Metal-organic frameworks (MOFs) have recently been shown to exhibit unique mechanisms of luminescence based on charge transfer between structural units in the framework. These MOFs have the potential to be structural tuned for targeted emission with little or no metal participation. A computationally led, material design and synthesis methodology is presented here that elucidates the mechanisms of light emission in interpenetrated structures comprised of metal centers (M = In, Ga, InGa, InEu) and BTB (1,3,5-Tris(4-carboxyphenyl)benzene) linkers, forming unique luminescent M-BTB MOF frameworks. Gas phase and periodic electronic structure calculations indicate that the intensity of the emission and the wavelength are overwhelmingly controlled by a combination of the number of interacting stacked linkers and their interatomic spacings, respectively. In the MOF, the ionic radii of the metal centers primarily control the expansion or shrinkage of the linker stacking distances. Experimentally, multiple M-BTB-based MOFs are synthesized and their photoluminescence was tested. Experiments validated the modeling by confirming that shifts in the crystal structure result in variations in light emission. Through this material design method, the mechanisms of tuning luminescence properties in interpenetrated M-BTB MOFs have been identified and applied to the design of MOFs with specific wavelength emission based on their structure.
Optical anticounterfeiting tags utilize the photoluminescent properties of materials to encode unique patterns, enabling identification and validation of important items and assets. These tags must combine optical complexity with ease of production and authentication to both prevent counterfeiting and to remain practical for widespread use. Metal-organic frameworks (MOFs) based on polynuclear, rare earth clusters are ideal materials platforms for this purpose, combining fine control over structure and composition, with tunable, complex energy transfer mechanisms via both linker and metal components. Here we report the design and synthesis of a set of heterometallic MOFs based on combinations of Eu, Nd, and Yb with the tetratopic linker 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene. The energetics of this linker facilitate the intentional concealment of the visible emissions from Eu while retaining the infrared emissions of Nd and Yb, creating an optical tag with multiple covert elements. Unique to the materials system reported herein, we document the occurrence of a previously not observed 11-metal cluster correlated with the presence of Yb in the MOFs, coexisting with a commonly encountered 9-metal cluster. We demonstrate the utility of these materials as intricate optical tags with both rapid and in-depth screening techniques, utilizing orthogonal identifiers across composition, emission spectra, and emission decay dynamics. This work highlights the important effect of linker selection in controlling the resulting photoluminescent properties in MOFs and opens an avenue for the targeted design of highly complex, multifunctional optical tags.
Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Herein we report a design strategy to encode multilayer complexity in a family of heterometallic rare-earth metal–organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near-infrared, NIR) properties, with concomitant multi-emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult-to-counterfeit optical tags.
A novel metal-organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE-Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV-Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal X-ray diffraction (SCXRD), scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.
Commercial-Off-The-Shelf (COTS) electronics offer cutting-edge capability at lower prices compared to their space-grade counterparts. However, their use in space missions has been limited due to concerns around survivability in a space environment; COTS devices are not designed to survive the harsh radiation environment of space. Nonetheless, for space missions with short durations it may be possible to use COTS electronics. This study evaluates the use of several families of COTS electronics for a specific short-term mission. An assembled database including selected space grade and COTS components is discussed. High confidence FPGAs, microprocessors, and optocouplers COTS are identified. Medium confidence Memory, ADCs, DACs, power electronics, and RFMMICs COTS are also included, as well as testing to improve confidence in medium confidence parts. An experimental approach for evaluating tin whisker susceptibility for tin-leaded COTS components is described. Using COTS electronics in Short-Term Geostationary Satellites is feasible; this report includes enabling tools.
Muniz, Collin N.; Patel, Hiral; Fast, Dylan B.; Rohwer, Lauren E.; Reinheimer, Eric W.; Dolgos, Michelle; Graham, Matt W.; Nyman, May
Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. Here we described the synthesis of a heterometallic rare-earth coordination compound ((CH3)2SO)3(RE)NbO(C2O4)3 ((CH3)2SO) = dimethylsulfoxide, DMSO, (C2O2 = oxalate), (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb). The structure was obtained from single crystal X-ray diffraction of the La analogue. The NbËO and DMSO terminal-bonding character guides assembly of an open framework structure with noncentrosymmetric RE-coordination geometry, and large spacing between the RE centers. A second structure was observed by PXRD for the smaller rare earths (Dy, Ho, Er, Yb); this structure has not yet been determined. The materials were further characterized using FTIR, and photoluminescence measurements. Characteristic excitation and emission transitions were observed for RE = Nd, Sm, Eu, and Tb. Quantum yield (QY) measurements were performed by exciting Eu and Tb analoges at 394 nm (QY 66%) and 464 nm (QY 71%) for Eu; and 370 nm (QY=40%) for Tb. We attribute the high QY and bright luminescence to two main structure-function properties of the system; namely the absence of water in the structure, and absence of concentration quenching.
