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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Impact of Transition Metal Doping on the Structural and Optical Properties of Halide Perovskites

Metal ion doping into halide perovskite materials is a promising approach to enhance long-term film stability and improve solar cell performance. Moreover, the idea of doping metals into halide perovskites is also driven by applications in heterogeneous catalysis. Here, we investigate the incorporation of the transition metals Pt and Pd into mixed-halide perovskite materials. We find that Pt aggregates in large clusters in iodine- and bromine-rich perovskite film compositions, whereas Pd incorporation depends on the underlying bromine to iodine ratio. Furthermore, by using optical and structural characterization methods, we observe that phase segregation in the perovskite layer is suppressed upon doping of either of these metals into the material. This approach further shows the potential to obtain catalytically active halide perovskite films in which the perovskite can serve as a host matrix.

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

3-D Geological Modeling for Numerical Flow Simulation Studies of Gas Hydrate Reservoirs at the Kuparuk State 7-11-12 Pad in the Prudhoe Bay Unit on the Alaska North Slope

Accurate reservoir evaluation requires reliable three-dimensional (3-D) geological models. Here, this study conducted 3-D geological modeling for numerical flow simulation of the B1 sand gas hydrate reservoir at the Kuparuk State 7-11-12 pad, Prudhoe Bay Unit, Alaska North Slope. The model integrates well logs, core, and seismic data to address spatial heterogeneity in geological structures and reservoir properties. Two modeling types were performed: structural framework modeling and petrophysical property modeling. For structural framework modeling, seismic data and well log markers were used to reproduce subsurface structures characterized by a normal fault system. A volume-based modeling algorithm and stair-stepping grid were applied. The resulting 3-D model comprised 2,640,000 grid cells across 264 layers, including seven fault grids. For petrophysical property modeling, total porosity was initially modeled using sequential Gaussian simulation with collocated cokriging. To reproduce the upward coarsening of the B1 sand, upscaled log-derived total porosity and a three-dimensional (3-D) trend depicting total porosity variation were used as primary and secondary data, respectively. Gas hydrate saturation distribution was modeled similarly, with secondary data from estimated porosity distribution and seismic-derived acoustic impedance map enhancing accuracy. Results indicate higher gas hydrate saturation in the upper part of the B1 sand and areas with higher acoustic impedance. Intrinsic permeability was modeled from the total porosity and clay-bound water volume, and effective permeability was derived from the gas hydrate saturation and intrinsic permeability distributions based on the “Tokyo model”. Effective permeability distributions were influenced by the total porosity, gas hydrate saturation, and intrinsic permeability. Within the same layer, higher gas hydrate saturation leads to decreased effective permeability. In total, 100 sets of multiple scenarios were prepared, providing input data for dynamic flow simulations to evaluate the effects of lateral heterogeneity in reservoir properties and the hydraulic characteristics of faults on production behavior for preassessment before the long-term production test.

58 GEOSCIENCES↗
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 OSTI2020

A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes

Here, an approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, C 8 H 8 , with a solution obtained from the reduction of Cp' 3 Pu (Cp' = C 5 H 4 SiMe 3 ) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of C 8 H 8 by a putative Pu(II) complex, (Cp' 3 Pu II ) 1– , generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C 8 H 8 ) 2 Pu III ], 1-Pu , and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp' 4 Pu III ], 2-Pu . Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C 8 H 8 ) 2 Pu IV , 3-Pu . Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C 8 H 8 ) 2– rings. The (Cp' 4 Pu III ) – anion in 2-Pu features three η 5 -Cp' rings and one η 1 -Cp' ring, which is a rare example of a formal Pu–C η 1 -bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available Pu IV O 2 was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu . Pu IV O 2 was converted to Pu III Br 3 (DME) 2 (DME = CH 3 OCH 2 CH 2 OCH 3 ) and subsequently Pu III Br 3 (THF) x , which was used to independently synthesize 1-Pu , 2-Pu , and 3-Pu .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride

Reported are the syntheses, structural characterizations and luminescence properties of three novel [UO 2 Cl 4 ] 2- bearing compounds containing substituted 1,1’-dialkyl-4,4’-bipyridinum dications (i.e. viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. Further, this reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion and photoelectron transfer to the viologen which constitutes the formal transfer of one electron from the [UO 2 Cl 4 ] 2- to the viologen species. This behavior is elucidated using electron paramagnetic resonance (EPR) spectroscopy and further probed through a series of characterization and computational techniques including Rehm-Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work provides a systematic study of the photoreactivity of the uranyl unit in the solid state, an under-described aspect of fundamental uranyl chemistry.

