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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Trinuclear Copper(I) and Silver(I) Complexes of a Pentafluorosulfanyl-Decorated Pyrazolate

Here, this study reports the synthesis and characterization of the first fluorinated coinage metal pyrazolates with SF 5 groups, specifically {[3-(SF 5 )­Pz]­M} 3 (M = Cu, Ag), and compares them to trifluoromethylated analogs. X-ray analysis reveals different pyrazolyl ligand orientations and metallophilic interactions, as well as supramolecular structures influenced by fluorinated substituents and metals. The {[3-(SF 5 )­Pz]­M} 3 complexes form face-to-face sandwich adducts with benzene. Photophysical investigations show that copper complexes exhibit long-lived phosphorescence, while silver analogs display fast fluorescence, with emission properties modulated by substituents, solvent environment, and intermolecular interactions. Computational studies confirm the experimental geometries and demonstrate that SF 5 substituents increase the π-acidity and enhance arene binding over the analogs featuring the smaller and less-electron-withdrawing CF 3 groups and provide insights into metallophilic interactions and photoluminescence. These newly uncovered SF 5 decorated materials, with enhanced π-acidity and arene-binding ability, are promising materials for molecular sensing and tunable luminescence.

Vanga, Mukundam [University of Texas, Arlington, T↗
DOE OSTI2025

Density Functional Tight Binding Insights into Plasmonic Silver–Platinum Nanoparticles and Alloys for Enhanced Photocatalysis

Developing accurate and efficient Slater-Koster (SK) tight-binding parameter sets is essential for quantum plasmonic studies of alloyed metal nanoparticles, as conventional time dependent density functional theory (TD-DFT) calculations are computationally prohibitive for larger clusters. In this work, we develop and validate density functional tight binding (DFTB) parameter sets for both ground state (GS-SK) and excited state (ES-SK) calculations to study the structural, electronic, and optical properties of silver (Ag), platinum (Pt), and Ag–Pt nanoalloys. Our investigation of the ground state properties demonstrates that the GS-SK parameters enable DFTB to closely reproduce the electronic structures of platinum clusters with diverse sizes and geometries – showing qualitative agreement with DFT for density of states (DOS) profiles and energy levels. The ES-SK parameters accurately describe excited-state properties compared to TD-DFT reference calculations, including the broad, featureless absorption profiles of Pt that are dominated by interband transitions. Using the ES-SK parameters within a real-time TD-DFTB framework, we compute size-dependent optical absorption spectra of Ag, Pt and Ag-Pt nanocubes containing up to 1099 atoms (size ∼4.18 nm). A detailed study of Ag–Pt and Pt-Ag core–shell nanoparticles shows quenching of the Ag plasmon resonance even at monolayer coverage for Ag-Pt, but not for Pt-Ag. We also show how to define submonolayer Ag-core Pt-shell cubic structures that have similar optical properties to those generated experimentally for much larger particles, which offers potential for describing plasmon-enhanced photocatalysis. Collectively, the GS-SK and ES-SK parameter sets provide an accurate, computationally efficient approach for modeling the complex optical and electronic behavior of noble–transition metal nanostructures and their alloys.

SPR↗
DOE OSTI2026

Depth-Dependent Emission from Silver Dopants in Single CdSe Nanoplatelets

Dopants in semiconductor nanostructures offer tremendous control over electronic, optical, and magnetic properties beyond what is achievable in bulk materials. We demonstrate that the broad dopant emission in semiconductor nanoplatelets effectively maps the electron wave function across the nanoplatelet thickness. Both the emission energy and lifetime of the dopant transition depend strongly on the depth of the dopant within the nanoplatelet. This dependence arises from the electrostatic self-interaction of the charged dopant, which varies with proximity to the dielectric discontinuity at the nanoplatelet surface. Through comprehensive single-particle spectroscopy of silver-doped CdSe nanoplatelets, we verify that acceptors near the center emit at higher energies with shorter lifetimes, while those near the surface emit at lower energies with longer lifetimes. This spatial mapping also reveals unusual two-color emission from individual nanoplatelets, with enhanced Auger recombination yielding exceptional photon antibunching (>90% purity) at room temperature, suggesting potential applications in quantum information technologies.