Herein, we describe a novel multifunctional metal–organic framework (MOF) materials platform that displays both porosity and tunable emission properties as a function of the metal identity (Eu, Nd, and tuned compositions of Nd/Yb). Their emission collectively spans the deep red to near-infrared (NIR) spectral region (~614–1350 nm), which is highly relevant for in vivo bioimaging. These new materials meet important prerequisites as relevant to biological processes: they are minimally toxic to living cells and retain structural integrity in water and phosphate-buffered saline. To assess their viability as optical bioimaging agents, we successfully synthesized the nanoscale Eu analog as a proof-of-concept system in this series. In vitro studies show that it is cell-permeable in individual RAW 264.7 mouse macrophage and HeLa human cervical cancer tissue culture cells. The efficient discrimination between the Eu emission and cell autofluorescence was achieved with hyperspectral confocal fluorescence microscopy, used here for the first time to characterize MOF materials. Importantly, this is the first report that documents the long-term conservation of the intrinsic emission in live cells of a fluorophore-based MOF to date (up to 48 h). As a result this finding, in conjunction with the materials’ very low toxicity, validates the biocompatibility in these systems and qualifies them as promising for use in long-term tracking and biodistribution studies.
The bearings used in energy storage flywheels dissipate a significant amount of energy and can fail catastrophically. Magnetic bearings would both reduce energy dissipation and increase flywheel reliability. The component of magnetic bearing that creates lift is a magnetically soft material embedded into a rebate cut into top of the inner annulus of the flywheel. Because the flywheels stretch about 1% as they spin up, this magnetic material must also stretch and be more compliant than the flywheel itself, so it does not part from the flywheel during spin up. At the same time, the material needs to be sufficiently stiff that it does not significantly deform in the rebate and must have a sufficiently large magnetic permeability and saturation magnetization to provide the required lift. It must also have high electrical resistivity to prevent heating due to eddy currents. In this paper we investigate whether adequately magnetic, mechanically stiff composites that have the tensile elasticity, high electrical resistivity, permeability and saturation magnetism required for flywheel lift magnet applications can be fabricated. We find the best composites are those comprised of bidisperse Fe particles in the resin G/Flex 650. The primary limiting factor of such materials is the fatigue resistance to tensile strain.
Reliable methods for tin whisker mitigation are needed for applications that utilize tin-plated commercial components. Tin can grow whiskers that can lead to electrical shorting, possibly causing critical systems to fail catastrophically. The mechanisms of tin whisker growth are unclear and this makes prediction of the lifetimes of critical components uncertain. The development of robust methods for tin whisker mitigation is currently the best approach to eliminating the risk of shorting. Current mitigation methods are based on unfilled polymer coatings that are not impenetrable to tin whiskers. In this paper we report tin whisker mitigation results for several filled polymer coatings. The whisker-penetration resistance of the coatings was evaluated at elevated temperature and high humidity and under temperature cycling conditions. The composite coatings comprised Ni and MgF2-coated Al/Ni/Al platelets in epoxy resin or silicone rubber. In addition to improved whisker mitigation, these platelet composites have enhanced thermal conductivity and dielectric constant compared with unfilled polymers.
