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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Protonierung von CH 3 N 3 und CF 3 N 3 in Supersäuren: Isolierung und strukturelle Charakterisierung von langlebigen Methyl‐ und Trifluormethylamino‐Diazonium‐Ionen

Abstract Die Methylaminodiazonium‐Kationen [CH 3 N(H)N 2 ] + und [CF 3 N(H)N 2 ] + wurden als ihre bei niedriger Temperatur stabilen [AsF 6 ]‐Salze durch Protonierung von Azidomethan und Azidotrifluormethan in supersauren Systemen hergestellt. Sie wurden durch NMR‐ und Raman‐Spektroskopie charakterisiert. Ein eindeutiger Nachweis der Protonierungsstelle wurde durch die Kristallstrukturen beider Salze erhalten, welche die Bildung der Alkylaminodiazonium‐Ionen bestätigte. Die Lewis‐Addukte CH 3 N 3 ⋅AsF 5 und CF 3 N 3 ⋅AsF 5 wurden ebenfalls hergestellt und durch Tieftemperatur‐NMR‐ und Raman‐Spektroskopie sowie im Falle von CH 3 N 3 ⋅AsF 5 durch Röntgenstrukturbestimmung charakterisiert. Elektronische Strukturberechnungen wurden durchgeführt, um zusätzliche Einblicke zu erhalten. Versuche zur elektrophilen Aminierung von Aromaten wie Benzol und Toluol mit Methyl‐ und Trifluormethylamino‐Diazonium‐Ionen waren erfolglos.

Saal, Thomas↗
DOE OSTI2020

Protonation of CH 3 N 3 and CF 3 N 3 in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions

Abstract The methylamino diazonium cations [CH 3 N(H)N 2 ] + and [CF 3 N(H)N 2 ] + were prepared as their low‐temperature stable [AsF 6 ] − salts by protonation of azidomethane and azidotrifluoromethane in superacidic systems. They were characterized by NMR and Raman spectroscopy. Unequivocal proof of the protonation site was obtained by the crystal structures of both salts, confirming the formation of alkylamino diazonium ions. The Lewis adducts CH 3 N 3 ⋅AsF 5 and CF 3 N 3 ⋅AsF 5 were also prepared and characterized by low‐temperature NMR and Raman spectroscopy, and also by X‐ray structure determination for CH 3 N 3 ⋅AsF 5 . Electronic structure calculations were performed to provide additional insights. Attempted electrophilic amination of aromatics such as benzene and toluene with methyl‐ and trifluoromethylamino diazonium ions were unsuccessful.

Saal, Thomas↗
DOE OSTI2020

Single crystal neutron and magnetic measurements of Rb 2 Mn 3 (VO 4 ) 2 CO 3 and K 2 Co 3 (VO 4 ) 2 CO 3 with mixed honeycomb and triangular magnetic lattices

Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I, Rb 2 Mn 3 (VO 4 ) 2 CO 3 , crystallizes in the trigonal crystal system in the space group P[3 with combining macron]1c, and compound II, K 2 Co 3 (VO 4 ) 2 CO 3 , crystallizes in the hexagonal space group P6 3 /m. Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO 6 octahedra and MO 5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c-axis through tetrahedral [VO 4 ] groups. The MO 5 units are connected with each other by carbonate groups in the ab-plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO 6 -honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO 5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K 2 Co 3 (VO 4 ) 2 CO 3 (II) exhibits a canted antiferromagnetic ordering below T N = 8 K. Here, the Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of –42 K suggesting a dominant antiferromagnetic coupling in the Co 2+ magnetic sublattices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Insulating band gaps both below and above the Néel temperature in d -electron LaTi O 3 , LaV O 3 , SrMn O 3 , and LaMn O 3 perovskites as a symmetry-breaking event

