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At least 19 records

Luminescence and Scintillation in the Niobium Doped Oxyfluoride Rb4Ge5O9F6:Nb

A new niobium-doped inorganic scintillating oxyfluoride, Rb4Ge5O9F6:Nb, was synthesized in single crystal form by high-temperature flux growth. The host structure, Rb4Ge5O9F6, crystallizes in the orthorhombic space group Pbcn with lattice parameters a = 6.98430(10) Å, b = 11.7265(2) Å, and c = 19.2732(3) Å, consisting of germanium oxyfluoride layers made up of Ge3O9 units connected by GeO3F3 octahedra. In its pure form, Rb4Ge5O9F6 shows neither luminescence nor scintillation but when doped with niobium, Rb4Ge5O9F6:Nb exhibits bright blue luminescence and scintillation. The isostructural doped structure, Rb4Ge5O9F6:Nb, crystallizes in the orthorhombic space group Pbcn with lattice parameters a = 6.9960(3) Å, b = 11.7464(6) Å, and c = 19.3341(9) Å. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements suggest that the niobium is located in an octahedral coordination environment. Optical measurements inform us that the niobium dopant acts as the activator. The synthesis, structure, and optical properties are reported, including radioluminescence (RL) measurements under X-ray irradiation.

Carone, Darren (ORCID:0000000164014098)↗

Luminescence analysis of lunar samples returned by Apollo: Luminescence of Apollo 14 and Apollo 15 lunar samples

Luminescence measurements were made of Apollo 14 lunar samples with far UV X-ray, and proton irradiation and of Apollo 15 lunar samples with X-ray irradiation. Preliminary efficiencies with the far UV are in the range 0.001 to 0.01; efficiencies with X-rays and protons are in the range 10 to the -8th to 10 to the -6th powers. The crystalline igneous rocks show higher efficiencies, in general, than the breccias and glasses, and the ratio of intensity of the green to the blue luminescence peak tends to be higher for the crystalline igneous rocks than for breccias and glasses. Therefore, both the efficiency and the spectral character appear to have a systematic relationship to lithologic type (granitic versus gabbroic versus fragmental) and to geologic history and processes on the moon (shocked versus unshocked or only mildly shocked material).

Greenman, N. N.↗

Fabrication of luminescent porous silicon with stain etches and evidence that luminescence originates in amorphous layers

Simple immersion of Si in stain etches of HF:HNO3:H2O or NaNO2 in aqueous HF was used to produce films exhibiting luminescence in the visible similar to that of anodically-etched porous Si. All of the luminescent samples consist of amorphous porous Si in at least the near surface region. No evidence was found for small crystalline regions within these amorphous layers.

Fathauer, R. W.↗

Heterometallic UO 2 2+ /Ag + Complexes: Structural Design and Luminescence Properties

Reported here are the synthesis, structural characterization, and luminescence properties of 11 novel UO 2 2+ /Ag + heterometallic complexes. Halogenated benzoic acids (2,6-dihalobenzoic acid (halo = F, Br), 3,5-dichlorobenzoic acid, and 3-halobenzoic acid (halo = Br, I)) and N-donor polycyclic ligands (2,2′-bipyridine, 2,2’;6′,2″-terpyridine, 1,10-phenanthroline, 2,2′-bipyrimidine) were employed to synthesize a set of compounds and induce structural diversity. The primary mode of coordination with the uranyl cation is hexagonal bipyramidal monomeric units with three halobenzoate ligands in the equatorial plane, though 1-D chains with pentagonal bipyramidal uranyl centers also form. The Ag + cations coordinate preferentially to the N-donor ligands and serve as counter-cations for the anionic uranyl motifs. The soft ligand character of the N-donor molecules is found to be a requirement for the inclusion of the Ag + cation into the structures. Anionic uranyl units and cationic silver units assemble via noncovalent interactions between π systems on adjacent rings and between halogens (when Br and I are present). Solid-state emission spectra display the usual uranyl band with superimposed vibronic fine structure, except for that of compound 1 , which shows emission from the 2,2′-bipyridine center. This family of compounds represents a substantial contribution to the already rich library of UO 2 2+ /Ag + compounds, and the synthetic parameters discussed within reveal a platform for the design of new heterometallic uranyl-containing materials.

