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At least 487 records · Page 27

Achieving a blue-excitable yellow-emitting Ca-LMOF phosphor via water induced phase transformation

Luminescent metal-organic frameworks (LMOFs) with diverse structural features and promising fluorescence-based applications have attracted wide attention in the past two decades. In this work, a LMOF with the formula [Ca 4 (tcbpe-F) 2 (H 2 O) 3 ] (1, LMOF-411) has been constructed from calcium (Ca) and 1,1,2,2-tetrakis(4-(4-carboxyphenyl)phenyl)ethene (H 4 tcbpe-F). Compound 1 features a three-dimensional framework with a 10-nodal net topology. Due to the relatively high hydration energy of Ca 2+ , compound 1 readily transforms into a new phase formulated as [Ca(H 2 tcbpe-F)(H 2 O) 2 ] (1') upon exposure to water. Combining experimental characterization and theoretical calculations, we elucidated the mechanism of H 2 O-induced phase transition from 1 to 1'. Notably, the water induced phase transformation can be detected visibly from the change in luminescence, which originates from the fluorescent linker. Compound 1 emits green light ( λ em = 490 nm) under UV excitation, while compound 1' emits bright yellow light ( λ em = 550 nm) under blue excitation (450 nm). Compound 1' represents the first Ca based LMOF yellow phosphor and its luminescence quantum yield reaches 68%. It can be coated directly onto a commercial blue light-emitting-diode (LED) chip to fabricate a white LED (WLED).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupled Charge and Radiation Transport Processes in Thermophotovoltaic and Thermoradiative Cells

Accurate modeling of charge transport and both thermal and luminescent radiation is crucial to the understanding and design of radiative thermal energy converters. Charge-carrier dynamics in semiconductors are well-described by the Poisson-drift-diffusion equations, and thermal radiation in emitter-absorber structures can be computed using multilayer fluctuational electrodynamics. These two types of energy flows interact through radiation absorption or luminescence and charge-carrier generation or recombination. However, past research has typically only assumed limited interaction, with thermal radiation absorption as an input for charge-carrier models to predict device performance. To examine this assumption, we develop a fully coupled iterative model of charge and radiation transport in semiconductor devices, and we use our model to analyze near-field and far-field GaSb thermophotovoltaic and thermoradiative systems. By comparing our results with past methods that do not consider cross-influences between charge and radiation transport, we find that a fully coupled approach is necessary to accurately model photon recycling and near-field enhancement of external luminescence. As these effects can substantially alter device performance, our modeling approach can aid in the design of efficient thermophotovoltaic and thermoradiative systems.

30 DIRECT ENERGY CONVERSION↗

Carbon complexes in highly C-doped GaN

We investigate the properties of heavily C-doped GaN grown by hydride vapor phase epitaxy using both optical experiments and hybrid density functional theory calculations. Previous work has established that carbon acceptors (C N ) give rise to a yellow luminescence band near 2.2 eV along with a blue luminescence band near 2.9 eV. Photoluminescence measurements show the yellow band shifting as a function of carbon concentration, suggesting a change in the behavior of carbon species as carbon content increases. With hybrid density functional theory we calculate the electrical and optical behavior of carbon centers containing multiple carbon impurities, which may arise in heavily doped material. We compare the behavior of these complexes to the isolated centers, and find that the dicarbon donor-acceptor (C Ga –C N ) complex is a candidate to explain the shift in the yellow luminescence peak. Tricarbon complexes have high formation energies and modest binding energies, and also give rise to optical transitions that are inconsistent with the observed spectra. We also identify the split dicarbon interstitial on the gallium site as a low-energy species with a large binding energy that may act to compensate carbon acceptors. Here, local vibrational modes are calculated for carbon impurity centers, and we compare these results to recent experiments. Dicarbon and tricarbon complexes involving C Ga and C N exhibit modes that are only slightly higher than the isolated species, while carbon interstitials and related complexes give rise to vibrational modes much higher than C Ga and C N .