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

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K + salts from crude solids of the monomer building block UO 2 (O 2 ) 3 4– (K–U 1 ), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K + salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K 6 [(UO 2 ) 2 (O 2 ) 4 (OH) 2 ]·7H 2 O (K–U 2 ) and a hexamer face frequently observed in the capsules, K 12 [(UO 2 ) 6 (O 2 ) 9 (OH) 6 ]$·x$H 2 O(K–U 6 ). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U 1 (days) < K–U 2 (hours) < K–U 6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.

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

La-Based Perovskite Oxide Catalysts for Alkaline Oxygen Reduction: The Importance of Electrochemical Stability

Alkaline fuel cells represent a promising energy conversion technology since they enable the use of precious metal-free electrocatalysts for the oxygen reduction reaction. Among these, La-based perovskite oxides, with great compositional and structural tunability, are especially attractive. However, we believe that the current literature lacks a thorough understanding of their inherent (in)stability issues. Here, in this study, we report on nine La-based perovskite oxide electrocatalysts for the oxygen reduction reaction, including LaMO 3 (M = Mn, Co, Ni) and LaCo x M 1–x O 3 (M = Mn, Ni; x = 0.9, 0.5, 0.1). While some exhibited initial promising activity, they all degraded significantly, even after brief electrochemical testing. Through comprehensive structural characterization of LaCo 0.9 Mn 0.1 O 3 , particularly scanning transmission electron microscopy, we found evidence to support a degradation mechanism in which the B-site cation species irreversibly leach from the perovskite under testing conditions. A sample cycled 10 000 times from +0.4 to +1.2 V vs reversible hydrogen electrode (RHE) showed an amorphous La oxide shell 1–2 nm thick. Bulk analyses showed that B-site leaching also occurs for samples soaked in 1 M KOH or pure EtOH. The mechanistic insights provided here should help inform the future design of La-based perovskite oxide electrocatalysts for alkaline fuel cells and stress the importance of stability metrics validating claims of promising electrocatalytic activity.

Seok, Jeesoo↗
DOE OSTI2022

Enhancement of Emission from Lanthanide Dopants in Perovskite Nanocrystals through a Temperature-Dependent Phase Transformation of the Perovskite Lattice

The excited states of lanthanide ions (Ln 3+ ) exhibit ultranarrow emission and long spin dephasing lifetimes suitable for optoelectronic and quantum applications but are not directly optically accessible. One effective strategy to excite Ln 3+ ions is to dope them into a semiconductor host lattice, which acts as a photosensitizer. This work describes enhancement of emission intensity by a factor of 19 with decreasing temperature (from 300 to S K) from Sm 3+ ions in CsPbCl 3 nanocrystal hosts. Structural characterization over the same temperature region reveals that this enhancement is primarily due to a symmetry-lowering cubic-to-orthorhombic phase transition of the host lattice, which reduces the local site symmetry of the dopant and increases the Sm 3+ * emission quantum yield.

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

Optical and Plasmonic Properties of High-Electron-Density Epitaxial and Oxidative Controlled Titanium Nitride Thin Films

The present paper reports on the fabrication, detailed structural characterizations, and theoretical modeling of titanium nitride (TiN) and its isostructural oxide derivative, titanium oxynitride (TiNO) thin films that have excellent plasmonic properties and that also have the potential to overcome the limitation of noble metal and refractory metals. The TiNO films deposited at 700 °C in high vacuum conditions have the highest reflectance (R = ~ 95%), largest negative dielectric constant (ε 1 = –161), and maximal plasmonic figure of merit (FoM = –ε 1 /ε 2 ) of 1.2, followed by the 600 °C samples deposited in a vacuum (R = ~ 85%, ε 1 = –145, FoM = 0.8) and 700 °C–5 mTorr sample (R = ~ 82%, ε 1 = –8, FoM = 0.3). To corroborate our experimental observations, we calculated the phonon dispersions and Raman active modes of TiNO by using the virtual crystal approximation. From the experimental and theoretical studies, a multilayer optical model has been proposed for the TiN/TiNO epitaxial thin films for obtaining individual complex dielectric functions from which many other optical parameters can be calculated. The advantages of oxide derivatives of TiN are the continuation of similar free electron density as in TiN and the acquisition of additional features such as oxygen-dependent semiconductivity with a tunable bandgap.