anions↗

Bridging the Void: Halogen Bonding and Aromatic Interactions to Program Luminescence and Electronic Properties of π -Conjugated Materials in the Solid State

π-Conjugated materials are promising candidates for emerging organic optoelectronic devices empowered by molecular design. The unsolved challenges of predicting and controlling their packing as solids, central to their properties and performance, currently limits their practical application. As noncovalent interactions drive packing, control over such interactions are critical to bridging from chemical structure to functional properties. In molecular crystals, halogen bonding and interactions of aromatic rings have emerged as versatile tools for noncovalent control with tailored luminescence and electronic properties. Here, we describe how the interplay of these directional and tunable interactions can engineer properties, including stimuli-responsive behavior. Specifically, halogen bonding can provide robust designs for directing 2D molecular assembly, whereas the intentional interactions of aromatic rings can yield metastable, switchable packing modes, as well as programmed stacking between layers of chromophores. Examples, herein, demonstrate clear relationships between assembly by design and resulting solid-state properties, and strategies presented offer guidance for future designs of π-conjugated molecular materials using specific aromatic interactions and halogen bonding.

36 MATERIALS SCIENCE↗

Unidirectional luminescence from InGaN/GaN quantum-well metasurfaces

III–nitride light-emitting diodes (LEDs) are the backbone of ubiquitous lighting and display applications. Imparting directional emission is an essential requirement for many LED implementations. Although optical packaging, nanopatterning and surface roughening4 techniques can enhance LED extraction, directing the emitted light requires bulky optical components. Optical metasurfaces provide precise control over transmitted and reflected waveforms, suggesting a new route for directing light emission. However, it is difficult to adapt metasurface concepts for incoherent light emission, due to the lack of a phase-locking incident wave. Here, we demonstrate a metasurface-based design of InGaN/GaN quantum-well structures that generate narrow, unidirectional transmission and emission lobes at arbitrary engineered angles. We further demonstrate 7-fold and 100-fold enhancements of total and air-coupled external quantum efficiencies, respectively. The results present a new strategy for exploiting metasurface functionality in light-emitting devices.

inorganic LEDs↗

High-Temperature Thermometer Using Cr-Doped GdAlO3 Broadband Luminescence

A new concept has been developed for a high-temperature luminescence-based optical thermometer that both shows the desired temperature sensitivity in the upper temperature range of present state-of-the-art luminescence thermometers (above 1,300 C), while maintaining substantial stronger luminescence signal intensity that will allow these optical thermometers to operate in the presence of the high thermal background radiation typical of industrial applications. This objective is attained by using a Cr-doped GdAlO3 (Cr:GdAlO3) sensor with an orthorhombic perovskite structure, resulting in broadband luminescence that remains strong at high temperature due to the favorable electron energy level spacing of Cr:GdAlO3. The Cr:GdAlO3 temperature (and pressure) sensor can be incorporated into, or applied onto, a component s surface when a non-contact surface temperature measurement is desired, or alternatively, the temperature sensor can be attached to the end of a fiber-optic probe that can then be positioned at the location where the temperature measurement is desired. In the case of the fiber-optic probe, both the pulsed excitation and the luminescence emission travel through the fiber-optic light guide. In either case, a pulsed light source provides excitation of the luminescence, and the broadband luminescence emission is collected. Real-time temperature measurements are obtain ed using a least-squares fitting algorithm that determines the luminescence decay time, which has a known temperature dependence established by calibration. Due to the broad absorption and emission bands for Cr:GdAlO3, there is considerable flexibility in the choice of excitation wavelength and emission wavelength detection bands. The strategic choice of the GdAlO3 host is based on its high crystal field, phase stability, and distorted symmetry at the Cr3+ occupation sites. The use of the broadband emission for temperature sensing at high temperatures is a key feature of the invention and is novel since broadband luminescence emission normally shows severe thermal quenching. The tightly bound AlO6 octahedra in GdAlO3 results in a larger energy barrier to nonradiative decays than in other materials and therefore makes using broadband emission for temperature sensing possible at high temperatures. This approach results in a substantial increase in temperature capability. For example, the most commonly used Cr-doped crystal used for luminescence-based temperature measurements, ruby, has only been demonstrated up to 600 C, whereas the Cr:GdAlO3 optical thermometer under development has already been shown to exhibit useful luminescence up to 1,300 C. Because GdAlO3 is non-reactive and is stable in harsh, high-temperature environments, sensors composed of Cr:GdAlO3 will be very well suited for remote high-temperature measurements in engine or industrial environments where its intense high-temperature luminescence will stand out above significant thermal radiation background levels.

