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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Back in bismuth: controlling triplet energy transfer, phosphorescence, and radioluminescence via supramolecular interactions

Five bismuth(III)-organic phases that consist of supramolecular assemblies of Bi-2,6-pyridinedicarboxylate structural units and substituted 1,10-phenanthroline molecules (R-Phen; R = H, 5-methyl, 5-chloro, 2,9-dimethyl, and 2,9-dicholoro) were synthesized. All five compounds exhibited solid-state photoluminescence. Whereas the phases containing 2,9-dimethylphenanthroline (Me 2 Phen) and 2,9-dichlorophenanthroline (Cl 2 Phen) displayed solely phosphorescence, the structures built from 5-methylphenanthroline and 5-chlorophenanthroline showed exclusively fluorescence. The remaining phase, consisting of phenanthrolinium, exhibited both fluorescence and phosphoresence. It was determined that phosphorescence arises from triplet state emission (T 1 → S 0 ) of substituted R-Phen units while fluorescence originates from Bi(III) coordinated pyrdinedicarboxylate ligands. Bismuth induces spin–orbit coupling for triplet state population and additionally acts as a heavy metal attenuator for X-ray luminescence (radioluminescence). The electronic structure was mapped and excitation pathway investigated via density functional theory calculations. Computational findings indicate favorable conditions for triplet energy transfer from donor Bi(III)-organic units to acceptor R-Phen derivatives. It is proposed that for the phosphorescent compounds, strong π–π interactions promote electron transfer, whereas the compounds that exhibit purely fluorescence lack any such π–π interactions and undergo triplet energy transfer. In conclusion, these results provide a useful platform for probing structure–property relationships of luminescent bismuth-organic compounds, and specifically highlights the role of noncovalent interactions in achieving room temperature phosphorescence and radioluminescence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Fluorescent, phosphorescent, magnetic resonance contrast and radioactive tracer labelling of extracellular vesicles

This review focusses on the significance of fluorescent, phosphorescent labelling and tracking of extracellular vesicles (EVs) for unravelling their biology, pathophysiology, and potential diagnostic and therapeutic uses. Various labeling strategies, such as lipid membrane, surface protein, luminal, nucleic acid, radionuclide, quantum dot labels, and metal complex-based stains, are evaluated for visualizing and characterizing EVs. Direct labelling with fluorescent lipophilic dyes is simple but generally lacks specificity, while surface protein labelling offers selectivity but may affect EV-cell interactions. Luminal and nucleic acid labelling strategies have their own advantages and challenges. Here, each labelling approach has strengths and weaknesses, which require a suitable probe and technique based on research goals, but new tetranuclear polypyridylruthenium(II) complexes as phosphorescent probes have strong phosphorescence, selective staining, and stability. Future research should prioritize the design of novel fluorescent probes and labelling platforms that can significantly enhance the efficiency, accuracy, and specificity of EV labeling, while preserving their composition and functionality. It is crucial to reduce false positive signals and explore the potential of multimodal imaging techniques to gain comprehensive insights into EVs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Color‐Stable, All‐Phosphorescent White Organic Light Emitting Diodes Using the Polariton‐Enhanced Purcell Effect

Abstract The short operational lifetimes of high efficiency phosphorescent organic blue light emitting devices (PHOLEDs) has limited their use in displays and lighting. Previously, this problem has been avoided by using less efficient fluorescent blue devices in separately biased red, green, and blue emissive elements to achieve stable full color emission. However, the operational lifetime of blue phosphorescent OLEDs has been significantly improved through the utilization of the plasmon‐exciton‐polariton‐enhanced (PEP) Purcell effect. Here, a white emitting PHOLED comprising stacked red, green, and blue elements is demonstrated that exploits PEPs to extend the operational lifetime of the blue element such that all emissive layers degrade at the same rate. The device features white light emission with an external quantum efficiency of 19.1 ± 0.4%, luminous power efficiency of 13.3 ± 0.3 lm W −1 at a luminance of 1000 cd m −2 when measured over 4π solid angle, with a color rendering index of 76 unchanged throughout the device aging to 70% of its initial luminance, T 70 . A 2.9 times enhancement in the operational lifetime of the Purcell‐enhanced device is achieved to yield T 70 = 2900 ± 100 h for an initial luminance of 1000 cd m −2 , compared to devices lacking this enhancement with T 70 = 1000 ± 100 h.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Modeling the Charge and Exciton Distributions in Phosphorescent White Organic Light-Emitting Diodes