36 MATERIALS SCIENCE↗

Incident excitation effects on ZnO-based photoluminescence

Zinc oxide (ZnO) is an attractive semiconductor material owing to a wide band gap, large exciton binding energy, and strong luminescent properties. Two distinct spectral regions are present in the room temperature emission of this material: a narrow line in the UV/near-UV region that is excitonic in nature and a lower energy broad emission band centered in the green/yellow region. Commercially available ZnO particles containing excess Zn and oxygen vacancy defect sites (referred to as ZnO:Zn) were excited using three light sources to study different radiative recombination regimes of the as-received powders. First, a UV LED at a center wavelength of 365 nm provided low irradiance (0.02–0.08 W/cm 2 ) with varying pulse widths (continuous operation to 16 ns). Second, the third harmonic of a pulsed Nd:YAG laser provided high irradiances (∼10 4 –10 6 W/cm 2 ) at a fixed nominal pulse width of 5 ns. Finally, a continuous polychromatic synchrotron X-ray source was also used to excite the ZnO:Zn powders. During UV LED excitation, a low number of carriers are created in the material, leading to an anticipated linear relationship between luminescence and irradiance. This held true for defect luminescence; however, there was an observed enhancement of exciton emission relative to the UV LED intensity as the pulse width was decreased, independent of irradiance. During UV laser excitation, the number of carriers was significantly increased, raising the material into a bimolecular recombination regime, which produced exciton emission much stronger than visible band emission. Finally, spectra obtained during synchrotron X-ray excitation, whose continuous illumination and higher penetration depth yielded higher emission from defect sites relative to exciton emission. A redshift in the exciton emission was also observed as excitation pulse width and sample temperature were varied, and is discussed.

Westphal, Eric Robert [Sandia National Lab. (SNL-N↗

Performance of Scintillation Detectors Based on Quantum Dots in a Semiconductor Matrix (Final Technical Report)

InAs Quantum Dots (QDs) embedded into GaAs semiconductor waveguide have unique scintillation properties, valuable for nuclear security, medical imaging, and high energy physics. In this work, we developed thick (~25um) epitaxial heterostructres with high luminescence efficiency composed of self-assembled nano-engineered InAs QDs grown by molecular beam epitaxy. In this type of detector, the GaAs matrix acts as a stopping material for charged particles or photons generating electrons captured by the QDs acting as luminescence centers. The QD medium is designed to provide fast capture of electrons into QDs (few ps), high QD luminescence efficiency at room temperature (>50%), and strong red-shift of photoluminescence (PL) from the GaAs absorption edge (>250nm). Typical devices consist of a 10-25um thick GaAs layer with embedded sheets of modulation p-type doped InAs QDs and an InGaAs photodetector tuned to the QD emission wavelength. The thick GaAs layer acts also as a waveguide when layer-transferred onto a low-index substrate. Waveguiding and self-absorption (~1cm -1 ) were studied using photoluminescence with scanning laser excitation and modeled with ray optics approximation and geometrical coupling of high-index waveguide to a collection fiber. Scintillating signals from α-particles were analyzed with both an external photodiode (PD) and an integrated PD which provided an improved optical coupling. In the former case, the external InGaAs PD was air-coupled to the scintillator and had the light collection efficiency of about 1% corresponding to limited light extraction through a planar interface with air due to total internal reflection. The mean charge collected by the integrated PD was in the range of (3÷5)×10 4 photoelectrons per 1 MeV of deposited energy, or ~13-20% of the theoretically achievable light yield. Timing of the integrated device was measured by wire-bonding it to the input of an 8 GHz IC. The scintillation response shows an extremely fast 0.3-0.6 ns decay constant and about 40-70 ps time resolution, limited by the system noise. The combined light yield and decay time makes the InAs/GaAs QD heterostructures the fastest high yield scintillation material reported making it valuable for high energy physics and medical imaging applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Optimization of Conditions for Photoluminescence-Based Sensing of Critical Minerals: Strategies and Outlook