Metal d-electron oxides having an odd number of electrons per cell should exhibit band degeneracy at the Fermi energy, making them, in band theory, formally metallic. In many cases, however, these are “false metals”, as evidenced by the observation that many ABO 3 oxide perovskites with a magnetic 3d B-atom are observed to be insulators both below and above the Néel temperature. These inconsistencies between experimental observation and expectation have historically been resolved by invoking degeneracy-breaking physics, based largely on -pure electron effects, such as strong interelectronic correlation for d-electron compounds (the Mott mechanism). Such explanations generally consider microscopic lattice or magnetic degrees of freedom (m-DOF) as largely passive spectators, not a cause of the formally metallic being an insulator. Yet, it has long been known that ABO 3 perovskites can manifest an arrangement of m-DOFs in the form of octahedral tilting, bond dimerization, Jahn-Teller distortions, and ordering of local magnetic moments. It appears reasonable that such structural and magnetic local degrees of freedom need to be allowed to compete with purely electronic strong correlation. To answer this question, we explored a range of d-electron oxide perovskites exemplified by the archetypes LaTiO 3 , LaVO 3 , SrMnO 3 , and LaMnO 3 with 1, 2, 3, or 4 d -electrons, respectively. Using a mean-field-like electronic structure method (here, density functional theory), we find that a combination of magnetic symmetry breaking with structural distortions can account for insulating band gaps in this series while at the same time correctly predicting for the control case an intrinsic paramagnetic metal in SrVO 3 as symmetry-breaking is insufficiently strong to remove the degeneracy. Finally, this indicates that calculating quantitatively local magnetic and positional symmetry-breaking motifs in unit cells that avoid averaging at the outset over the low symmetry motifs can provide consistent trends in a Mott transition without Mott U.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Pascal conductance series in ballistic one-dimensional LaAlO 3 /SrTiO 3 channels

One-dimensional electronic systems can support exotic collective phases because of the enhanced role of electron correlations. We describe the experimental observation of a series of quantized conductance steps within strongly interacting electron waveguides formed at the lanthanum aluminate–strontium titanate (LaAlO 3 /SrTiO 3 ) interface. The waveguide conductance follows a characteristic sequence within Pascal’s triangle: (1, 3, 6, 10, 15, …) e 2 /h , where e is the electron charge and h is the Planck constant. This behavior is consistent with the existence of a family of degenerate quantum liquids formed from bound states of n = 2, 3, 4, … electrons. Our experimental setup could provide a setting for solid-state analogs of a wide range of composite fermionic phases.

Science & Technology - Other Topics↗
DOE OSTI2026

Iodine Close Packing in Hybrid Halide Bismuth(III) and Antimony(III) Semiconductors: (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10

Simple features in complex hybrid inorganic–organic crystalline materials provide opportunities for targeted discovery of materials with desired optoelectronic properties. In this study, we report the structure and optoelectronic properties of isostructural (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10 . The crystal structures are characterized by corner-connected metal-iodide octahedral chains that form a cubic close-packed iodine inorganic framework. Variable temperature UV–visible diffuse reflectance spectroscopy reveals stark contrasts in the onset of absorption and color changes between the [MX6]3– based structures, due to differences in the interaction of the (NH 3 (CH 2 ) 7 NH 3 ) 2+ organic ammonium cation and the iodine packing of the inorganic framework. Density functional theory (DFT) calculations reveal flat bands reflective of the pseudo-1D crystal structure. Dark microwave conductivity (DMC) and time-resolved microwave conductivity (TRMC) reveal an excitonic character with long carrier lifetimes, consistent with the electronically confined octahedral chains. Comparison of the structural features with those of other diammonium-containing crystals reveals that diammoniumheptane can substitute into structures, displacing inorganic octahedra while retaining a close-packed anion framework. This provides a means for targeting new hybrid materials in which “vacancy-ordering” provides a crystal chemical approach for targeting desirable optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Efficient Self-Sensitized Photochemical CO 2 Reduction Using [Re(bpy 2+ )(CO) 3 (I)] 2+ and [Re(bpy 2+ )(CO) 3 (CH 3 CN)] 3+ Photocatalysts with Pendent Ammonium Cations

Rhenium(I) tricarbonyl complexes fac-[Re(bpy)(CO) 3 (L)]n + are the classical examples of self-sensitized photocatalysts capable of the dual roles of light absorption and catalysis. Here, in this work, a series of dicationic halido or tricationic solvento complexes fac-[Re(bpy 2+ )(CO) 3 X] n+ (PF 6 ) n (where X = Cl - or I - (n = 2), or CH 3 CN (n = 3) and bpy 2+ is bipyridine modified by two -CH 2 -(NMe3) + tetra-alkylammonium cations) have been investigated as self-sensitized and sensitized CO 2 reduction photocatalysts. Four structural isomers differing in the cation position have been tested in N,Nʹ-dimethylacetamide solvent (DMA) using 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (BIH) as the electron donor, and the position of the cationic pendants has a significant impact on the catalyst turnover number and quantum efficiency (ϕ). Up to 455 self-sensitized turnovers of CO and a high photon efficiency (ϕ CO ) of 22% have been achieved. Time-resolved infrared spectroscopy and theoretical calculations were used to characterize the catalytic cycle including the ligand exchange between one-electron reduced (OER) halido and solvento species as well as the binding of CO 2 to the putative two-electron reduced (TER) species. The CO 2 -reactive TER catalyst was formed by disproportionation or intramolecular electron transfer between two forms of the OER catalyst as indicated by the formation of the fully oxidized catalyst concurrent with CO 2 binding. When [Ru(bpy) 3 ] 2+ was used as a sensitizer, catalyst durability improved, and the selectivity toward formate increased as high as 3.3:1 over CO (total TON = 1370) due to acidification of the reaction, which promotes formation of the hydride intermediate, as BIH was consumed and deprotonated.