A comprehensive numerical model is developed to quantitatively analyze the charge and exciton distributions in phosphorescent white organic light emitting diodes (WOLEDs). The model encompasses bipolar charge drift-diffusion transport with doping-dependent charge mobilities, field-dependent charge hopping across multiple interfaces, exciton generation, diffusion, energy transfer, radiative decay, and non-radiative exciton annihilation. The model is validated by direct measurement of the exciton distribution in monochromatic phosphorescent OLEDs. It is then applied to complex, multilayer WOLEDs where it is used to accurately predict their intensity and current-dependent spectral shifts. The magnitudes of different exciton loss channels in WOLEDs are calculated and quantitatively compared. This model provides an alternative for the many experimental iterations commonly used to optimize the color balance of complex OLEDs. In this context, the model inspired the addition of a hole blocking layer in the WOLED to balance the charge conduction and reduce spectral shifts – a design that is verified by experiment.

42 ENGINEERING↗
DOE OSTI2024

Effect of molecular permanent dipole moment on guest aggregation and exciton quenching in phosphorescent organic light emitting diodes

This study explores the effect of molecular permanent dipole moment (PDM) on aggregation of guest molecules in phosphorescent host–guest organic light-emitting diodes (OLEDs). Through a combination of photoluminescence measurements, high-angle annular dark-field scanning transmission electron microscopy analysis, and an Ising model based physical vapor-deposition simulation, we show that higher PDM of tris[2-phenylpyridinato-C2,N]iridium(III) guest can actually lead to a reduced aggregation relative to tris[bis[2-(2-pyridinyl-N)phenyl-C] (acetylacetonato)iridium(III) when doped into a non-polar host 1,3,5-tris(carbazol-9-yl)benzene. This study further explores the effect of host polarity by using a polar host 3′,5′-di(carbazol-9-yl)-[1,1′-biphenyl]-3,5-dicarbonitrile, and it is shown that the polar host leads to reduced guest aggregation. In conclusion, this study provides a comprehensive understanding of the impact of molecular PDM on OLED material efficiency and stability, providing insights for optimizing phosphorescent OLED materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Organic light-emitting diodes with fluorescent and phosphorescent emitters

A light emitting device includes a first electrode, a hole transporting layer in contact with the first electrode, a second electrode, an electron transporting layer in contact with the second electrode; and an emissive layer between the hole transporting layer and the electron transporting layer. The emissive layer includes a phosphorescent emitter, a fluorescent emitter, and a host, and the phosphorescent emitter harvests electrogenerated excitons and transfers energy to the fluorescent emitter.

Li, Jian↗
DOE OSTI2023

Efficient, Color-Stable, and Long-Lived White Organic Light-Emitting Diodes Utilizing Phosphorescent Molecular Aggregates

Highly efficient and stable single-stack hybrid white organic light-emitting diode (WOLED) devices are developed using two emissive layers: one with amber-colored phosphorescent molecular-aggregate emission from the Pd(II) complex, Pd(II) 7-(3-(pyridine-2-yl-κN)phenoxy-κC)(benzo-κC)([c]benzo[4,5]imidazo-κN)[1,2-a][1,5]naphthyridine, Pd3O8-Py5, and the other with blue fluorescence emission. Here, an optimized device structure achieves high color stability under various current densities, an external quantum efficiency (EQE) of 45.5%, a power efficiency of 97.4 Lm W -1 , and an estimated LT 95 (operational time to 95% of the initial luminance) of 50 744 h at an initial luminance of 1000 cd m -2 .

36 MATERIALS SCIENCE↗
DOE OSTI2023

Solid-State Lighting Using Side-by-Side White Phosphorescent Organic Light-Emitting Diodes

White organic light-emitting diodes (WOLEDs) have become increasingly popular for use in solid-state illumination, where diffuse, large area light sources that achieve a high color rendering index and luminous power efficiency are desirable. Color-tunable emission, where the light source combines emission from multiple, separately addressed color elements, is conveniently provided by WOLEDs for the purpose of adapting the lighting source to a particular illumination requirement. In this work, we demonstrate a method for side-by-side positioning of monochromatic blue and yellow phosphorescent OLED stripes that are combined to create tunable white light, using a high resolution mechanical peel-off patterning method. We achieve a peak luminous power efficiency of 17.1 ± 0.3 lm W –1 and an external quantum efficiency of 11.8 ± 0.2% and demonstrate color tunability of the 1960 Commission Internationale d’Eclairage chromaticity coordinates from (u,v) = (0.33,0.36) to (0.12,0.32). This corresponds to a tuning rnge of the color rendering index from 74 ± 1 to 86 ± 1 and the correlated color temperature from 2000 to 8000 ± 500 K. Here, due to the nondestructive nature of the peel-off technique, patterned devices exhibit a lifetime comparable to conventional, shadow mask-patterned devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