Economically critical minerals and metals are vital to America’s security, with application areas in energy, advanced technologies, and defense systems. The growing implementation of renewable energy sources such as electric vehicles is expected to significantly increase demand for these minerals, while the global supply is monopolistic, with most of the production occurring in a few countries outside of the US. To mitigate potential supply chain vulnerabilities, the domestic production of economically critical metals has become a bipartisan priority of the US government, and unconventional sources such as coal and its utilization byproducts such as fly ash and acid mine drainage are being actively explored as an alternative method for meeting domestic demand. Slow and expensive characterization methods for critical metals present a significant pain point for domestic production, which has led to the exploration of alternative low-cost, portable platforms capable of detecting target metals during resource prospecting and downstream process monitoring. The National Energy Technology Laboratory has developed a portable fiber optic-based luminescence spectrometer that utilizes a metal-organic framework (MOF) material to detect and distinguish parts-per-billion levels of the visible-emitting rare earth elements terbium, dysprosium, samarium, and europium, which are all economically critical metals. Although preliminary results with this system are promising, a crucial barrier to practical deployment is the ability to operate in low pH, high ionic strength environments, as acidic conditions and the presence of other metal ions can significantly reduce luminescence signal. Here, current strategies related to sample treatment, material design, and sensor configuration are discussed in the context of improving sensor performance in application-relevant conditions. Additionally, future opportunities, such as the optimization of the sensing binding environment through computational methods and specific metals to be removed for treatment will be discussed, presenting a forward-looking view for innovation in luminescent sensing of critical metals.

36 MATERIALS SCIENCE↗

An Optical Spectrum of the Diffuse Galactic Light from BOSS and IRIS

We present a spectrum of the diffuse Galactic light (DGL) between 3700 and 10,000 Å, obtained by correlating optical sky intensity with far-infrared dust emission. We use nearly 250,000 blank-sky spectra from BOSS/SDSS-III together with IRIS-reprocessed maps from the IRAS satellite. The larger sample size compared to SDSS-II results in a factor-of-2 increase in signal to noise. We combine these data sets with a model for the optical/far-infrared correlation that accounts for self-absorption by dust. The spectral features of the DGL agree remarkably well with the features present in stellar spectra. There is evidence for a difference in the DGL continuum between the regions covered by BOSS in the northern and southern Galactic hemispheres. We interpret the difference at red wavelengths as the result of a difference in stellar populations, with mainly old stars in both regions, but a higher fraction of young stars in the south. There is also a broad excess in the southern DGL spectrum over the prediction of a simple radiative transfer model, without a clear counterpart in the north. We interpret this excess, centered at ~6500 Å, as evidence for luminescence in the form of extended red emission. The observed strength of the 4000 Å break indicates that at most ~7% of the dust-correlated light at 4000 Å can be due to blue luminescence. Our DGL spectrum provides constraints on dust scattering and luminescence, independent of measurements of extinction.

79 ASTRONOMY AND ASTROPHYSICS↗

Testing the Fraunhofer line discriminator by sensing fluorescent dye

The experimental Fraunhofer Line Discriminator (FLD) has detected increments of Rhodamine WT dye as small as 1 ppb in 1/2 meter depths. It can be inferred that increments considerably smaller than 1 ppb will be detectable in depths considerably greater than 1/2 meter. Turbidity of the water drastically reduces luminescence or even completely blocks the transmission of detectable luminescence to the FLD. Attenuation of light within the water by turbidity and by the dye itself are the major factors to be considered in interpreting FLD records and in relating luminescence coefficient to dye concentration. An airborne test in an H-19 helicopter established feasibility of operating the FLD from the aircraft power supply, and established that the rotor blades do not visibly affect the monitoring of incident solar radiation.

Stoertz, G. E.↗

Hibonite, Ca2/Al, Ti/24O38, from the Leoville and Allende chondritic meteorites.

Hibonite was discovered in light-colored, Ca-Al-Ti-rich and Si-Fe-poor, achondritic inclusions of the Leoville and Allende HL-group chondrites. Two varieties of hibonite occur: one emits a bright red-orange luminescence under electron bombardment and has high amounts of Al2O3 (87.7; 87.9) and low amounts of MgO (0.65; 0.8) and TiO2 (0.68; 0.8). The other emits a bright blue luminescence and is low in Al2O3 (78.7; 79.2) and high in MgO (3.3; 3.7) and TiO2 (6.5; 7.9) (in wt. %). The oxide CaO is about the same in both varieties. It is suggested that the change in the color of the visible luminescence results from changes in composition. The origin of hibonite which occurs in complex mineral assemblages together with anorthite, gelhenite, wollastonite, aluminous diopside, andradite, Ca-pyroxene, perovskite, spinel, taenite, chromite, and pentlandite, and in close proximity to nodules containing calcite, whewellite, forsterite and many of the aforementioned phases, is discussed. The proposition that hibonite and associated phases originated by contact metamorphism and metasomatism of calcite-dolomite bearing assemblages cannot, at this time, be completely ruled out.

