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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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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Ultrafast Triplet Generation at the Lead Halide Perovskite/Rubrene Interface

Triplet sensitization of rubrene by bulk lead halide perovskites has recently resulted in efficient infrared-to-visible photon upconversion via triplet-triplet annihilation. Notably, this process can occur under solar relevant fluxes, potentially paving the way toward integration with photovoltaic devices. In order to further improve the upconversion efficiency, the fundamental photophysical pathways at the perovskite/rubrene interface must be clearly understood to maximize charge extraction. Here, we utilize ultrafast transient absorption spectroscopy to elucidate the processes underlying triplet generation at the perovskite/rubrene interface. In this work, our results point to a triplet generation mechanism based on hot carriers; thermally excited charge carriers in the perovskite cool more rapidly in the presence of rubrene, suggesting rapid extraction of these thermally excited carriers on the picosecond time scale. Subsequent triplet formation in rubrene is observed on a subnanosecond time scale.

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

Exchange controlled triplet fusion in metal–organic frameworks

Abstract Triplet-fusion-based photon upconversion holds promise for a wide range of applications, from photovoltaics to bioimaging. The efficiency of triplet fusion, however, is fundamentally limited in conventional molecular and polymeric systems by its spin dependence. Here, we show that the inherent tailorability of metal–organic frameworks (MOFs), combined with their highly porous but ordered structure, minimizes intertriplet exchange coupling and engineers effective spin mixing between singlet and quintet triplet–triplet pair states. We demonstrate singlet–quintet coupling in a pyrene-based MOF, NU-1000. An anomalous magnetic field effect is observed from NU-1000 corresponding to an induced resonance between singlet and quintet states that yields an increased fusion rate at room temperature under a relatively low applied magnetic field of 0.14 T. Our results suggest that MOFs offer particular promise for engineering the spin dynamics of multiexcitonic processes and improving their upconversion performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Astronomical demonstration of an infrared upconverter

An upconverter has been used to convert infrared photons from astronomical sources to higher frequency quanta that were detected with a pulse-counting photomultiplier photometer. It is pointed out that these observations represent the first successful astronomical demonstration of infrared upconversion. Upconversion is carried out in an optically nonlinear medium, which in the upconverter described is a lithium iodate crystal. A 0.6943-micrometer high peak power ruby laser pump was developed for the demonstration.

Gurski, T. R.↗
NASA NTRS1983

A theory of Jovian decameter radiation

A theory of the Jovian decameter radiation is presented based on the assumed existence of beams of energetic electrons in the inner Jovian magnetosphere. Beam-like electron distributions are shown to be unstable to the growth of both upper hybrid and lower hybrid electrostatic waves. The upconversion of these waves to fast extraordinary mode electromagnetic radiation is calculated by using a fluid model. Two possibilities are considered. First, a random phase approximation is made which leads to a very conservative estimate of intensity that can be expected in decameter radiation. The alternative possibility is also considered, viz, that the upconversion process is coherent. A comparison of both processes suggests that an incoherent interaction may be adequate to account for the observed intensity of decametric radiation, except perhaps near the peak of the spectrum (8 MHz). The coherent process is intrinsically more efficient and can easily produce the observed intensity near 8 MHz if only 0.01% of the energy in the beam is converted to electrostatic energy.

Goldstein, M. L.↗
NASA NTRS1983

Stochastic three-wave interaction in flaring solar loops

A model is proposed for the dynamic structure of high-frequency microwave bursts. The dynamic component is attributed to beams of precipitating electrons which generate electrostatic waves in the upper hybrid branch. Coherent upconversion of the electrostatic waves to electromagnetic waves produces an intrinsically stochastic emission component which is superposed on the gyrosynchrotron continuum generated by stably trapped electron fluxes. The role of the density and temperature of the ambient plasma in the wave growth and the transition of the three wave upconversion to stochastic, despite the stationarity of the energy source, are discussed in detail. The model appears to reproduce the observational features for reasonable parameters of the solar flare plasma.