cadmium selenide↗
DOE OSTI2025

Excitation Laser Energy Dependence of the Gap-Mode TERS Spectra of WS 2 and MoS 2 on Silver

In this work we present a systematic study of the dependence of the gap mode tip-enhanced Raman scattering (TERS) response of the mono- and bi-layer WS 2 and MoS 2 on silver as a function of the excitation laser energy in a broad spectral range from 473nm to 830 nm. For this purpose, we collected consecutive TERS maps of the same area in the sample containing mono-and bi-layer regions with the same TERS probe with 6 different excitation lasers. To decrease the number of collected TERS maps, we used for the first time to the best of our knowledge, concurrent excitation and collection with two lasers simultaneously. We found that the E 2g /A 1g peak intensity ratio for the bilayer WS 2 @Ag and the ratio of the A’/A 1g peak intensity of the out-of-plane mode for the mono- and the bilayer, change in a significantly non-monotonous way as the excitation laser energy is swept from 1.58 eV to 2.62 eV. The former ratio increases at energies corresponding to A and B excitons (~2.0 eV and 2.4 eV correspondingly) in bilayer WS 2 . The absolute intensity of the A’ peak in the monolayer, and correspondingly the A’/A 1g ratio, is surprisingly high at lower excitation energies, but dips dramatically at the energy corresponding to the A exciton, being restored partially in between A and B excitons, but still showing the descending trend as the excitation laser energy increases. A somewhat similar picture was observed in mono- and bi-layers of MoS 2 @Ag, though the existing set of excitation lasers did not match the excitonic profile of this material as nicely as for the case of WS 2 . We attribute the observed behavior to the presence of intermediate (Fano resonance) or strong (Rabi splitting) coupling between the excitons in transition metal dichalcogenides (TMDs) and the plasmons in the tip-substrate nanocavity. This is akin to the so-called Fano (Rabi) transparency experimentally observed in far field scattering from transition metal dichalcogenides between two plasmonic metals. The possibility of the formation of intermediate/strong coupling between the excitonic resonances in TMDs and the nanocavity re-evaluates the role of various resonances in the gap-mode TERS and should become an important factor to be considered by TERS practitioners during planning the experiments. Lastly, based on observed phenomena and its explanation, we propose the “ideal” substrate for efficient TERS and tip enhanced photoluminescence (TEPL) measurements.

Raman spectroscopy↗
DOE OSTI2025

Electro-activated indigos intensify ampere-level CO 2 reduction to CO on silver catalysts

The electrochemical reduction of carbon dioxide (CO 2 ) to carbon monoxide (CO) is challenged by a selectivity decline at high current densities. Here we report a class of indigo-based molecular promoters with redox-active CO 2 binding sites to enhance the high-rate conversion of CO 2 to CO on silver (Ag) catalysts. Theoretical calculations and in situ spectroscopy analyses demonstrate that the synergistic effect at the interface of indigo-derived compounds and Ag nanoparticles could activate CO 2 molecules and accelerate the formation of key intermediates (*CO 2 – and *COOH) in the CO pathway. Indigo derivatives with electron-withdrawing groups further reduce the overpotential for CO production upon optimizing the interfacial CO 2 binding affinity. By integrating the molecular design of redox-active centres with the defect engineering of Ag structures, we achieve a Faradaic efficiency for CO exceeding 90% across a current density range of 0.10 − 1.20 A cm –2 . The Ag mass activity toward CO increases to 174 A mg –1 Ag . This work showcases that employing redox-active CO 2 sorbents as surface modification agents is a highly effective strategy to intensify the reactivity of electrochemical CO 2 reduction.