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

Vapor Pressures of RDX and HMX Explosives Measured at and Near Room Temperature: 1,3,5-Trinitro-1,3,5-triazinane and 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane

Knowing accurate saturated vapor pressures of explosives at ambient conditions is imperative to provide realistic boundaries on available vapor for ultra-trace detection. In quantifying vapor content emanating from low-volatility explosives, we observed discrepancies between the quantity of explosive expected based on literature vapor pressure values and the amount detected near ambient temperatures. Most vapor pressure measurements for low-volatility explosives, such as RDX (1,3,5-trinitro-1,3,5-triazinane) and HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), have been made at temperatures far exceeding 25 °C and linear extrapolation of these higher temperature trends appears to underestimate vapor pressures near room temperature. Our goal was to measure vapor pressures as a function of temperature closer to ambient conditions. We used saturated RDX and HMX vapor sources at controlled temperatures to produce vapors that were then collected and analyzed via atmospheric flow tube-mass spectrometry (AFT-MS). The parts-per-quadrillion (ppqv) sensitivity of AFT-MS enabled measurement of RDX vapor pressures at temperatures as low as 7 °C and HMX vapor pressures at temperatures as low as 40 °C for the first time. Furthermore, these vapor pressures were corroborated with analysis of vapor generated by nebulizing low concentration solutions of RDX and HMX. We report updated vapor pressure values for both RDX and HMX. Based on our measurements, the vapor pressure of RDX at 25 °C is 3 ± 1 x 10-11 atm (i.e. 30 parts per trillion by volume, pptv), the vapor pressure of HMX is 1.0 ± 0.6 x 10-14 atm (10 ppqv) at 40 °C and, with extrapolation, HMX has a vapor pressure of 1.0 ± 0.6 x 10-15 atm (1.0 ppqv) at 25 °C.

RDX, HMX, explosives, vapor pressure, vapor detect↗
DOE OSTI2024

Reverse Polarizability of Rare Earth Ions (La 3+ , Gd 3+ , Lu 3+ , Y 3+ ) in Tellurite Glasses and Glass Ceramics for Optical Limiting

All-optical modulation using inherent third-order optical nonlinearity of a medium has garnered considerable interest in photonics and optoelectronics. Herein, nonlinear optical (NLO) properties of tellurite glasses and glass ceramics (GCs) containing four different rare earths (RE = La, Gd, Lu, and Y) have been deliberated in near-infrared regions under an ultrafast regime. The La-based glass exhibits ~10 times higher nonlinear refraction (n 2 ) and absorption (α 2 ) than reported NLO materials. The NLO susceptibility [χ (3) ] trend in the studied glasses is La > Gd > Lu > Y, matching with RE 3+ polarizability. Furthermore, Ln 2 Te 6 O 15 nanocrystallite-embedded transparent GCs exhibit a larger NLO coefficient due to the enhanced local field from oxygen vacancies in crystallites. Interestingly, the trend of χ (3) in GCs follows the sequence of Y > Lu > Gd > La, precisely opposite to the glasses. This observation challenges the general polarizability approach of RE 3+ ions, emphasizing that quadratic hyperpolarizability of RE 3+ is pivotal for NLO properties of GCs. Among the studied matrices, Y-containing GCs showed the lowest optical limiting (OL) threshold (5.4 mJ/cm 2 at 800 nm), much lower than those of the reported NLO materials, suggesting its potential as a femtosecond NIR-laser safety material. A combination of large α 2 and n 2 from the studied matrices indicates their advantage for harmonic generation, potentially aiding in the design of ultrafast signal processing devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Tandem In 2 O 3 -Pt/Al 2 O 3 catalyst for coupling of propane dehydrogenation to selective H 2 combustion