Vlahos, L.↗
NASA NTRS1991

Gain and energy storage in holmium YLF

It is demonstrated that Q-switched holmium lasers are capable of high-gain and high-energy operation at 300 K. Small-signal gain coefficients of 0.50 and 0.12/cm have been measured in YLF and YAG, respectively. Small-signal gains of 0.50/cm are comparable to those achievable in Nd:YAG and are not typical of low-gain materials. This large gain in the Ho:YLF material is made possible by operating the amplifier in the ground state depletion mode. The amplifier performance data and associated analysis presented demonstrate that efficient energy storage is possible with very high excited state ion densities of the Ho 5I7 upper laser level. This is an important result since upconversion can limit the 5I7 population. Although upconversion was still present in this experiment, it was possible to achieve efficient energy storage, demonstrating that the problem is manageable even at high excitation densities in YLF.

Storm, Mark E.↗
NASA NTRS1998

HO:LULF and HO:LULF Laser Materials

A laser host material LULF (LuLiF4) is doped with holmium (Ho) and thulium (Tm) to produce a new laser material that is capable of laser light production in the vicinity of 2 microns. The material provides an advantage in efficiency over conventional Ho lasers because the LULF host material allows for decreased threshold and upconversion over such hosts as YAG and YLF. The addition of Tm allows for pumping by commonly available GaAlAs laser diodes. For use with flashlamp pumping, erbium (Er) may be added as an additional dopant. For further upconversion reduction, the Tm can be eliminated and the Ho can be directly pumped.

Barnes, Norman P.↗
NASA NTRS2011

Monitoring Delamination of Thermal Barrier Coatings During Interrupted High-Heat-Flux Laser Testing using Luminescence Imaging

This presentation showed progress made in extending luminescence-base delamination monitoring to TBCs exposed to high heat fluxes, which is an environment that much better simulates actual turbine engine conditions. This was done by performing upconversion luminescence imaging during interruptions in laser testing, where a high-power CO2 laser was employed to create the desired heat flux. Upconverison luminescence refers to luminescence where the emission is at a higher energy (shorter wavelength) than the excitation. Since there will be negligible background emission at higher energies than the excitation, this methods produces superb contrast. Delamination contrast is produced because both the excitation and emission wavelengths are reflected at delamination cracks so that substantially higher luminescence intensity is observed in regions containing delamination cracks. Erbium was selected as the dopant for luminescence specifically because it exhibits upconversion luminescence. The high power CO2 10.6 micron wavelength laser facility at NASA GRC was used to produce the heat flux in combination with forced air backside cooling. Testing was performed at a lower (95 W/sq cm) and higher (125 W/sq cm) heat flux as well as furnace cycling at 1163C for comparison. The lower heat flux showed the same general behavior as furnace cycling, a gradual, "spotty" increase in luminescence associated with debond progression; however, a significant difference was a pronounced incubation period followed by acceleration delamination progression. These results indicate that extrapolating behavior from furnace cycling measurements will grossly overestimate remaining life under high heat flux conditions. The higher heat flux results were not only accelerated, but much different in character. Extreme bond coat rumpling occurred, and delamination propagation extended over much larger areas before precipitating macroscopic TBC failure. This indicates that under the higher heat flux (and surface & interface temperatures), the TBC was more tolerant of damage. The main conclusions were that high heat flux conditions can not only accelerate TBC debond progression but can also grossly alter the pathway of delamination.

Eldridge, Jeffrey I.↗
DOE OSTI2022

Triplet photodynamic and up-conversion luminescence in donor–acceptor dyads with slip-stacked vs. co-facial arrangement

We report the design/synthesis and characterization of organic donor–acceptor (D–A) dyads can provide precious data allowing to improve the efficiency of classical photo-induced bimolecular interactions/processes. In this report, two novel triplet D–A dyads (4 and 5) were synthesized and fully characterized. While the optical absorption and emission profiles of these new systems exhibit similar spectral structures as that of the triplet donor/sensitizer quinoidal thioamide (QDN), the transient absorption (TA) spectra of these two dyads produced new features that can be associated with triplet transients and charge transfer species. However, the kinetics of the excited-state processes/dynamics is significantly influenced by the geometrical arrangement(s) of donor/acceptor chromophores. Further analysis of the TA data suggests that the dyad with slip-stack geometry (4) is less effective in undergoing both intra- and inter-dyad triplet energy transfer than the dyad with co-facial geometry (5). Subsequently, triplet sensitization of 9,10-diphenylanthracene (DPA) using both dyads led to upconverted photoluminescence via triplet–triplet annihilation of DPA triplet transients. But, it was found that a maximum upconversion quantum yield could be achieved at a low power density using the co-facial type dyad 5. Altogether, these results provide valuable guidance in the design of triplet donor–acceptor dyads, which could be used for light-harvesting/modulation applications.