Eldridge, Jeffrey↗

Monitoring Delamination of Plasma-Sprayed Thermal Barrier Coatings by Reflectance-Enhanced Luminescence

Highly scattering plasma-sprayed thermal barrier coatings (TBCs) present a challenge for optical diagnostic methods to monitor TBC delamination because scattering attenuates light transmitted through the TBC and usually degrades contrast between attached and delaminated regions of the TBC. This paper presents a new approach where reflectance-enhanced luminescence from a luminescent sublayer incorporated along the bottom of the TBC is used to identify regions of TBC delamination. Because of the higher survival rate of luminescence reflecting off the back surface of a delaminated TBC, the strong scattering exhibited by plasma-sprayed TBCs actually accentuates contrast between attached and delaminated regions by making it more likely that multiple reflections of luminescence off the back surface occur before exiting the top surface of the TBC. A freestanding coating containing sections designed to model an attached or delaminated TBC was prepared by depositing a luminescent Eu-doped or Er-doped yttria-stabilized zirconia (YSZ) luminescent layer below a plasma-sprayed undoped YSZ layer and utilizing a NiCr backing layer to represent an attached substrate. For specimens with a Eu-doped YSZ luminescent sublayer, luminescence intensity maps showed excellent contrast between unbacked and NiCr-backed sections even at a plasma-sprayed overlayer thickness of 300 m. Discernable contrast between unbacked and NiCr-backed sections was not observed for specimens with a Er-doped YSZ luminescent sublayer because luminescence from Er impurities in the undoped YSZ layer overwhelmed luminescence originating form the Er-doped YSZ sublayer.

Eldridge, Jeffrey I.↗

Monitoring Delamination of Thermal Barrier Coatings by Near-Infrared and Upconversion Luminescence Imaging

Previous work has demonstrated that TBC delamination can be monitored by incorporating a thin luminescent sublayer that produces greatly increased luminescence intensity from delaminated regions of the TBC. Initial efforts utilized visible-wavelength luminescence from either europium or erbium doped sublayers. This approach exhibited good sensitivity to delamination of electron-beam physical-vapor-deposited (EB-PVD) TBCs, but limited sensitivity to delamination of the more highly scattering plasma-sprayed TBCs due to stronger optical scattering and to interference by luminescence from rare-earth impurities. These difficulties have now been overcome by new strategies employing near-infrared (NIR) and upconversion luminescence imaging. NIR luminescence at 1550 nm was produced in an erbium plus ytterbium co-doped yttria-stabilized zirconia (YSZ) luminescent sublayer using 980-nm excitation. Compared to visible-wavelength luminescence, these NIR emission and excitation wavelengths are much more weakly scattered by the TBC and therefore show much improved depth-probing capabilities. In addition, two-photon upconversion luminescence excitation at 980 nm wavelength produces luminescence emission at 562 nm with near-zero fluorescence background and exceptional contrast for delamination indication. The ability to detect TBC delamination produced by Rockwell indentation and by furnace cycling is demonstrated for both EB-PVD and plasma-sprayed TBCs. The relative strengths of the NIR and upconversion luminescence methods for monitoring TBC delamination are discussed.