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

Superconducting Fourfold Fe(Te,Se) Film on Sixfold Magnetic MnTe via Hybrid Symmetry Epitaxy

Epitaxial Fe(Te,Se) thin films have been grown on various substrates but never been grown on magnetic layers. In this work, we report the epitaxial growth of fourfold Fe(Te,Se) film on a sixfold antiferromagnetic insulator, MnTe. The Fe(Te,Se)/MnTe heterostructure shows a clear superconducting transition at around 11 K, and the critical magnetic field measurement suggests the origin of the superconductivity to be bulk-like. Structural characterizations suggest that the uniaxial lattice match between Fe(Te,Se) and MnTe allows a hybrid symmetry epitaxy mode, which was recently discovered between Fe(Te,Se) and Bi 2 Te 3 . Furthermore, the Te/Fe flux ratio during deposition of the Fe(Te,Se) layer is found to be critical for its superconductivity. Now that superconducting Fe(Te,Se) can be grown on two related hexagonal platforms, Bi 2 Te 3 and MnTe, this result opens a new possibility of combining topological superconductivity of Fe(Te,Se) with the rich physics in the intrinsic magnetic topological materials (MnTe) n (Bi 2 Te 3 ) m family.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Intrinsic Formamidinium Tin Iodide Nanocrystals by Suppressing the Sn(IV) Impurities

The long search for non-toxic alternatives to lead halide perovskites (LHPs) has shown that some compelling properties of LHPs, such as low effective masses of carriers, can only be attained in their closest Sn(II) and Ge(II) analogs, despite their tendency to oxidation. Judicious choice of chemistry allowed formamidinium tin iodide (FASnI 3 ) to reach a power conversion efficiency of 14.81% in photovoltaic devices. This progress motivated us to develop a synthesis of colloidal FASnI 3 NCs with a concentration of Sn(IV) reduced to an insignificant level and probe their intrinsic structural and optical properties. Intrinsic FASnI 3 NCs exhibit unusually low absorption coefficients of 4 x 10 3 cm -1 at the first excitonic transition, a 190 meV increase of the bandgap as compared to the bulk material, and a lack of excitonic resonances. These features are attributed to a highly disordered lattice, distinct from the bulk FASnI 3 as supported by structural characterizations and first-principles calculations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Surface-Doped Zinc Gallate Colloidal Nanoparticles Exhibit pH-Dependent Radioluminescence with Enhancement in Acidic Media

As abnormal acidic pH symbolizes dysfunctions of cells, it is highly desirable to develop pH-sensitive luminescent materials for diagnosing disease and imaging-guided therapy using high-energy radiation. Herein, we explored near-infrared-emitting Cr-doped zinc gallate ZnGa 2 O 4 nanoparticles (NPs) in colloidal solutions with different pH levels under X-ray excitation. Ultrasmall NPs were synthesized via a facile hydrothermal method by controlling the addition of ammonium hydroxide precursor and reaction time, and structural characterization revealed Cr dopants on the surface of NPs. The synthesized NPs exhibited different photoluminescence and radioluminescence mechanisms, confirming the surface distribution of activators. It was observed that the colloidal NPs emit pH-dependent radioluminescence in a linear relationship, and the enhancement reached 4.6-fold when pH = 4 compared with the colloidal NPs in the neutral solution. This observation provides a strategy for developing new biomaterials by engineering activators on the nanoparticle surfaces for potential pH-sensitive imaging and imaging-guided therapy using high-energy radiation.

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

Sn-InAs Nanowire Shadow-Defined Josephson Junctions

Hybrid superconductor–semiconductor platforms are foundational to advancing quantum information technologies, motivating the integration of materials with clean interfaces, robust superconductivity, and scalable architectures. Here, in this work, we report the synthesis and analysis of inclined InAs nanowires, conformally coated with β-Sn shells. These nanowires extend in opposite in-plane directions, forming a self-aligned, criss-cross network. This enables the deterministic formation of nanowire-shadow Josephson junctions through angle-controlled, low-temperature Sn deposition. Structural characterization shows uniform polycrystalline β-Sn shells forming a sharp, diffusion-free interface with InAs. Low-temperature transport measurements reveal a hard induced superconducting gap ≈ 600 μeV, switching currents up to ≈ 500 nA, and parallel magnetic field resilience beyond 1T. These results establish β-Sn/InAs nanowire networks as a promising platform for superconducting qubits, low-noise microwave devices, and the exploration of exotic superconducting phases including triplet pairing and topological superconductivity.