Keil, K.↗

Ion microprobe, electron microprobe and cathodoluminescence data for Allende inclusions with emphasis on plagioclase chemistry

Three Type B inclusions from the Allende meteorite have been analyzed. A grain-to-grain characterization of mineral chemistry and isotopic content was made possible by the use of a range of techniques, including luminescence and scanning electron microscopy and electron and ion microprobe analysis. Cathodoluminescence was used in fine-grained, optically opaque regions to distinguish between sub-micrometer phases, such as garnet and Si-rich material, subsequently identified by electron probe and scanning electron microscope analyses. Four types of luminescence patterns, due to twinning, primary sector zoning, alteration of boundaries and fractures, and shock effects, were identified in Allende plagioclase. Luminescence color exhibited a strong correlation with Mg content and provided a guide for an electron probe quantitative map of Mg and Na distributions. Ion microprobe studies of individual grains revealed large excesses of Mg-26.

Hutcheon, I. D.↗

Pressure-sensitive paint measurements on a supersonic high-sweep oblique wing model

The pressure-sensitive paint method was used in the test of a high-sweep oblique wing model, conducted in the NASA Ames 9- by 7-ft Supersonic Wind Tunnel. Surface pressure data was acquired from both the luminescent paint and conventional pressure taps at Mach numbers between M = 1.6 and 2.0. In addition, schlieren photographs of the outer flow were used to determine the location of shock waves impinging on the model. The results show that the luminescent pressure-sensitive paint can capture both global and fine features of the static surface pressure field. Comparison with conventional pressure tap data shows good agreement between the two techniques, and that the luminescent paint data can be used to make quantitative measurements of the pressure changes over the model surface. The experiment also demonstrates the practical considerations and limitations that arise in the application of this technique under supersonic flow conditions in large-scale facilities, as well as the directions in which future research is necessary in order to make this technique a more practical wind-tunnel testing tool.

McLachlan, B. G.↗

Fluorescence of Pentavalent Chromium in SiO2 Sol-Gel Glasses

Chromium ions are very attractive to optical spectroscopy and laser physics. It is well known that the first laser in the history is a ruby laser activated with Cr(3+). It was found in early nineties that Cr(4+) was also an interesting lasing ion in the near infrared, and various Cr(4+) lasers have been developed. Very recently, it was reported that Cr(2+) doped in CdSe crystals showed lasing action in the infrared. The above achievement have stimulated an interest in searching for Cr(5+) and investigating its optical properties. Cr(5+) is isoelectronic with Ti(3+) and V(4+), having electron configuration 3d1. Ti(3+) is the active center of commercial cw and femtosecond sapphire lasers, tunable in the range 680-1100 nm. V(4+) doped in YAlO3 and Al2O3 showed broad band emission near 635 nm. Although EPR results of Cr(5+) were reported, the optical properties were less studied. Herren et al. reported an observation of luminescence from Cr doped in SiO2 sol-gel glass. The luminescence spectrum was assigned to pentavalent ions in their first paper, and later it was identified to be the emission from the charge transfer transition of Cr(6+). The first observation of photoluminescence from octahedrally coordinated Cr(5+) in BaCaMg aluminate glasses was reported very recently. In this work, we report luminescence results of Cr doped SiO2 sol-gel glasses. The fluorescence spectra are very different from Herrens' results, and we believe it originates from pentavalent Cr.

