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At least 145 records · Page 8

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↗

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↗

Silver Adsorption on Calcium Niobate(001) Nanosheets: Calorimetric Energies That Explain Sinter-Resistant Support

Metal nanoparticles deposited on oxide supports are essential to many technologies, including catalysts, fuel cells and electronics. Therefore, understanding the chemical bonding strength between metal nanoparticles and oxide surfaces is of great interest. The adsorption energetics, adhesion energy and adsorbate structure of Ag on dehydrated HCa 2 Nb 3 O 10 (001) nanosheets at 300 K have been studied using metal adsorption calorimetry and surface spectroscopies. These dehydrated (“dh”) calcium niobate nanosheets “(dh-HCa 2 Nb 3 O 10 (001))” have stoichiometry Ca 4 Nb 6 O 19 . They impart unusual stability to metal nanoparticles when used as catalyst supports and are easy-to-prepare by Langmuir-Blodgett (LB) techniques, highly ordered, and essentially single-crystal surfaces of mixed oxides with a huge ratio of terrace to edge sites. Below monolayer coverage, Ag grows on dh-HCa 2 Nb 3 O 10 (001) as 2D islands of thickness ~2 layers. The differential heat of Ag adsorption is initially ~303 kJ/mol, increasing slowly to ~338 kJ/mol by 0.8 ML. At higher coverages, Ag atoms mainly add on top of these 2D islands, growing 3D nanoparticles of increasing thickness, as the heat decreases asymptotically towards silver’s heat of sublimation (285 kJ/mol). The adhesion energy of Ag(s) to this Ca niobate surface is estimated to be 4.33 J/m 2 , larger than on any oxide surface previously measured. This explains the sinter resistance reported for metal nanoparticles on this support. Electron transfer from Ag into the calcium niobate is also measured. Furthermore, these results demonstrate an easy way to do singlecrystal-type surface science studies - and especially thermochemical measurements - on the complex surfaces of mixed oxides: using LB-deposited perovskite nanosheets and ultrahigh vacuum annealing in O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Silver nanoparticle enhanced metal-organic matrix with interface-engineering for efficient photocatalytic hydrogen evolution

Integrating plasmonic nanoparticles into the photoactive metal-organic matrix is highly desirable due to the plasmonic near field enhancement, complementary light absorption, and accelerated separation of photogenerated charge carriers at the junction interface. The construction of a well-defined, intimate interface is vital for efficient charge carrier separation, however, it remains a challenge in synthesis. Here we synthesize a junction bearing intimate interface, composed of plasmonic Ag nanoparticles and matrix with silver node via a facile one-step approach. The plasmonic effect of Ag nanoparticles on the matrix is visualized through electron energy loss mapping. Moreover, charge carrier transfer from the plasmonic nanoparticles to the matrix is verified through ultrafast transient absorption spectroscopy and in-situ photoelectron spectroscopy. The system delivers highly efficient visible-light photocatalytic H 2 generation, surpassing most reported metal-organic framework-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic nanoparticles and organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Inorganic cesium lead mixed halide based perovskite solar materials modified with functional silver iodide

Inorganic CsPbIBr 2 perovskites have recently attracted enormous attention as a viable alternative material for optoelectronic applications due to their higher efficiency, thermal stability, suitable bandgap, and proper optical absorption. However, the CsPbIBr 2 perovskite films fabricated using a one-step deposition technique is usually comprised of small grain size with a large number of grain boundaries and compositional defects. In this work, silver iodide (AgI) will be incorporated as an additive into the CsPbIBr 2 perovskite precursor solution to prepare the unique perovskite CsI(PbBr 2 ) 1-x (AgI) x . The AgI additive in the precursor solution works as a nucleation promoter which will help the perovskite to grow and merge into a continuous film with reduced defects. With detailed characterizations, we found that incorporating AgI additive resulted in a uniform perovskite film with fewer grain boundaries, increased grain size, crystallinity, optical absorption while decreasing carrier recombination and trap density. Using the AgI in an optimum amount, we fabricated CsPbIBr 2 perovskite solar cells (PSCs) with a simple structure and achieved a power conversion efficiency (PCE) of 7.2% with a reduced hysteresis index. This work offers an alternative approach towards preparing high-quality CsPbIBr 2 perovskite films for solar cells with higher stability and other optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aggregation-induced phosphorescence sensitization in two heptanuclear and decanuclear gold–silver sandwich clusters

The strategy of aggregation-induced emission enhancement (AIEE) has been proven to be efficient in wide areas and has recently been adopted in the field of metal nanoclusters. Furthermore, the relationship between atomically precise clusters and AIEE is still unclear. Herein, we have successfully obtained two few-atom heterometallic gold–silver hepta-/decanuclear clusters, denoted Au 6 Ag and Au 9 Ag, and determined their structures by X-ray diffraction and mass spectrometry. The nature of the AuI…AgI interactions thereof is demonstrated through energy decomposition analysis to be far-beyond typical closed-shell metal–metal interaction dominated by dispersion interaction. Furthermore, a positive correlation has been established between the particle size of the nanoaggregates and the photoluminescence quantum yield for Au 6 Ag, manifesting AIEE control upon varying the stoichiometric ratio of Au : Ag in atomically-precise clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Silver salt enabled H/D exchange at the β-position of thiophene rings: synthesis of fully deuterated thiophene derivatives