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

Size-Dependent Photon Avalanching in Tm 3+ Doped LiYF 4 Nano, Micro, and Bulk Crystals

Photon avalanche (PA) is a highly nonlinear mode of upconversion that is characterized by 100–1000-fold increase in luminescence intensity upon minute increments of pumping power. The practical realization of numerous possible nano-bio-technology applications utilizing the PA phenomenon will require information on its susceptibility to the material volume and surface. In this report these parameters are investigated via experimental and theoretical PA. The two-color, highly nonlinear PA emission at 475 and 800 nm is clearly observed in bulk single crystal, individual microcrystals, and ensembles of colloidal core and core–shell nanoparticles of LiYF 4 host doped with either 3 or 8% of thulium ions. The properties of PA emission, such as PA nonlinearity, PA gain, PA intensity, and luminescence kinetics in these materials show dependence on crystal volume and surface quenching. Theoretical simulations provide understanding of key physical processes that influence PA performance. Moreover, photon avalanche single beam super-resolution imaging is realized for the first time in 3% Tm 3+ doped LiYF 4 core–shell nanoparticles. The obtained insights and predictions form a solid background for further development and applications of new optimized PA materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

2D Ionic Liquid-Like State of Charged Rare-Earth Clusters on a Metal Surface

Rare-earth complexes are vital for separation chemistry and useful in many advanced applications including emission and energy upconversion. Here, 2D rare-earth clusters having net charges are formed on a metal surface, enabling investigations of their structural and electronic properties on a one-cluster-at-a-time basis using scanning tunneling microscopy. While these ionic complexes are highly mobile on the surface at ≈100 K, their mobility is greatly reduced at 5 K and reveals stable and self-limiting clusters. In each cluster, a pair of charged rare-earth complexes formed by electrostatic and dispersive interactions act as a basic unit, and the clusters are chiral. Unlike other non-ionic molecular clusters formed on the surfaces, these rare-earth clusters show mechanical stability. Moreover, their high mobility on the surface suggests that they are in a 2D liquid-like state.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Fully Integrated Ultra-thin Intraoperative Micro-imager for Cancer Detection Using Upconverting Nanoparticles

Abstract Purpose Intraoperative detection and removal of microscopic residual disease (MRD) remain critical to the outcome of cancer surgeries. Today’s minimally invasive surgical procedures require miniaturization and surgical integration of highly sensitive imagers to seamlessly integrate into the modern clinical workflow. However, current intraoperative imagers remain cumbersome and still heavily dependent on large lenses and rigid filters, precluding further miniaturization and integration into surgical tools. Procedures We have successfully engineered a chip-scale intraoperative micro-imager array—without optical filters or lenses—integrated with lanthanide-based alloyed upconverting nanoparticles (aUCNPs) to achieve tissue imaging using a single micro-chip. This imaging platform is able to leverage the unique optical properties of aUCNPs (long luminescent lifetime, high-efficiency upconversion, no photobleaching) by utilizing a time-resolved imaging method to acquire images using a 36-by-80-pixel, 2.3 mm $$\times$$ × 4.8 mm silicon-based electronic imager micro-chip, that is, less than 100-µm thin. Each pixel incorporates a novel architecture enabling automated background measurement and cancellation. We have validated the performance, spatial resolution, and the background cancellation scheme of the imaging platform, using resolution test targets and mouse prostate tumor sample intratumorally injected with aUCNPs. To demonstrate the ability to image MRD, or tumor margins, we evaluated the imaging platform in visualizing a single-cell thin section of the injected prostate tumor sample. Results Tested on USAF resolution targets, the imager is able to achieve a resolution of 71 µm. We have also demonstrated successful background cancellation, achieving a signal-to-background ratio of 8 when performing ex vivo imaging on aUCNP-injected prostate tumor sample, improved from originally 0.4. The performance of the imaging platform on single-cell layer sections was also evaluated and the sensor achieved a signal-to-background ratio of 4.3 in resolving cell clusters with sizes as low as 200 cells. Conclusion The imaging system proposed here is a scalable chip-scale ultra-thin alternative for bulky conventional intraoperative imagers. Its novel pixel architecture and background correction scheme enable visualization of microscopic-scale residual disease while remaining completely free of lenses and filters, achieving an ultra-miniaturized form factor—critical for intraoperative settings.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Ligand design in lanthanide complexes for luminescence, therapy, and sensing