II-VI quantum dots, such as CdSe and CdTe, are attractive as downconversion materials for solid-state lighting, because of their narrow linewidth, tunable emission. However, for these materials to have acceptable quantum yields (QYs) requires that they be coated with a II-VI shell material whose valence band offset serves to confine the hole to the core. Confinement prevents the hole from accessing surface traps that lead to nonradiative decay of the exciton. Examples of such hole-confined core/shell QDs include CdTe/CdSe and CdSe/CdS. Unfortunately, the shell can also cause problems due to lattice mismatch, which ranges from 4-6% for systems of interest. This lattice mismatch can create significant interface energies at the heterojunction and places the core under radial compression and the shell under tangential tension. At elevated temperatures (~240°C) interfacial diffusion can relax these stresses, as can surface reconstruction, which can expose the core, creating hole traps. But such high temperatures favor the hexagonal Wurtzite structure, which has lower QY than the cubic zinc blende structure, which can be synthesized at lower temperatures, ~140°C. In the absence of alloying the core/shell structure can become metastable, or even unstable, if the shell is too thick. This can cause result in an irregular shell or even island growth. But if the shell is too thin thermallyactivated transport of the hole to surface traps can occur. In our LDRD we have developed a fundamental atomistic modeling capability, based on Stillinger-Weber and Bond-Order potentials we developed for the entire II-VI class. These pseudo-potentials have enabled us to conduct large-scale atomistic simulations that have led to the computation of phase diagrams of II-VI QDs. These phase diagrams demonstrate that at elevated temperatures the zinc blende phase of CdTe with CdSe grown on it epitaxially becomes thermodynamically unstable due to alloying. This is accompanied by a loss of hole confinement and a severe drop in the QY and emission lifetime, which is confirmed experimentally for the zinc blende core/shell QDs prepared at low temperatures. These QDs have QYs as high as 95%, which makes them very attractive for lighting. Finally, to address strain relaxation in these materials we developed a model for misfit dislocation formation that we have validated through atomistic simulations.
An ideal red phosphor for blue LEDs is one of the biggest challenges for the solid-state lighting industry. The appropriate phosphor material should have good adsorption and emission properties, good thermal and chemical stability, minimal thermal quenching, high quantum yield, and is preferably inexpensive and easy to fabricate. Tantalates possess many of these criteria, and lithium lanthanum tantalate materials warrant thorough investigation. In this study, we investigated red luminescence of two lithium lanthanum tantalates via three mechanisms: (1) Eu-doping, (2) Mn-doping and (3) self-activation of the tantalum polyhedra. Of these three mechanisms, Mn-doping proved to be the most promising. These materials exhibit two very broad adsorption peaks; one in the UV and one in the blue region of the spectrum; both can be exploited in LED applications. Furthermore, Mn-doping can be accomplished in two ways; ion-exchange and direct solid-state synthesis. One of the two lithium lanthanum tantalate phases investigated proved to be a superior host for Mn-luminescence, suggesting the crystal chemistry of the host lattice is important.
This late-start LDRD explores chemical strategies that will enable sub-micron alignment accuracy of dies and wafers by exploiting the interfacial energies of chemical ligands. We have micropatterned commensurate features, such as 2-d arrays of micron-sized gold lines on the die to be bonded. Each gold line is functionalized with alkanethiol ligands before the die are brought into contact. The ligand interfacial energy is minimized when the lines on the die are brought into registration, due to favorable interactions between the complementary ligand tails. After registration is achieved, standard bonding techniques are used to create precision permanent bonds. We have computed the alignment forces and torque between two surfaces patterned with arrays of lines or square pads to illustrate how best to maximize the tendency to align. We also discuss complex, aperiodic patterns such as rectilinear pad assemblies, concentric circles, and spirals that point the way towards extremely precise alignment.
This SAND report is the final report on Sandia's Grand Challenge LDRD Project 27328, 'A Revolution in Lighting -- Building the Science and Technology Base for Ultra-Efficient Solid-state Lighting.' This project, which for brevity we refer to as the SSL GCLDRD, is considered one of Sandia's most successful GCLDRDs. As a result, this report reviews not only technical highlights, but also the genesis of the idea for Solid-state Lighting (SSL), the initiation of the SSL GCLDRD, and the goals, scope, success metrics, and evolution of the SSL GCLDRD over the course of its life. One way in which the SSL GCLDRD was different from other GCLDRDs was that it coincided with a larger effort by the SSL community - primarily industrial companies investing in SSL, but also universities, trade organizations, and other Department of Energy (DOE) national laboratories - to support a national initiative in SSL R&D. Sandia was a major player in publicizing the tremendous energy savings potential of SSL, and in helping to develop, unify and support community consensus for such an initiative. Hence, our activities in this area, discussed in Chapter 6, were substantial: white papers; SSL technology workshops and roadmaps; support for the Optoelectronics Industry Development Association (OIDA), DOE and Senator Bingaman's office; extensive public relations and media activities; and a worldwide SSL community website. Many science and technology advances and breakthroughs were also enabled under this GCLDRD, resulting in: 55 publications; 124 presentations; 10 book chapters and reports; 5 U.S. patent applications including 1 already issued; and 14 patent disclosures not yet applied for. Twenty-six invited talks were given, at prestigious venues such as the American Physical Society Meeting, the Materials Research Society Meeting, the AVS International Symposium, and the Electrochemical Society Meeting. This report contains a summary of these science and technology advances and breakthroughs, with Chapters 1-5 devoted to the five technical task areas: 1 Fundamental Materials Physics; 2 111-Nitride Growth Chemistry and Substrate Physics; 3 111-Nitride MOCVD Reactor Design and In-Situ Monitoring; 4 Advanced Light-Emitting Devices; and 5 Phosphors and Encapsulants. Chapter 7 (Appendix A) contains a listing of publications, presentations, and patents. Finally, the SSL GCLDRD resulted in numerous actual and pending follow-on programs for Sandia, including multiple grants from DOE and the Defense Advanced Research Projects Agency (DARPA), and Cooperative Research and Development Agreements (CRADAs) with SSL companies. Many of these follow-on programs arose out of contacts developed through our External Advisory Committee (EAC). In h s and other ways, the EAC played a very important role. Chapter 8 (Appendix B) contains the full (unedited) text of the EAC reviews that were held periodically during the course of the project.