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

Thermal energy transport in laser-driven high x-ray conversion efficiency metallic silver nanowire foams

Here, we report on record brightness from Ag x-ray emission obtained using a novel laser-produced plasma source. The reported K-shell conversion efficiency of nearly 1% with a radiant energy of ≈ 0.6 kJ/sr from Ag ions is the highest presently recorded and is about twofold greater than more conventional metal-lined cavity targets. He-like Ag ions are the dominant radiators at ≈ 22.7 keV, which contrast the x-ray sources from other pulse power facilities that produce K-shell x-rays from Auger processes in near-neutral ions driven by the nonthermal hot electrons produced in the Z-pinch implosion. The reported x-ray emission was produced from a 4-mm-diameter, 4-mm-long underdense silver nanowire target at 10⁢ mg/⁢cm 3 . The National Ignition Facility laser beams deposited ≈ 1000 kJ of 3ω light into the target with a ≈ 400 TW, 2.5 ns square pulse. Finally, we show via comparisons of data with radiation-hydrodynamics simulations that flux-limited classical thermal energy transport models are inadequate in correctly modeling the behavior of these non-local thermodynamic equilibrium plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Seniority Structure in Neutron-Rich Nucleus 128 Ag : Evidence for Robustness of 𝑁 = 82 Shell Closure in Silver Isotopes

The spectroscopic studies of very neutron-rich nucleus 128 Ag have been performed for the first time at the Radioactive Isotope Beam Factory of RIKEN. A new seniority isomer with a half-life of 1.60(7) μs has been identified and is proposed to have a spin-parity of 16 - with a maximally aligned configuration comprising three proton holes in the g 9/2 orbital and one neutron hole in the h 11/2 orbital. The new level structure in 128 Ag is quite well described by shell model calculations without invoking excitations across the Z = 50 and N = 82 shell gaps, and presents a good case of seniority scheme in odd-odd nuclei in the south vicinity of the double-magic nucleus 132 Sn. With a classification of various components of the proton-neutron interaction, the inversion of lowest-lying 9 - and 10 - states between 128 Ag and its neighboring isotone 130 In is found to be dynamically ascribed to the seniority-nonconserving proton-neutron interaction components. The structure above 10 - up to the 16 - isomer in 128 Ag shows remarkable similarities to seniority structures in the semimagic nuclei 128 Pd and 130 Cd. These spectroscopic features in 128 Ag indicate that the N = 82 shell closure is still robust in silver isotopes.

Luo, D. W. [Peking University, Beijing (China); et↗
DOE OSTI2025

Nickel promotes selective ethylene epoxidation on silver

Over the last 80 years, chlorine (Cl) has been the primary promoter of the ethylene epoxidation reaction valued at ~40 billion USD per year, providing a ~25% selectivity increase over unpromoted silver (Ag) (~55%). Promoters such as cesium, rhenium, and molybdenum each add a few percent of selectivity enhancements to achieve 90% overall, but their codependence on Cl makes optimizing and understanding their function complex. Here, we took a theory-guided, single-atom alloy approach to identify nickel (Ni) as a dopant in Ag that can facilitate selective oxidation by activating molecular oxygen (O 2 ) without binding oxygen (O) too strongly. Surface science experiments confirmed the facile adsorption/desorption of O 2 on NiAg, as well as demonstrating that Ni serves to stabilize unselective nucleophilic oxygen. Supported Ag catalyst studies revealed that the addition of Ni in a 1:200 Ni to Ag atomic ratio provides a ~25% selectivity increase without the need for Cl co-flow and acts cooperatively with Cl, resulting in a further 10% initial increase in selectivity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Porous Interlayers that Getter Surface-Segregating Species for Improved Silver Wetting, Adhesion, and Electrical Contact on Stainless Steel SOFC Components