Tandem catalysis couples multiple reactions and promises to improve chemical processing, but precise spatiotemporal control over reactive intermediates remains elusive. We used atomic layer deposition to grow In 2 O 3 over Pt/Al 2 O 3 , and this nanostructure kinetically couples the domains through surface hydrogen atom transfer, resulting in propane dehydrogenation (PDH) to propylene by platinum, then selective hydrogen combustion by In 2 O 3 , without excessive hydrocarbon combustion. Other nanostructures, including platinum on In 2 O 3 or platinum mixed with In 2 O 3 , favor propane combustion because they cannot organize the reactions sequentially. The net effect is rapid and stable oxidative dehydrogenation of propane at high per-pass yields exceeding the PDH equilibrium. Tandem catalysis using this nanoscale overcoating geometry is validated as an opportunity for highly selective catalytic performance in a grand challenge reaction.

Yan, Huan↗
DOE OSTI2023

Genetic encoding of 3–nitro–tyrosine reveals the impacts of 14–3–3 nitration on client binding and dephosphorylation

14–3–3 proteins are central hub regulators of hundreds of phosphorylated “client” proteins. They are subject to over 60 post–translational modifications (PTMs), yet little is known how these PTMs alter 14–3–3 function and its ability to regulate downstream signaling pathways. An often neglected, but well–documented 14–3–3 PTM found under physiological and immune–stimulatory conditions is the conversion of tyrosine to 3–nitro–tyrosine at several Tyr sites, two of which are located at sites considered important for 14–3–3 function: Y130 (β–isoform numbering) is located in the primary phospho–client peptide–binding groove, while Y213 is found on a secondary binding site that engages with clients for full 14–3–3/client complex formation and client regulation. By genetically encoding 3–nitro–tyrosine, we sought to understand if nitration at Y130 and Y213 effectively modulated 14–3–3 structure, function, and client complexation. The 1.5 Å resolution crystal structure of 14–3–3 nitrated at Y130 showed the nitro group altered the conformation of key residues in the primary binding site, while functional studies confirmed client proteins failed to bind this variant of 14–3–3. But, in contrast to other client–binding deficient variants, it did not localize to the nucleus. Further, the 1.9 Å resolution structure of 14–3–3 nitrated at Y213 revealed unusual flexibility of its C–terminal α–helix resulting in domain swapping, suggesting additional structural plasticity though its relevance is not clear as this nitrated form retained its ability to bind clients. Collectively, our data suggest that nitration of 14–3–3 will alter downstream signaling systems, and if uncontrolled could result in global dysregulation of the 14–3–3 interactome.

14-3-3↗
DOE OSTI2023

Two-Step Chemical Looping Cycle for Renewable NH 3 Production Based on Non-Catalytic Co 3 Mo 3 N/Co 6 Mo 6 N Reactions

A two-step solar thermochemical looping cycle based on Co 3 Mo 3 N/Co 6 Mo 6 N reduction/nitridation reactions offers a pathway for green NH 3 production that utilizes concentrated solar irradiation, H 2 O, and air as feedstocks. The NH 3 production cycle steps both derive process heat from concentrated solar irradiation and encompass 1) the reduction of Co 3 Mo 3 N in H 2 to Co 6 Mo 6 N and NH 3 ; and 2) nitridation of Co 6 Mo 6 N to Co 3 Mo 3 N with N 2 . Co 3 Mo 3 N reduction/nitridation reactions are examined at different H 2 and/or N 2 partial pressures and temperatures. NH 3 production is quantified in situ using liquid conductivity measurements coupled with mass spectrometry (MS). Solid-state characterization is performed to identify a surface oxygen layer that necessitates the addition of H 2 during cycling to prevent surface oxidation by trace amounts of O 2 . H 2 concentrations of > 5% H 2 /Ar and temperatures >500 °C are required to reduce Co 3 Mo 3 N to Co 6 Mo 6 N and form NH 3 at 1 bar. Complete regeneration of Co 3 Mo 3 N from Co 6 Mo 6 N is achieved at conditions of 700 °C under 25–75% H 2 /N 2 . H 2 pressure-swings are observed to increase NH 3 production during Co 3 Mo 3 N reduction. In conclusion, the results represent the first comprehensive characterization of and definitive non-catalytic production of NH 3 via chemical looping with metal nitrides and provide insights for technology development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Discovery of a Ferromagnetic Nickel Chalcogenide Nanocluster Ni 3 S 3 H(PEt 3 ) 5

