance (PLDMR) results in π -conjugated materials and devices. We show that resonance line shapes calculated within the two models differ dramatically in several regards. First, in the PPR model, the line shape exhibits unusual behavior upon increasing the microwave power: it evolves from fully positive at weak power to fully negative at strong power. In contrast, in the TPQ model, the PLDMR is completely positive, showing a monotonic saturation. Second, the two models predict different dependencies of the resonance signal on the photoexcitation power, P L . At low P L , the resonance amplitude Δ I / I is ∝ P L within the PPR model, while it is ∝ P 2 L crossing over to P 3 L within the TPQ model. On the physical level, the differences stem from different underlying spin dynamics. Most prominently, a negative resonance within the PPR model has its origin in the microwave-induced spin-Dicke effect, leading to the resonant quenching of photoluminescence. The spin-Dicke effect results from the spin-selective recombination, leading to a highly correlated precession of the on-resonance pair partners under the strong microwave power. This effect is not relevant for TPQ mechanism, where the strong zero-field splitting renders the majority of triplets off resonance. On the technical level, the analytical evaluation of the line shapes for the two models is enabled by the fact that these shapes can be expressed via the eigenvalues of a complex Hamiltonian. This bypasses the necessity of solving the much larger complex linear system of the stochastic Liouville equations. Our findings pave the way towards a reliable discrimination between the two mechanisms via cw PLDMR

Enhanced Light Extraction from OLEDs Fabricated on Patterned Plastic Substrates

A key scientific and technological challenge in organic light-emitting diodes (OLEDs) is enhancing the light outcoupling factor ηout, which is typically \u3c20%. This paper reports experimental and modeling results of a promising approach to strongly increase ηout by fabricating OLEDs on novel flexible nanopatterned substrates that result in a \u3e2× enhancement in green phosphorescent OLEDs (PhOLEDs) fabricated on corrugated polycarbonate (PC). The external quantum efficiency (EQE) reaches 50% (meaning ηout ≥50%); it increases 2.6x relative to a glass/ITO device and 2× relative to devices on glass/poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) or flat PC/PEDOT:PSS. A significant enhancement is also observed for blue PhOLEDs with EQE 1.7× relative to flat PC. The corrugated PC substrates are fabricated efficiently and cost-effectively by direct room-temperature molding. These substrates successfully reduce photon losses due to trapping/waveguiding in the organic+anode layers and possibly substrate, and losses to plasmons at the metal cathode. Focused ion beam gauged the conformality of the OLEDs. Dome-shaped convex nanopatterns with height of ∼280–400 nm and pitch ∼750–800 nm were found to be optimal. Substrate design and layer thickness simulations, reported first for patterned devices, agree with the experimental results that present a promising method to mitigate photon loss paths in OLEDs

Molecular-wire Behavior Of Oled Materials: Exciton Dynamics In Multichromophoric Alq(3)-oligofluorene-pt(ii) Porphyrin Triads

Donor-bridge-acceptor triads consisting of the Alq3 complex, oligofluorene bridge, and PtII tetraphenylporphyrin (PtTPP) were synthesized. The triads were designed to study the energy level/distance-dependence in energy transfer both in a solution and in solid state. The materials show effective singlet transfer from the Alq3-fluorene fluorophore to the porphyrin, while the triplet energy transfer, owing to the shorter delocalization of triplet excitons, appears to take place via a triplet energy cascade. Using femtosecond transient spectroscopy, the rate of the singlet−singlet energy transfer was determined. The exponential dependence of the donor−acceptor distance and the respective energy transfer rates of 7.1 × 1010 to 1.0 × 109 s-1 with the attenuation factor â of 0.21 ± 0.02 Å-1 suggest that the energy transfer proceeds via a mixed incohererent wire/superexchange mechanism. In the OLEDs fabricated using the Alq3-oligofluorene-PtTPP triads with better triplet level alignment, the order of a magnitude increase in efficacy appears to be due to facile triplet energy transfer. The devices, where the triplet−triplet energy transfer is of paramount importance, showed high color purity emission (CIE X,Y:  0.706, 0.277), which is almost identical to the emission from thin films. Most importantly, we believe that the design principles demonstrated above are general and may be used to prepare OLED materials with enhanced quantum efficacy at lowered operational potentials, being crucial for improved lifespan of OLEDs

Bright Deep Blue TADF OLEDs: The Role of Triphenylphosphine Oxide in NPB/TPBi:PPh3O Exciplex Emission

Very bright (≈14 000 cd m−2) deep blue exciplex organic light emitting diodes (OLEDs) peaking at ≈435 nm, where the photopic response is ≈0.033, and with CIE color coordinates (0.1525, 0.0820), are described. The OLED properties are interestingly linked to PPh3O (triphenylphosphine oxide) and attributes of the emitting layer (EML) comprising NPB interfacing host:guest TPBi:PPh3O 5:1 weight ratio. A neat PPh3O layer that is central for device performance follows the EML (NPB/TPBi:PPh3O 5:1/PPh3O). The bright electroluminescence originates from NPB/TPBi:PPh3O exciplexes involving triplets via thermally activated delayed fluorescence, as evident from the strong quenching of the photoluminescence (PL) by oxygen and interestingly, the monomolecular emission process. The transient PL decay times of a NPB/TPBi:PPh3O 5:1/PPh3O film are 43 ns in air versus 136, 610, and weak ≈2000 ns in N2. For comparison, the respective PL decay times of films of NPB:TPBi are 16 ns in air versus 131 and 600 ns in N2, and of NPB:PPh3O they are 29 ns in air versus 56, 483, and weak ≈2000 ns in N2. It is suspected that slow emitting states are associated with a PPh3O aggregate interacting with NPB