An intermediate model for fitting triplet–triplet annihilation in phosphorescent organic light emitting diode materials

Triplet–triplet annihilation (TTA) is one of the primary contributors to efficiency roll-off and permanent material degradation in phosphorescent organic light-emitting diodes. Here, the two limiting case models typically used to quantify this quenching mechanism are multi-step Dexter and single-step Förster, which, respectively, assume ideal Fickian diffusion or perfect trapping of triplet excitons. For device-relevant guest doping levels (typically 5–12 vol. %), both significant diffusion of excitons and trapping due to spatial and energetic disorder exist, so neither conventional model fits experimental data well. We develop and validate an intermediate TTA model, which is a weighted average of the limiting cases of pure radiative decay (no TTA) and multi-step Dexter based TTA that returns an effective TTA rate constant and a parameter quantifying the portion of well-isolated excitons. Kinetic Monte-Carlo simulations and time-resolved photoluminescence measurements of an archetype host–guest system demonstrate that our intermediate model provides significantly improved fits with more realistic physical values, is more robust to variations in experimental conditions, and provides an analysis framework for the effects of trapping on TTA.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Photostability of blue phosphorescent films on plasmonic surfaces

Organometallic phosphors are an important class of emissive materials used in high-efficiency organic light-emitting devices. However, problems of low photostability arise for blue-emitting phosphors due to chemical and environmental degradation and triplet quenching processes. Various approaches have been developed to improve the photostability of such phosphors, including the design of new organometallic molecules and control of host-dopant composition in thin films. Here, we demonstrate a different approach for improving the photostability of blue organometallic phosphors that uses localized surface plasmon resonances to increase the triplet recombination rate. The increased recombination rate improves the photostability of the phosphor due to the reduction in triplet quenching pathways. We show that the lifetime of phosphorescence is decreased significantly by nanoparticle-based plasmonic surfaces, which improves the photostability of the blue organometallic phosphor by up to a factor of 3.6. Other plasmonic surfaces are also tested and exhibit less significant photostability improvements due to a reduced spectral overlap of the plasmonic modes with the emitter and lower mode confinement. The use of plasmonic surfaces to improve phosphor photostability at blue wavelengths is distinct from other approaches because it involves modification to the local electromagnetic environment of the phosphor rather than modifications to the phosphor molecular structure or the emitting material composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Improved Light Extraction by Engineering Molecular Properties of Square Planar Phosphorescent Emissive Materials

The ultimate objective of this project was to develop a cost-effective technology which could significantly improve the light outcoupling efficiency up to 70% and higher and the key tasks were listed as follows: (i) improving light extraction efficiency through a better control of horizontally aligned emitting dipoles of square planar phosphorescent emitters; (ii) fabricating high-efficiency monochromic and amber OLED in the device settings; (iii) fabricating high-efficiency white OLED in the device settings. With both materials innovation and device structure optimization, we realized OLEDs with an EQE of 66% with a LT 95 lifetime of over 100 khrs at a brightness of 1,000 cd/m 2 . This proposed research is a high impact project which could potentially revolutionize OLED lighting technology and expedite the commercialization process of OLED technology for solid state lighting. This project outcomes contributed to meet the targeted performance of organic solid state lighting set in the DOE MYPP.