Jia, Weiyi↗

Using Temperature Sensitive Paint Technology

New facilities and test techniques afford research aerodynamicists many opportunities to investigate complex aerodynamic phenomena. For example, NASA Langley Research Center's National Transonic Facility (NTF) can hold Mach number, Reynolds number, dynamic pressure, stagnation temperature and stagnation pressure constant during testing. This is important because the wing twist associated with model construction may mask important Reynolds number effects associated with the flight vehicle. Beyond this, the NTF's ability to vary Reynolds number allows for important research into the study of boundary layer transition. The capabilities of facilities such as the NTF coupled with test techniques such as temperature sensitive paint yield data that can be applied not only to vehicle design but also to validation of computational methods. Development of Luminescent Paint Technology for acquiring pressure and temperature measurements began in the mid-1980s. While pressure sensitive luminescent paints (PSP) were being developed to acquire data for aerodynamic performance and loads, temperature sensitive luminescent paints (TSP) have been used for a much broader range of applications. For example, TSP has been used to acquire surface temperature data to determine the heating due to rotating parts in various types of mechanical systems. It has been used to determine the heating pattern(s) on circuit boards. And, it has been used in boundary layer analysis and applied to the validation of full-scale flight performance predictions. That is, data acquired on the same model can be used to develop trends from off design to full scale flight Reynolds number, e.g. to show the progression of boundary layer transition. A discussion of issues related to successfully setting-up TSP tests and using TSP systems for boundary layer studies is included in this paper, as well as results from a variety of TSP tests. TSP images included in this paper are all grey-scale so that similar to pictures from sublimating chemical tests areas of laminar flow appear "lighter," or white, and areas of turbulent flow appear "darker."

Hamner, M. P.↗

Diffusion Time-Scale of Porous Pressure-Sensitive Paint

Pressure-sensitive paint (PSP) is an optical pressure sensor that utilizes the oxygen quenching of luminescence. PSP measurements in unsteady aerodynamic flows require fast time response of the paint. There are two characteristic time-scales that are related to the time response of PSP. One is the luminescent lifetime representing an intrinsic physical limit for the achievable temporal resolution of PSP. Another is the time-scale of oxygen diffusion across the PSP layer. When the time-scale of oxygen diffusion is much larger than the luminescent lifetime, the time response of PSP is controlled by oxygen diffusion. In a thin homogenous polymer layer where diffusion is Fickian, the oxygen concentration 1021 can be described by the diffusion equation in one-dimension.

Liu, Tianshu↗

Atmospheric Electron-induced X-Ray Spectrometer (AEXS) Instrument Development

Instrument Development: The membrane properties were investigated in detail due to its critical role. A series of experiments determined that our designed membranes have high electron transmission, yet are capable of isolating high vacuum, are able to withstand differential pressure in excess of one atmosphere, survive vibrational shocks of a magnitude to be expected during a planetary mission. Our initial work has been with a 10 keV source and a 200 nm thick Silicon Nitride (SiN) encapsulation membrane micro-fabricated within a Si support frame (1.5 mm x 1.5 mm window openings. Fig 2 compares the spectra taken with the 10 keV source with spectra taken within SEM. Introduction: This paper describes the progress in the development of the AEXS instrument in our laboratory at JPL. The AEXS is a novel miniature instrument[1-3] based on the excitation of characteristic X-Ray Fluorescence (XRF) and luminescence spectra using a focused electron beam, for non-destructive evaluation of surfaces of samples in planetary ambient atmosphere. In situ operation is obtained through the use of a thin electron transmissive membrane to isolate the vacuum within the AEXS electron source from the outside ambient atmosphere. The impinging electrons excite XRF spectra from the irradiated spots on samples in external atmosphere with high-to-medium (sub-mm to cm-scale) spatial resolution at Mars atmospheric pressure. The XRF spectra are analyzed using an energy-dispersive detector to determine surface elemental composition, or in the case of electron-induced luminescence to identify unusual formations on surface that cathodo-luminescence (CL). The AEXS system (Fig 1) consists of a high-energy (>10keV) electron gun encapsulated by the isolation membrane, an EDX detection and analyzer system to determine the elemental abundance, an optional CL detection system, and a high voltage power supply. The approach to demonstrating a proof of concept of the AEXS has been through 1) demonstrating the viability of micro-fabricated membranes, 2) assembling AEXS setups with increasingly integrated functional components, and 3) simulating the AEXS observational capabilities. This paper will focus on description of the development of the instrument.