Here, porous nickel interlayers or porous platinum interlayers were shown to promote the wetting, spreading, and adhesion of silver on alumina-forming ferritic stainless steel (AFFSS) and chromia-forming ferritic stainless steel (CFFSS). These interlayers resulted in dense, crack-free AFFSS|Ag-Ni|CFFSS and AFFSS|Ag-Pt|CFFSS braze joints that, after 300 h in 650 °C air, displayed shear strengths up to 70 MPa similar to, or larger than, those of AFFSS|Ag-CuO|CFFSS or AFFSS|Ag|CFFSS joints subjected to identical treatment. Similarly, after exposure to 25 cycles of (50 switches between) 12 h of 650 °C air and 12 h of 650 °C 4%H 2 –96%N 2 , AFFSS|Ag-Ni|CFFSS and AFFSS|Ag-Pt|CFFSS braze joints displayed shear strengths significantly larger than those of AFFSS|Ag-CuO|CFFSS or AFFSS|Ag|CFFSS joints subjected to identical treatment. In addition, nickel and platinum were found to chemically getter surface-segregating steel constituents, particularly Al from the AFFSS. As a result, Ag-Ni and Ag-Pt electrical contact resistances on AFFSS and CFFSS substrates were several orders of magnitude lower than those of conventional Ag-CuO reactive air brazes or Heraeus C8710 Ag contact pastes. Together, these results suggest that Ag-Pt and especially Ag-Ni may be useful for the fabrication of durable joints, seals, and/or electrical contacts in electrical/electrochemical devices exposed to high temperatures and/or variable oxygen partial pressure environments.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Iodine Capture Studies of Silver Mordenite and Novel Alternative Metal Sorbents

Radioiodine is one of the radionuclides of concern when considering reprocessing of used nuclear fuel (UNF). It is expected to be released primarily in the dissolver off-gas (DOG) stream. Sorbents that target I 2 removal from a UNF processing off gas must perform efficiently under elevated temperatures in the presence of water vapor and nitrogen oxide gasses (NOx). Many studies have been conducted that examine the adsorption of iodine species in the presence of NOx gases through reduced silver-exchanged mordenite (Ag 0 Z), a zeolite mineral. This study characterizes the effects of iodine, water vapor, and nitrogen dioxide on the adsorption of I 2 by Ag 0 Z at lower temperatures suitable for comparison with novel Cu- and Bi- bearing sorbents which offer a non-RCRA alternative. When exposed to ‘harsh’ conditions such as I 2 , H 2 O, and NO 2 vapors carried by air, Cu 2 S-polyacrylonitrile (PAN) is more efficient than Ag 0 Z and all other novel sorbents, providing with 11% I capture efficiency. However, under ‘ideal’ conditions in which I 2 is carried by dry air), Ag 0 Z is more efficient than Cu 2 S-PAN and other novel sorbents, providing 74% I capture efficiency. To investigate this result and the overall performance of all sorbents tested, several characterization techniques were employed, including thermal gravimetric analysis, scanning electron microscopy – electron dispersion X-Ray spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy. These techniques are discussed within this report. This document also includes a design and test plan update from Idaho National Laboratory as the next step in testing the high performing sorbents from thin-bed tests carried out by Oak Ridge National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Screen-Printed SHJ Solar Cells with Complex Silver Inks

Metallization using complex metal inks has gained significant research interest due to its cost-effectiveness and ability to achieve performance comparable to traditional nanoparticle pastes. This study introduces the use of complex silver (Ag) inks applied via industrial screen-printing for silicon heterojunction (SHJ) solar cell metallization. The printed Ag lines exhibit a contact resistivity on SHJ tin-doped indium oxide (ITO) surfaces as low as approximately 0.2-12 mO cm2. Photoluminescence imaging reveals minimal surface passivation degradation (iVoc < 3.5 mV), while scanning electron microscopy (SEM) shows a denser structure compared to Ag layer from nanoparticle pastes. The printed Ag grid features thin (approximately 1 micrometer), continuous fingers approximately 100-120 micrometer wide, significantly thinner than conventional approximately 20-30 micrometer fingers produced with nanoparticle-based pastes. Double printing achieves SHJ device efficiencies exceeding 20%, the highest reported for industrial solar cell precursors using this technology. These findings highlight the potential of complex Ag inks as a sustainable alternative to particle-based pastes, reducing Ag consumption and processing temperatures without compromising efficiency.