Atomically precise ligated nanoclusters (NC) are promising cluster-based materials with novel molecular architectures and tunable magnetic properties. Herein, the synthesis and characterization of a nickel sulfide NC Ni 3 S 3 H(PEt 3 ) 5 (PEt 3 = triethylphosphine) with distinct magnetic properties are reported. Magnetization measurements reveal its magnetic moment of 1.5 µ B in the solid phase, consistent with the existence of one unpaired electron predicted by density functional theory (DFT) calculations. Additionally, experimental measurements indicate the presence of ferromagnetic ordering within each Ni 3 S 3 H(PEt 3 ) 5 NC and strong coercivity at temperatures below 20 K. Ion mobility-mass spectrometry is employed in conjunction with DFT calculations and collision cross-section simulations to investigate the structure of the isolated Ni 3 S 3 H(PEt 3 ) 5 . Theoretical studies show that [Ni 3 S 3 H(PEt 3 ) 5 ] + has a planar Ni 3 S 3 core where three Ni atoms are arranged in a triangle with three bridging S atoms residing in the same plane. This structure is preserved in both solution and solid phases, which is confirmed by spectroscopic studies of Ni 3 S 3 H(PEt 3 ) 5 . Additionally, DFT calculations indicate that all spins at the Ni sites are aligned parallel, confirming the presence of ferromagnetic coupling. Overall, this study provides key insights into the structure and magnetic properties of Ni 3 S 3 H(PEt 3 ) 5 , which will facilitate the design of new NC-based magnetic materials.

Nickel sulfide nanocluster↗
DOE OSTI2022

Synthesis of Trimethyltriazacyclohexane (Me 3 tach) Sandwich Complexes of Uranium, Neptunium, and Plutonium Triiodides: (Me 3 tach) 2 AnI 3

1,3,5-Trimethyl-1,3,5-triazacyclohexane (Me 3 tach) readily complexes uranium triiodide to form (Me 3 tach) 2 UI 3 . Further, the complex is soluble in THF and arenes and can function as a source of UI 3 to form organometallic U(III) complexes. When dissolved in pyridine (py), (Me3tach)2UI3 forms (Me 3 tach)UI 3 (py) 2 . A related complex with the larger 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 tacn) ligand, namely (Me 3 tacn)UI 3 (THF), was synthesized for comparison. Since X-ray quality crystals of (Me 3 tach) 2 UI 3 can be synthesized in high yield even with small-scale reactions, the system is ideal for extension to transuranium elements. Accordingly, the neptunium and plutonium complexes (Me 3 tach) 2 NpI 3 and (Me 3 tach) 2 PuI 3 were synthesized in an analogous manner from NpI 3 (THF) 4 and PuI 3 (THF) 4 , respectively.

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

[(MeCN)Ni(CF 3 ) 3 ] - and [Ni(CF 3 ) 4 ] 2– : Foundations toward the Development of Trifluoromethylations at Unsupported Nickel

Nickel anions [(MeCN)Ni(CF 3 ) 3 ] - and [Ni(CF 3 ) 4 ] 2– were prepared by the formal addition of 3 and 4 equiv, respectively, of AgCF 3 to [(dme)NiBr 2 ] in the presence of the [PPh 4 ] + counterion. Detailed insights into the electronic properties of these new compounds were obtained through the use of density functional theory (DFT) calculations, spectroscopy-oriented configuration interaction (SORCI) calculations, X-ray absorption spectroscopy, and cyclic voltammetry. The data collectively show that trifluoromethyl complexes of nickel, even in the most common oxidation state of nickel(II), are highly covalent systems whereby a hole is distributed on the trifluoromethyl ligands, surprisingly rendering the metal to a physically more reduced state. In the cases of [(MeCN)Ni(CF 3 ) 3 ] - and [Ni(CF 3 ) 4 ] 2- , these complexes are better physically described as d 9 metal complexes. [(MeCN)Ni(CF 3 ) 3 ] - is electrophilic and reacts with other nucleophiles such as phenoxide to yield the unsupported [(PhO)Ni(CF 3 ) 3 ] 2– salt, revealing the broader potential of [(MeCN)Ni(CF 3 ) 3 ] - in the development of “ligandless” trifluoromethylations at nickel. Proof-in-principle experiments show that the reaction of [(MeCN)Ni(CF 3 ) 3 ] - with an aryl iodonium salt yields trifluoromethylated arene, presumably via a high-valent, unsupported, and formal organonickel(IV) intermediate. Evidence of the feasibility of such intermediates is provided with the structurally characterized [PPh 4 ] 2 [Ni(CF 3 ) 4 (SO 4 )], which was derived through the two-electron oxidation of [Ni(CF 3 ) 4 ] 2– .