In this chapter, we explore the research done by the de Bettencourt-Dias group in luminescent lanthanide complexes. The group has isolated ligands that sensitize the luminescence of lanthanide ions, and that bear additional functional groups that impart unique properties to the resulting complexes, such as the ability to generate cytotoxic singlet oxygen, or report on, through changes in emission intensity, viscosity or temperature at the nanoscale. The energy transfer processes are accessed through one-photon excitation or two-photon excitation through the ligand, as well as upconversion. Moreover, the group explored unique coordination chemistry of lanthanides, taking advantage of secondary interactions to isolate outer-sphere complexes of these ions.

Barber, Patrick S.↗
DOE OSTI2020

Visible-Light-Initiated Free-Radical Polymerization by Homomolecular Triplet-Triplet Annihilation

Polymerization reactions initiated by ultraviolet light are ubiquitous in scores of industrial applications but would markedly benefit from visible-light activation to overcome stability, energy consumption, light penetration, and sample geometry limitations. The current work leverages visible-light-driven homomolecular triplet-triplet annihilation (TTA) in zinc(II) meso-tetraphenylporphyrin (ZnTPP) to initiate facile free-radical polymerization in trimethylolpropane triacrylate (TMPTA) and methyl acrylate (MA) monomers through ultrafast electron transfer quenching. Selective Q-band (S 1 ) excitation of ZnTPP in the green or yellow sensitizes TTA occurring between two 3 ZnTPP* energized chromophores, ultimately generating the highly reducing S 2 excited state on one ZnTPP molecule (E red = –2.13 V versus saturated calomel electrode, SCE). Subsequently, this S 2 state engages in electron transfer with TMPTA or MA, thereby initiating the radical polymerization process. Bimolecular electron transfer was confirmed through optically gated fluorescence upconversion. In conclusion, FT-IR and EPR spin-trapping experiments verified visible-light-initiated polymerization leading to the formation of well-defined macro- and microscopic objects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

New red phosphor ceramic K 2 SiF 6 :Mn 4+

We report a new transparent ceramic phosphor for use in LED lighting has been fabricated. The previously reported and optimized narrow-emitting red phosphor, K 2 SiF 6 :Mn 4+ (KSF), has been consolidated into a transparent ceramic phosphor for the first time, accomplished via hot-pressing the feedstock phosphor powder in a die under vacuum. KSF ceramics were fabricated with varying doping concentrations of Mn 4+ and their properties studied. The absorption and emission spectra of the ceramics were identical to the feedstock phosphor powders and are ideal for LED lighting with strong absorption at 450 nm and narrow emission around 630 nm. The absorbance of the ceramics was directly proportional to the doping concentration. The ceramics were excited at various blue light fluxes and their emission intensities measured to study the effect of Mn 4+ concentration on intensity-driven “droop” in the emission output. The ceramics with a lower Mn 4+ doping were more efficient under higher light fluxes due to a decrease in Auger upconversion losses. KSF ceramics can allow a much longer path length of the diode light through the phosphor, as compared to phosphor-in-silicone, enabling the use of low optical absorption and the associated reduced activator concentration. The ceramics are measured to have a thermal conductivity of ~1.0 W/m-K, higher than that of phosphor-in-silicone or phosphor-in-glass. Several of these properties make KSF ceramics potentially desirable for use in white light LEDs. Greater thermal conductivity helps with heat dissipation, the lower surface area of the ceramic compared to the powder minimizes the environmental vulnerability of KSF, and the ability to lower the Mn 4+ concentration reduces Auger recombination losses and mitigates the temperature rise, particularly at higher light flux.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Chemically Tunable Aspect Ratio Control and Laser Refrigeration of Hexagonal Sodium Yttrium Fluoride Upconverting Materials