36 MATERIALS SCIENCE↗
DOE OSTI2022

N-heterocyclic carbene platinum-butadiyne Click/iClick complexes. Towards blue-violet phosphorescence

By employing two different methods, namely, Click and iClick, a series of four trans-NHC-Pt(II) triazole-acetylide complexes containing benzyl (3a), methylnaphthalene (3b), methylanthracene (3c), and phenyl (3d) substituents at the terminal triazole ring were synthesized and characterized. The traditional click approach involves first synthesizing a triazole-acetylene and then attaching to the Pt ion. In the iClick approach, the triazole is formed via cycloaddition by combining a trans-platinum butadiyne with the corresponding organic azide. The complexes were interrogated to determine the effects of conjugation and ligand substituent on their photophysical properties. Complex 3a exhibits a photoluminescence lifetime of 4.3 μs at 77 K. Ascribed to emission from conformers differing due to the torsion of the aryl acetylide ligands, employing different excitation wavelengths results in different emission spectra. Complex 3a emits in the violet region with CIE coordinates of (0.159, 0.021) under 290 nm excitation and shifts to CIE coordinates of (0.161, 0.019) under 320 nm excitation. Finally, complex 3d, having a photoluminescence lifetime of 13.1 μs at room temperature, emits in the sky-blue region with CIE coordinates of (0.237, 0.355).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cyclometalation Syntheses of Phosphorescent Complexes

This is a final close-out report for DOE contract DE-SC0010714 at Case Western Reserve University in Cleveland, Ohio, that funded organometallic and photophysical research from 1 May 2013–30 April 2020. Highlights of research results are presented along with lists of graduate and undergraduate students supported and original papers acknowledging DOE BES support.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Improved Operational Stability of Blue Phosphorescent OLEDs by Functionalizing Phenyl‐Carbene Groups of Tetradentate Pt(II) Complexes

Abstract Stable and efficient deep‐blue organic light‐emitting diodes (OLEDs) are in high demand for display and lighting applications but are rarely reported due to their poor operational lifetimes. Herein, the study designs and synthesizes two novel N ‐heterocyclic carbene (NHC)‐based tetradentate Pt(II) complexes PtON5‐dtb and PtON5N‐dtb, and thoroughly investigate their electrochemical and photophysical properties. Functionalization of the NHC moieties can increase the metal‐to‐ligand charge transfer ( 1/3 MLCT) characters in their lowest triplet excited‐states, resulting in significantly shortened photoluminescent lifetimes and remarkably improved device performance. A deep blue OLED employing PtON5N‐dtb as an emitter exhibits a narrow spectral bandwidth with a full‐width at half maximum (FWHM) of 30 nm and a CIE y value of 0.17 and demonstrates a maximum external quantum efficiency (EQE) of 20.4% with a small efficiency roll‐off, which maintains a high EQE of 18.5% at 1000 cd m −2 . Moreover, the deep blue OLED also realizes a long‐measured operational lifetime LT 90 (time to 90% of the initial luminance) of 71 hours with an initial brightness of 1134 cd m −2 , corresponding to an estimated device lifetime LT 90 of 85 h at 1000 cd m −2 . This represented an eightfold lifetime improvement for PtON5N‐dtb‐based deep blue OLED compared to PtON7‐dtb in the same device setting.

Li, Guijie↗
DOE OSTI2023

Display and lighting devices comprising phosphorescent excimers with preferred molecular orientation as monochromatic emitters

An organic light emitting diode having a substrate, a first electrode, a hole transporting layer proximate the first electrode, a second electrode, an electron transporting layer proximate the second electrode, and an emissive layer between the hole transporting layer and the electron transporting layer. The emissive layer includes a square planar tetradentate platinum or palladium complex, and excimers formed by two or more of the complexes are aligned such that emitting dipoles of the excimers are substantially parallel to a surface of the substrate.

Li, Jian↗
DOE OSTI2023

Spectrally tunable stacked OLED

An OLED lighting device comprising: a blue light-emitting unit with a blue-light fluorescent, phosphorescent or TADF emitter; a yellow light-emitting electroluminescent unit comprising a green phosphorescent emitter, a red phosphorescent emitter and at least one non-emitting host; wherein the blue light-emitting unit and the yellow light-emitting unit are separated by a mixed interlayer with two non-emitting charge-carrier materials. Desirably, the yellow-light emitting unit essentially consists of a green phosphorescent emitter, a red phosphorescent emitter and a single non-emitting host. The mixed interlayer desirably has more than 50% of a hole-transporting material and an electron-transporting material. The Triplet Energy of both materials in the mixed interlayer can be higher than the Triplet Energies of the R and G phosphorescent dopants. The HOMOs of both materials in the mixed interlayer are more negative than the HOMO of the host in the yellow unit but less negative than the HOMO of the host in the blue unit. The LUMOs of the materials in the mixed interlayer can be more negative than the LUMO of the host in the yellow unit but less negative than the LUMO of the host in the blue unit. The OLED lighting device is spectrally tunable according to the supplied power.

Spindler, Jeffrey↗