Wilcox, J. Z.↗

Nanorod-Based Fast-Response Pressure-Sensitive Paints

A proposed program of research and development would be devoted to exploitation of nanomaterials in pressuresensitive paints (PSPs), which are used on wind-tunnel models for mapping surface pressures associated with flow fields. Heretofore, some success has been achieved in measuring steady-state pressures by use of PSPs, but success in measuring temporally varying pressures has been elusive because of the inherent slowness of the optical responses of these materials. A PSP contains a dye that luminesces in a suitable wavelength range in response to photoexcitation in a shorter wavelength range. The luminescence is quenched by oxygen at a rate proportional to the partial pressure of oxygen and thus proportional to the pressure of air. As a result, the intensity of luminescence varies inversely with the pressure of air. The major problem in developing a PSP that could be easily applied to a wind-tunnel model and could be useful for measuring rapidly varying pressure is to provide very high gas diffusivity for rapid, easy transport of oxygen to and from active dye molecules. Most PSPs include polymer-base binders, which limit the penetration of oxygen to dye molecules, thereby reducing responses to pressure fluctuations. The proposed incorporation of nanomaterials (somewhat more specifically, nanorods) would result in paints having nanostructured surfaces that, relative to conventional PSP surfaces, would afford easier and more nearly complete access of oxygen molecules to dye molecules. One measure of greater access is effective surface area: For a typical PSP as proposed applied to a given solid surface, the nanometer-scale structural features would result in an exposed surface area more than 100 times that of a conventional PSP, and the mass of proposed PSP needed to cover the surface would be less than tenth of the mass of the conventional PSP. One aspect of the proposed development would be to synthesize nanorods of Si/SiO2, in both tangle-mat and regular- array forms, by use of chemical vapor deposition (CVD) and wet chemical processes, respectively. The rods would be coated with a PSP dye, and the resulting PSP signals would be compared with those obtained from PSP dye coats on conventional support materials. Another aspect of the proposed development would be to seek to exploit the quantum properties of nanorods of a suitable semiconductor (possibly GaN), which would be synthesized by CVD. These quantum properties of semiconductor nanorods include narrow-wavelength-band optical absorption and emission characteristics that vary with temperature. The temperature sensitivity might enable simultaneous measurement of fluctuating temperature and pressure and to provide a temperature correction for the PSP response.

Bencic, Timothy↗

Continued Development of Compact Multi-Gas Monitor for Life Support Systems Control in Space

Miniature optic gas sensors (MOGS) based on luminescent materials have shown great potential as alternatives to NIR-based gas sensor systems for the Portable Life Support System (PLSS). The unique capability of MOGS for carbon dioxide and oxygen monitoring under wet conditions has been reported, as has the fast recovery of MOGS humidity sensors after long periods of being wet. Lower volume and power requirements are also potential advantages of MOGS over both traditional and advanced Non-Dispersive Infrared (NDIR) gas sensors, which have shown so far longer life than luminescent sensors. In this paper we present the most recent results in the development and analytical validation of a compact multi-gas sensor unit based on luminescent sensors for the PLSS. Results of extensive testing are presented, including studies conducted at Intelligent Optical Systems laboratories, a United Technology Corporation Aerospace Systems (UTAS) laboratory, and a Johnson Space Center laboratory. The potential of this sensor technology for gas monitoring in PLSSs and other life support systems and the advantages and limitations found through detailed sensor validation are discussed.

Delgado, Jesus↗

Continued Development of Compact Multi-gas Monitor for Life Support Systems Control in Space

Miniature optic gas sensors (MOGS) based on luminescent materials have shown great potential as alternatives to Near-Infrared-based gas sensor systems for the advanced space suit portable life support system (PLSS). The unique capability of MOGS for carbon dioxide and oxygen monitoring under wet conditions has been reported, as has the fast recovery of MOGS humidity sensors after long periods of being wet. Lower volume and power requirements are also potential advantages of MOGS over both traditional and advanced Non-Dispersive Infrared (NDIR) gas sensors, which have shown so far longer life than luminescent sensors. This paper presents the most recent results in the development and analytical validation of a compact multi-gas sensor unit based on luminescent sensors for the PLSS. Results of extensive testing are presented, including studies conducted at Intelligent Optical Systems laboratories, a United Technology Corporation Aerospace Systems (UTAS) laboratory, and a Johnson Space Center laboratory. The potential of this sensor technology for gas monitoring in PLSSs and other life support systems and the advantages and limitations found through detailed sensor validation are discussed.

Delgado-Alonso, Jesús↗