Hexagonal sodium yttrium fluoride with Na 3x Y 2-x F 6 stoichiometry (β-NaYF) is a promising material for luminescence upconversion applications due to the narrow crystal field splitting of the Yb(III) ion’s lower 2 F 7/2 manifold. However, growing single crystals of β-NaYF remains an outstanding challenge due to thermal expansion stresses that cause cracking during melt growth. Here, we demonstrate a novel hydrothermal synthesis of β-NaYF with the ability to tune the aspect ratio from microplatelets to microrods with aspect ratios that match computationally predicted cavity (Mie) resonances. These crystals have a root-mean-square roughness below 1 nm after calcination, which makes them ideal for optical cavities. The β-NaYF microcrystals are doped with 10% Yb(III) cations and are used to build optomechanical laser-refrigeration devices consisting of a hexagonal β-NaYF crystal located at the end of a cantilever. Laser refrigeration of these devices by >12.5 °C is observed using calibrated measurements of both the cantilever’s fundamental eigenfrequency and a Boltzmann fit to crystal field luminescence from the Yb(III) ions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Homomolecular Triplet–Triplet Annihilation in Metalloporphyrin Photosensitizers

Metalloporphyrins are ubiquitous in their applications as triplet photosensitizers, particularly for promoting sensitized photochemical upconversion processes. In this study, bimolecular excited state triplet–triplet quenching kinetics, termed homomolecular triplet–triplet annihilation (HTTA), exhibited by the traditional triplet photosensitizers–zinc(II) tetraphenylporphyrin (ZnTPP), palladium(II) octaethylporphyrin (PdOEP), platinum(II) octaethylporphyrin (PtOEP), and platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP)–were revealed using conventional transient absorption spectroscopy. Nickel(II) tetraphenylporphyrin was used as a control sample as it is known to be rapidly quenched intramolecularly through ligand-field state deactivation and, therefore, cannot result in triplet–triplet annihilation (TTA). The single wavelength transients associated with the metalloporphyrin triplet excited state decay–measured as a function of incident laser pulse energy in toluene–were well modeled using parallel first- and second-order kinetics, consistent with HTTA being operable. The combined transient kinetic data enabled the determination of the first-order rate constants (k T ) for excited triplet decay in ZnTPP (4.0 × 10 3 s –1 ), PdOEP (3.6 × 10 3 s –1 ), PtOEP (1.2 × 10 4 s –1 ), and PtTPBP (2.1 × 10 4 s –1 ) as well as the second-order rate constant (k TT ) for HTTA in ZnTPP (5.5 × 10 9 M –1 s –1 ), PdOEP (1.1 × 10 10 M –1 s –1 ), PtOEP (7.1 × 10 9 M –1 s –1 ), and PtTPBP (1.6 × 10 10 M –1 s –1 ). In most instances, triplet excited state extinction coefficients are either reported for the first time or have been revised using ultrafast transient absorption spectroscopy and singlet depletion: ZnTPP (78,000 M –1 cm –1 ) at 470 nm, PdOEP (67,000 M –1 cm –1 ) at 430 nm, PtOEP (51,000 M –1 cm –1 ) at 418 nm, and PtTPBP (100,000 M –1 cm –1 ) at 460 nm. Furthermore, the combined experimental results establish competitive time scales for homo- and heteromolecular TTA rate constants, implying the significance of considering HTTA processes in future research endeavors harnessing TTA photochemistry using common metalloporphyrin photosensitizers.

14 SOLAR ENERGY↗
DOE OSTI2021

Interlayer Triplet-Sensitized Luminescence in Layered Two-Dimensional Hybrid Metal-Halide Perovskites

In this work, we review an emerging class of 2D layered metal-halide perovskites that exhibit important photophysical behavior involving inorganic exciton-to-molecular triplet energy flow. These novel systems have potential to impact several energy-related fields and processes, including optoelectronics, photon upconversion strategies, and triplet-based photocatalysis. Early studies provided initial guidance and revealed several intriguing questions that more recent developments, in terms of both expanded and diversified compositional tuning and more sophisticated characterization, have begun to answer. These questions center around the delicate interplay between physical and electronic structure that is perturbed by choice of perovskite structural motif and organic spacer properties. In addition to their distinct natures, the energy offsets between the metal-halide and molecular excitons can be leveraged for a variety of unique effects and emergent properties, including fast interlayer energy transfer. We review the key advances with an eye toward strategies for controlling photophysical outcomes based on structure-energy-function relationships.

14 SOLAR ENERGY↗