Eldridge, J. I.↗

Achieving Multimodal and Multicolor Luminescence in LaAlO 3 :Pr 3+ , Gd 3+ via Trap Engineering and Energy Transfer

Achieving multimodal luminescence within a single phosphor is vital for multifunctional applications but remains challenging due to complex color tuning and trap engineering. In this study, we report Pr 3+ and Gd 3+ co‐doped LaAlO 3 (LAO:PG) phosphors, designed through careful modulation of multilevel traps and Pr 3+ → Gd 3+ energy transfer dynamics. These materials exhibit diverse luminescence modes, including down‐conversion luminescence (DCL), up‐conversion luminescence (UCL), persistent luminescence (PersL), optically stimulated luminescence (OSL), and thermally stimulated luminescence (TSL) across a wide spectral range. Unlike previously studied Pr 3+ ‐doped LAO, the co‐doped LAO:PG shows DCL in both UV‐visible and NIR regions and displays ultraviolet‐C UCL under visible excitation. Notably, we observe, for the first time, PersL lasting several minutes in these phosphors—an improvement over the non‐PersL behavior of Pr 3+ ‐only doped LAO. Additionally, the LAO:PG phosphors exhibit strong OSL response. TSL analysis reveals five distinct trap levels linked to these properties. Density functional theory calculations further correlate intrinsic defects to these traps, supporting a proposed mechanism for the observed multimodal luminescence. These findings highlight LAO:PG as a promising platform for developing advanced phosphors with integrated luminescence modes, paving the way for future applications in data storage, phototherapy, and anti‐counterfeiting technologies.

Chemistry↗

Monitoring Temperatures of Tires Using Luminescent Materials

A method of noncontact, optical monitoring of the surface temperature of a tire has been devised to enable the use of local temperature rise as an indication of potential or impending failures. The method involves the use of temperature-sensitive paint (or filler): Temperature-sensitive luminescent dye molecules or other luminescent particles are incorporated into a thin, flexible material coating the tire surface of interest. (Alternatively, in principle, the luminescent material could be incorporated directly into the tire rubber, though this approach has not yet been tested.) The coated surface is illuminated with shorter-wavelength light to excite longer-wavelength luminescence, which is observed by use of a charge-coupled-device camera or a photodetector (see Figure 1). If temporally constant illumination is used, then the temperature can be deduced from the known temperature dependence of the intensity response of the luminescence. If pulsed illumination is used, then the temperature can be deduced from the known temperature dependence of the time or frequency response of the luminescence. If sinusoidally varying illumination is used, then the temperature can be deduced from the known temperature dependence of the phase response of the luminescence. Unlike a prior method of monitoring the temperature at a fixed spot on a tire by use of a thermocouple, this method is not restricted to one spot and can, therefore, yield information on the spatial distribution of temperature: in particular, it enables the discovery of newly forming hot spots where damage may be starting. Also unlike in the thermocouple method, the measurements in this method are not vulnerable to breakage of wires in repeated flexing of the tire. Moreover, unlike in another method in which infrared radiation is monitored as an indication of surface temperature, the luminescence measurements in this method are not significantly affected by changes in infrared emissivity. This method has been demonstrated in application to the outside surface of a tire (see Figure 2), using both constant and pulsed light sources for illumination and cooled, slow-scan, gated CCD cameras for detection. For observing the temperature of the inside surface of a tire (this has not yet been done), it would probably be necessary to use fiber optics and/or windows for coupling excitation light into, and coupling luminescence out of, the interior volume.

Bencic, Timothy J↗