Here, we disclose a silver catalyzed H/D exchange reaction, which can introduce the deuterium atom at the β position of thiophene rings without the assistance of any coordinating groups. The advantages of this reaction include operation in open air, usage of D 2 O as the deuterium source, good tolerance to a range of functional groups and obtaining high atom% deuterium incorporation. In addition, this H/D exchange reaction is employed for direct deuteration of a thiophene based monomer, which is usually prepared by multistep synthesis from expensive deuterated starting materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasmon-induced excitation energy transfer in silver nanoparticle dimers: A real-time TDDFTB investigation

Here, using real-time quantum dynamics calculations, we perform theoretical investigations of light-induced interactions and electronic excitation transfer in a silver nanoparticle dimer. Real-time time-dependent density functional tight-binding (RT-TDDFTB) calculations provide details of the quantum dynamical processes at an electronic/atomistic level with attosecond resolution. The computational efficiency of RT-TDDFTB allows us to examine electronic dynamics up to picosecond time scales. With time scales varying over six orders of magnitude, we provide insight into interactions between the nanoparticle and laser and between nanoparticles. Our results show that the coupling between nanoparticle monomers is dependent on the separation distance between the nanoparticles in the dimer. As the interparticle distance is varied, the dipole–dipole interactions and electronic excitation transfer mechanisms are markedly different. At large distances (from 50 to 20 Å), the energy transfer from NP1 to NP2 becomes more efficient as the interparticle distance decreases. The total dipole moment of the Ag 14 nanoparticle dimer increases linearly at an interparticle distance of 20 Å and reaches its maximum after 1.2 ps. The electronic excitation transfer is also the most efficient at 20 Å. At short distances, back-transfer effects reduce the ability of the dimer and NP1 to accept energy from the incident electric field. We attribute the distance-dependent features of the nanoparticle dimer to the beating between the laser acting on NP1 and the back transfer from NP2 to NP1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Antimicrobial Silver Touch Surfaces in an Occupational Medicine Clinic

Global efforts are being marshalled against the Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) pandemic. A key component of public health response is sanitizing or disinfecting the workplace, including the healthcare environment. Recently we launched what appears to be the first study of anti-microbial properties of silver hardware touch surfaces or fomites in an occupational health clinic setting. Here, we preview our major finding in order to emphasize the vital role of active sanitation measures, as opposed to reliance on passive controls, in public health response.

60 APPLIED LIFE SCIENCES↗

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↗

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↗

Fatigue-Like Behavior of Silver Metallization Gridlines and Proposed Damage Mechanics Model

In this work, we present a novel method to evaluate the fracture and fatigue-like behavior of crystalline silicon PV cell metallization. Initial results demonstrate that silver metal gridlines are capable of bridging a ~10–20 µm gap prior to becoming electrically open and do demonstrate fatigue-like behavior under cyclic straining conditions. This later phenomenon was well fit with a traditional power law equation for high cycle fatigue and enabled the development of a damage mechanics model for gridline failure.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Deuterium Permeation Through a Self-Supported Palladium-Silver Membrane in Helium Gas Mixtures

Palladium membranes and membrane reactors can separate and purify tritium from impurities in the plasma exhaust processing system for the fusion energy fuel cycle. Membranes can also act as a continuous separation method to remove tritium from helium streams in the breeder blanket tritium extraction system, such as from the purge gas of solid breeders. To investigate the potential of these membranes for these applications, we performed a deuterium permeation campaign with a self-supported palladium-silver (Pd-25Ag wt%) tube of 0.15 m length, 76 µ m wall thickness, and 3.0 mm inner diameter. A gas mixture of 3.95% D 2 and a balance of He was delivered to the inside of the tube and D permeated radially outwards through the membrane into a vacuum chamber. Permeation experiments were conducted at 300 ° C, 350 ° C, 400° C, and 450°C, from 100 to 1000 sccm total flow rate, and with total pressures of 90, 150, 190, and 250 kPa. Further, deuterium permeation was consistently lower than predicted from diffusion-limited permeation models, thus we developed a transport model that included gas-phase mass transfer and surface reactions to model experimental results. The dissociation constant was optimized to fit the developed model to experimental data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Molybdenum and silver photoemission survey spectra from hard x-rays

Electron emission from thick polished samples of polycrystalline molybdenum (Mo) and single crystalline $\langle$111$\rangle$ silver (Ag) was measured with hard x-ray photoemission spectroscopy. Six different excitation x-ray energies were used, nominally 8.0, 11.0, 13.0, 15.0, 18.0, and 21.5 keV. Survey spectra were recorded with each excitation to a kinetic energy of at most 15 keV, often capturing the entire emission range. The Mo 1s core peak was measured. Detailed LMM Auger spectra of Mo show marked increases in intensity and altered shape when x-ray energy exceeds the Mo 1s binding energy. The Mo and Ag L-shell photoelectron peaks are measured at four x-ray energies up to 18 keV showing the transition from 2p3/2 to 2s photoionization dominance.

47 OTHER INSTRUMENTATION↗