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

Comparing Pr 3+ and Nd 3+ for deactivating the Er 3+ : 4 I 13/2 level in lanthanum titanate glass

Erbium lanthanum titanate glasses were prepared by levitation melting for the spectroscopic study of ways to promote the mid-infrared fluorescence. Two series of heavily erbium doped glasses (15 wt%) were prepared with the addition of either Pr 3+ or Nd 3+ in amounts relative to Er 3+ of 0.05, 0.1, and 0.2. Both ions quench the lower Er 3+ laser level with the Pr 3+ doing so more rapidly. Although high co-dopant concentrations result in higher energy transfer, as clearly evidenced in upconversion and downconversion fluorescence measurements, the mid-infrared lifetime also suffers a reduction and, therefore, a balance must be struck in the co-dopant concentration. Lifetime and spectral measurements indicate that, at a fixed relative co-dopant amount, Pr 3+ is more effective than Nd 3+ at removing the bottleneck of the Er 3+ 4 I 13/2 level. Moreover, consideration of the lifetimes alongside the absorption data of the individual ions indicates that despite the large absorption cross-section of Nd 3+ at 808 nm, the concentration needed to yield more absorbed power than utilizing direct 976 nm excitation of Er 3+ results in unfavorable lifetimes of the mid-infrared transition. In the end, Pr 3+ prevails as the superior co-dopant in terms of the effects on fluorescence lifetimes as well as potential laser system design considerations. In a unique self-doping approach, a reducing melt atmosphere of Ar instead of O 2 creates a small fraction of Ti 3+ . In 5Er 2 O 3 -12La 2 O 3 -83TiO 2 glass, the presence of Ti 3+ quenches the 4 I 13/2 emission about 2.6 times more than the 4 I 11/2 when lifetimes are compared to an O 2 melt environment. As an additional means of increasing the mid-infrared emission, the effect of temperature on the mid- and near- infrared lifetimes of a lightly doped lanthanum titanate composition is investigated between 77-300 K. The mid-infrared lifetime increases by ∼30% while the near-infrared lifetime increases by ∼10%, which suggests in addition to co-doping, active cooling of the gain media will further enhance performance.

Materials Science↗
DOE OSTI2021

Computational study of Li 3 BO 3 and Li 3 BN 2 II: Stability analysis of pure phases and of model interfaces with Li anodes

Both Li 3 BO 3 and Li 3 BN 2 materials have promising properties for use in all solid-state batteries and other technologies dependent on electrolytes with significant ionic conductivity. As the second of a two-part study, the structural properties of Li 3 BO 3 and three reported phases of Li 3 BN 2 are investigated using first-principles modeling techniques. For alpha- Li 3 BN 2 , the tetragonal P4 2 / mnm structure reported in the literature is found to be unstable as evidenced by imaginary phonon modes near the M point of its Brillouin zone. Our simulations within the harmonic approximation suggest that the real α phase has the orthorhombic space group symmetry Pmmn formed with twice as many formula units and tiny adjustments of the equivalent lattice parameters and fractional coordinates. Extending the analysis of the Pmmn α- Li 3 BN 2 structure to the quasiharmonic approximation improves the agreement between the room-temperature x-ray pattern reported in the literature and the corresponding simulation results. In anticipation of the use of the monoclinic phases of Li 3 BO 3 and Li 3 BN 2 in Li ion conducting applications, chemical stability is investigated in terms of free-energy differences of possible decomposition and Li reaction processes, finding encouraging results. As further investigations of Li 3 BO 3 and β- Li 3 BN 2 as electrolyte or coating materials, particularly for use with Li metal anodes, idealized electrolyte/Li interfaces were investigated in terms of their geometric, energetic, and electronic properties. The results find the electrolyte/Li interfaces to be quite favorable, perhaps comparable to the pioneering LiPON/Li system.

36 MATERIALS SCIENCE↗