14 SOLAR ENERGY↗
DOE OSTI2024

Optimization and Multimachine Learning Algorithms to Predict Nanometal Surface Area Transfer Parameters for Gold and Silver Nanoparticles

Interactions between gold metallic nanoparticles and molecular dyes have been well described by the nanometal surface energy transfer (NSET) mechanism. However, the expansion and testing of this model for nanoparticles of different metal composition is needed to develop a greater variety of nanosensors for medical and commercial applications. In this study, the NSET formula was slightly modified in the size-dependent dampening constant and skin depth terms to allow for modeling of different metals as well as testing the quenching effects created by variously sized gold, silver, copper, and platinum nanoparticles. Overall, the metal nanoparticles followed more closely the NSET prediction than for Förster resonance energy transfer, though scattering effects began to occur at 20 nm in the nanoparticle diameter. To further improve the NSET theoretical equation, an attempt was made to set a best-fit line of the NSET theoretical equation curve onto the Au and Ag data points. An exhaustive grid search optimizer was applied in the ranges for two variables, 0.1≤C≤2.0 and 0≤α≤4, representing the metal dampening constant and the orientation of donor to the metal surface, respectively. Three different grid searches, starting from coarse (entire range) to finer (narrower range), resulted in more than one million total calculations with values C=2.0 and α=0.0736. The results improved the calculation, but further analysis needed to be conducted in order to find any additional missing physics. With that motivation, two artificial intelligence/machine learning (AI/ML) algorithms, multilayer perception and least absolute shrinkage and selection operator regression, gave a correlation coefficient, R2, greater than 0.97, indicating that the small dataset was not overfitting and was method-independent. This analysis indicates that an investigation is warranted to focus on deeper physics informed machine learning for the NSET equations.

Demers, Steven M. E. (ORCID:0000000192213246)↗
DOE OSTI2025

Fabricating Silver Nanowire–IZO Composite Transparent Conducting Electrodes at Roll-to-Roll Speed for Perovskite Solar Cells

This study addresses the challenges of efficient, large-scale production of flexible transparent conducting electrodes (TCEs). We fabricate TCEs on polyethylene terephthalate (PET) substrates using a high-speed roll-to-roll (R2R) compatible method that combines gravure printing and photonic curing. The hybrid TCEs consist of Ag metal bus lines (Ag MBLs) coated with silver nanowires (AgNWs) and indium zinc oxide (IZO) layers. All materials are solutions deposited at speeds exceeding 10 m/min using gravure printing. We conduct a systematic study to optimize coating parameters and tune solvent composition to achieve a uniform AgNW network. The entire stack undergoes photonic curing, a low-energy annealing method that can be completed at high speeds and will not damage the plastic substrates. The resulting hybrid TCEs exhibit a transmittance of 92% averaged from 400 nm to 1100 nm and a sheet resistance of 11 Ω/sq. Mechanical durability is tested by bending the hybrid TCEs to a strain of 1% for 2000 cycles. The results show a minimal increase (<5%) in resistance. The high-throughput potential is established by showing that each hybrid TCE fabrication step can be completed at 30 m/min. We further fabricate methylammonium lead iodide solar cells to demonstrate the practical use of these TCEs, achieving an average power conversion efficiency (PCE) of 13%. The high-performance hybrid TCEs produced using R2R-compatible processes show potential as a viable choice for replacing vacuum-deposited indium tin oxide films on PET.