B-Sn↗
DOE OSTI2021

Access to Perfluorometallacyclopentane Complexes of Cobalt through the [(MeCN) 4 Co(C 4 F 8 )][PF 6 ] Precursor

Here, the acetonitrile ligands in [(MeCN) 4 Co(C 4 F 8 )][PF 6 ] were found to be labile toward ligand substitution reactions, allowing for the preparation of [(MeCN)(tpy)Co(C 4 F 8 )][PF 6 ], [(tpy)CoBr(C 4 F 8 )], [(bpy) 2 Co(C 4 F 8 )][PF 6 ], and [(cis-κ 2 -pym-PPh 2 ) 2 Co(C 4 F 8 )][PF 6 ] (tpy = 2,2':6',2"-terpyridine, bpy = 2,2'-bipyridine, and pym-PPh 2 = diphenyl(2-pyrimidyl)phosphine). All of the aforementioned complexes have been structurally characterized by X-ray diffraction. Additionally, an improved procedure for the preparation of [(MeCN) 4 Co(C 4 F 8 )][X] (X = PF 6 or BF 4 ) is reported.

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

Differences in the Interfacial Mechanical Properties of Thiophosphate and Argyrodite Solid Electrolytes and Their Composites

Interfacial mechanics are a significant contributor to the performance and degradation of solid-state batteries. Spatially resolved measurements of interfacial properties are extremely important to effectively model and understand the electrochemical behavior. Herein, we report the interfacial properties of thiophosphate (Li 3 PS 4 )- and argyrodite (Li 6 PS 5 Cl)-type solid electrolytes. Using atomic force microscopy, we showcase the differences in the surface morphology as well as adhesion of these materials. Additionally we investigate solvent-less processing of hybrid electrolytes using UV-assisted curing. Physical, chemical, and structural characterizations of the materials highlight the differences in the surface morphology, chemical makeup, and distribution of the inorganic phases between the argyrodite and thiophosphate solid electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Multifunctional Effect of Fe Substitution in Na Layered Cathode Materials for Enhanced Storage Stability

In this study, developing stable cathode materials that are resistant to storage degradation is essential for practical development and industrial processing of Na-ion batteries, as many sodium layered oxide materials are susceptible to hygroscopicity and instability when exposed to ambient air. Among the various layered compounds, Fe-substituted O 3 -type Na(Ni 1/2 Mn 1/2 ) 1-x Fe x O 2 materials have emerged as a promising option for high-performance and low-cost cathodes. While previous reports have noted the decent air-storage stability of these materials, the role and origin of Fe substitution in improving storage stability remain unclear. In this study, we investigate the air resistant effect of Fe substitution in O 3 -Na(Ni 1/2 Mn 1/2 ) 1-x Fe x O 2 cathode materials by performing systematic surface and structural characterizations. We find that the improved storage stability can be attributed to the multifunctional effect of Fe substitution, which forms a surface protective layer containing an Fe-incorporated spinel phase and decreases the thermodynamical driving force for bulk chemical sodium extraction. With these mechanisms, the Fe-containing cathodes can suppress the cascades of cathode degradation processes and better retain the electrochemical performance after air storage.

25 ENERGY STORAGE↗
DOE OSTI2023

Ultrasmooth Epitaxial Pt Thin Films Grown by Pulsed Laser Deposition

Platinum (Pt) thin films are useful in applications requiring high-conductivity electrodes with excellent thermal and chemical stability. Ultrasmooth and epitaxial Pt thin films with single-crystalline domains have the added benefit of providing ideal templates for the subsequent growth of heteroepitaxial structures. Here, we grow epitaxial Pt (111) electrodes (ca. 30 nm thick) on sapphire (α-Al 2 O 3 (0001)) substrates with pulsed laser deposition. This versatile technique allows control of the growth process and fabrication of films with carefully tailored parameters. X-ray scattering, atomic-force microscopy, and electron microscopy provide structural characterization of the films. Various gaseous atmospheres and temperatures were explored to achieve epitaxial growth of films with low roughness. A two-step (500 °C/300 °C) growth process was developed, yielding films with improved epitaxy without compromising roughness. The resulting films possess ultrasmooth interfaces (<3 Å) and high electrical conductivity (6.9 × 10 6 S/m). Finally, Pt films were used as current collectors and templates to grow lithium manganese oxide (LiMn 2 O 4 (111)) epitaxial thin films, a cathode material used in Li-ion batteries. In conclusion, using a solid-state ionogel electrolyte, the films were highly stable when electrochemically cycled in the 3.5-4.3 V vs Li/Li + range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