An optical sensor system has been developed for the autonomous monitoring of NO{sub 2} evolution in energetic material aging studies. The system is minimally invasive, requiring only the presence of a small sensor film within the aging chamber. The sensor material is a perylene/PMMA film that is excited by a blue LED light source and the fluorescence detected with a CCD spectrometer. Detection of NO{sub 2} gas is done remotely through the glass window of the aging chamber. Irreversible reaction of NO{sub 2} with perylene, producing the non-fluorescent nitroperylene, provides the optical sensing scheme. The rate of fluorescence intensity loss over time can be modeled using a numerical solution to the coupled diffusion and a nonlinear chemical reaction problem to evaluate NO{sub 2} concentration levels. The light source, spectrometer, spectral acquisition, and data processing were controlled through a Labivew program run by a laptop PC. Due to the long times involved with materials aging studies the system was designed to turn on, warm up, acquire data, power itself off, then recycle at a specific time interval. This allowed the monitoring of aging HE material over the period of several weeks with minimal power consumption and stable LED light output. Despite inherent problems with gas leakage of the aging chamber they were able to test the sensor system in the field under an accelerated aging study of rocket propellant. They found that the propellant evolved NO{sub 2} at a rate that yielded a concentration of between 10 and 100 ppm. The sensor system further revealed that the propellant, over an aging period of 25 days, evolves NO{sub 2} with cyclic behavior between active and dormant periods.
The past several years rendered a resurgence of interest in phosphors for low-voltage flat panel displays utilizing cathodoluminescence (CL). A major selection criterion for these phosphors is CL efficiency. The objective is to maximize the efficiency at low voltages. This work focuses on understanding the materials properties that influence CL efficiency below 1 kV. Existing high-voltage CL efficiency models take into account intrinsic materials properties such as band-gap energy. Experimental data reveals that the CL efficiency also depends on physical properties such as particle and crystallite size. An update, predictive model of CL efficiency that includes the effects of crystallite size, radiative recombination probability, and electron accelerating potential was developed. The predicted efficiencies agree very well with experimental results. The experimental data were collected using a hot filament electron gun in a demountable high-vacuum chamber. To obtain measurement accuracy, secondary electrons were collected and the phosphor excited with a uniform beam profile. A CL characterization protocol for display phosphors was established at Sandia National Laboratories and made available to phosphor researchers.
Fine particle porous {alpha}-alumina has been prepared by a wet chemical method of combustion synthesis using an aqueous precursor containing aluminum nitrate (oxidizer) and carbohydrazide, an organic fuel as starting materials. The aluminum nitrate and carbohydrazide were reacted exothermically at 400--600 C. The synthesis of {alpha}-alumina ({alpha}-Al{sub 2}O{sub 3}) was used as a model for understanding the effects of processing parameters on physical properties such as surface area, average pore size, and residual carbon content. The porous powders were characterized using x-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area analysis and elemental analysis. The decomposition of the starting materials was investigated using differential thermal and thermogravimetric analyses (DTA/TGA). It has been shown that the furnace temperature, fuel/oxidizer ratio, and precursor water content can be tailored to produce powders with different physical properties.