14 SOLAR ENERGY↗
DOE OSTI2026

Nickel Interlayer for Improved Silver Complex Inks Metallization in GaAs Photovoltaic Devices

Large areas of III-V photovoltaic panels are essential to supplying operational energy for a growing demand of satellites of strategic importance to the United States military, covering a range of applications. High fabrication costs and low manufacturing throughput are key barriers to meeting the necessary supply, which can in turn jeopardize mission success. At the device level, metallization based on printing of complex metal inks has attracted significant research interest due to its potential to substantially reduce processing costs and increase throughput while achieving electrical performance comparable to those of conventional metallization schemes. For GaAs photovoltaic devices, however, reliable electrical contacting remains challenging due to the formation of an interfacial oxide layer at the metal-semiconductor interface. This oxide barrier severely limits current extraction from the PV absorber, resulting in unacceptably high contact resistance. In this study, we report the introduction of a reactive nickel (Ni) interfacial layer between the silver metal fingers and the GaAs substrate to suppress oxide formation while maintaining a low-resistance electrical interface, and show performance data from fully fabricated GaAs devices incorporating the Ni interlayer. These results demonstrate the potential of reactive Ni ink as an effective interfacial layer for improved electrical contacting in low-cost PV metallization schemes.

14 SOLAR ENERGY↗
DOE OSTI2026

Direct Air Capture-Compatible Azolate and Amino Acid Ionic Liquids for Electrochemical CO 2 Reduction to CO on a Silver Cathode

Direct air capture (DAC) compatible ionic liquids (ILs) are attractive for integrating CO 2 capture and conversion due to their high CO 2 solubility at low partial pressures, tunable chemisorption mechanisms, low volatility, and wide electrochemical windows. However, very few ILs have high CO 2 uptake at DAC conditions (420 ppm CO 2 ), and even fewer have been evaluated for chemical compatibility and mechanistic continuity for combined capture and electrochemical CO 2 reduction (eCO 2 RR). We demonstrate that two representative DAC-capable ILs, [P 4444 ][Val] (amino acid-based) and [P 66614 ][5-Me-Imd] (azolate-based), exhibit favorable electrochemical reduction behavior. CO and H 2 were the dominant gas-phase products by GC, while 1 H and 13 C NMR confirmed negligible liquid-phase HCOOH. Chronoamperometry at moderate applied potentials (−2.0 to −2.5 V vs Ag/AgCl) in a two-compartment H-cell with a Ag coated carbon paper as the working electrode yielded steady-state current densities of ∼10 mA cm −2 with CO FE of 96% for [P 4444 ][Val] and 95% for [P 66614 ][5-Me-Imd], highlighting the role of viscosity and chemically absorbed CO 2 -IL species to provide highly selective CO formation while suppressing H 2 evolution.

amino acid ionic liquid↗
DOE OSTI2023

Hybrid Data‐Driven Discovery of High‐Performance Silver Selenide‐Based Thermoelectric Composites

Optimizing material compositions often enhances thermoelectric performances. However, the large selection of possible base elements and dopants results in a vast composition design space that is too large to systematically search using solely domain knowledge. To address this challenge, a hybrid data-driven strategy that integrates Bayesian optimization (BO) and Gaussian process regression (GPR) is proposed to optimize the composition of five elements (Ag, Se, S, Cu, and Te) in AgSe-based thermoelectric materials. Data is collected from the literature to provide prior knowledge for the initial GPR model, which is updated by actively collected experimental data during the iteration between BO and experiments. Within seven iterations, the optimized AgSe-based materials prepared using a simple high-throughput ink mixing and blade coating method deliver a high power factor of 2100 µW m −1 K −2 , which is a 75% improvement from the baseline composite (nominal composition of Ag 2 Se 1 ). In conclusion, the success of this study provides opportunities to generalize the demonstrated active machine learning technique to accelerate the development and optimization of a wide range of material systems with reduced experimental trials.

36 MATERIALS SCIENCE↗