bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Plasma-Synthesized Coupled Nanoplasmonic Gold for DNA Sersing
Authors: Shvalya Vasyl , Modic Martina , Zavašnik Janez , Rozman Damjana , Abdulhalim Ibrahim , Cvelbar Uros 
Published: February 2024

The facilitated electrochemical properties of plasma play a critical role in enhancing the synthesis and design of functional nanomaterials for the development of novel sensors. The targeted challenge is to customize and tailor functionality at multiple scales to improve detection device performance. In the realm of optoelectronics, plasmonic sensing is considered an efficient tool for investigating molecular properties, often accompanied by Raman, FTIR or Fluorescent spectroscopy. Specifically, Raman scattering, also known as SERS (surface-enhanced Raman scattering), is commonly used to probe analytes at a reduced scale using plasmonic enhancers. This technique is especially useful for rapidly and accurately investigating biologically relevant samples, such as DNA and RNA. DNA/RNA-related investigations are crucial in modern nanomedicine due to the progress made in bionanotechnology, DNA vaccines, and functional gene engineering. DNA, in particular, is highly valued by microbiologists because it contains information about the nature of bio-species. Currently, PCR-related methods dominate the field for molecular-sensitive DNA-level studies, but it is challenging to investigate using optical techniques like SERS. Despite its promise, SERS still requires technological and analytical improvements. A sophisticated plasmonic nanomaterial provides considerably improved photon scattering due to the strongly localized field confinement effect, resulting in better performance. In this report, a nanoplasmonic sensor was designed using a plasma-driven electrochemical reduction mechanism, achieved through an atmospheric pressure He-plasma jet setup operating at kHz frequency. The reactive oxidative species donated electrons via liquid-gas electrochemistry towards the Ar-delivered Au(3+)-containing microdroplets, resulting in microscaled aggregates composed of AuNPs obtained from the nebulized ionic gold liquid precursor. Due to the strong coupling between nanoparticles, a high analytical enhancement factor of about 107 was achieved, and the substrate enabled obtaining Raman fingerprints of bacterial DNA fragments (M. luteus and S. aureus, E. coli, J. lividum) at nanovolume sample quantities. Additionally, the main DNA molecular vibrational signatures associated with nucleobase motions were extracted from the collected spectra and used to reliably classify bacterial strains using statistical principal component analysis.[1]
References
[1] Shvalya, V., Vasudevan, A., Modic, M., Abutoama, M., Skubic, C., Nadižar, N., ... & Cvelbar, U. (2022). Bacterial DNA Recognition by SERS Active Plasma-Coupled Nanogold. Nano Letters.
The Effect of Junction Composition of Polarization Behaviour of Bipolar Membranes
Authors: Kao Yi-Lin , Aili David 
Published: February 2024

Bipolar membranes (BPMs), i.e, laminates cationic and anionic polymer membranes, have a wide range of applications. Starting from an early application in electrodialysis systems, the application scope has more recently broaden to electrochemical energy conversion systems such as water electrolyzer and CO2 reduction reaction, fuel cells and flow batteries.1 In connection to CO2 reduction reaction, the implementation of BPM effectively mitigates CO2 crossover driven by (bi)carbonate migrations, but the rate capability is limited by the large overpotential across current state-of-the-art BPMs.2 The large overpotential primarily originates from the slow water dissociation (WD) kinetics at the interface between the cation exchange layer (CEL) and anion exchange layer (AEL), and largely depends on junction morphology. The detailed structure-properties relationships remain poorly understood, but physical properties of individual polymeric membranes and the composition and morphology of the WD catalyst are important parameters and the optimal combination of materials may be different for different systems. Furthermore, the WD performance of BPM in MEA water electrolyzer not only depends on BPM’s junction contact, but also the interface contact between electrodes and CEL/AEL.
In this work, a series of BPM system featuring different compositions of membrane layers and WD catalysts are explored and characterized by polarization behaviour (J-V curve) via H-cell and MEA water electrolyzer. We attempt to link the junction composition created by different BPM systems to its WD performance and provide a systematic choice of CEL/AEL and WD catalyst in the BPM system.
(1) Blommaert, M. A.; Aili, D.; Tufa, R. A.; Li, Q.; Smith, W. A.; Vermaas, D. A. Insights and Challenges for Applying Bipolar Membranes in Advanced Electrochemical Energy Systems. ACS Energy Lett.
2021, 2539–2548. https://doi.org/10.1021/acsenergylett.1c00618.
(2) Garg, S.; Giron Rodriguez, C. A.; Rufford, T. E.; Varcoe, J. R.; Seger, B. How Membrane Characteristics Influence the Performance of CO 2 and CO Electrolysis. Energy Environ. Sci.
2022. https://doi.org/10.1039/D2EE01818G.
Investigation of CMP Process of Silica Substrate by Ceria Abrasive: Insights from Molecular Dynamics Simulation with Neural Network Potential
Authors: Ota Fukiko , Hirakawa Teruo , Antoku Nanami , Iikura Daisuke , Orita Akihiro , Okuno Yoshishige , Nomura Satoyuki 
Published: February 2024

Chemical mechanical polishing (CMP) is a process of surface planarization by chemical and mechanical driving forces. CMP is expected to solve various problems, including the surface roughness on semiconductor devices. An aqueous slurry, including abrasive grains and chemical components, is used in the CMP process. Development of slurries with high polishing rate, excellent planarity, and superior processability is not only a key challenge, but also a significant opportunity for the future of our industry. In order to achieve the development, it is necessary to understand the detailed mechanism of CMP, which involves complex phenomena accompanied by interfacial chemical reactions and mechanical friction.
Computational scientific approaches, such as density functional theory (DFT) and molecular dynamics (MD) simulations, are powerful tools for understanding complex tribochemical phenomena at the atomic scale. However, these methods require much computation time and present difficulties for large-scale simulations. To overcome this limitation, a computational method called Neural Network Potential (NNP) is a powerful tool because it achieves a good balance between accuracy and computational efficiency by constructing potential energy surfaces based on a neural network-based method.
We performed NNP-MD simulations of the ceria/silica interface with the development of CMP slurry including ceria abrasive grains, which is typically used on the surfaces of silicon layered devices. As a result, we succeeded in observing polishing phenomena at the interface at the atomic scale, namely Ce-O-Si bond formation between ceria abrasive grains and silica substrate, hydrolysis reaction of Si-O bond, and associated mono-silica dissociation from the substrate. We also performed simulations of systems containing chemical compounds added to the slurry for the purpose of controlling the polishing rate and observed the role of additives on the CMP process. In this presentation, we will show simulation results and discuss the mechanism of CMP of silica substrates with ceria abrasive grains in terms of dependence on surface morphology at the atomic scale and the role of additives.

Reference

[1] Tran*, R., Lan*, J., Shuaibi*, M., Wood*, B., Goyal*, S., Das, A., Heras-Domingo, J., Kolluru, A., Rizvi, A., Shoghi, N., Sriram, A., Ulissi, Z., & Zitnick, C. (2022). The Open Catalyst 2022 (OC22) Dataset and Challenges for Oxide Electrocatalysis. arXiv preprint arXiv:2206.08917.
(Invited) Developing High-Energy All-Solid-State Batteries with Long Cycle Life
Authors: Yang Shuhao , Kim Se Young , Chen Guoying 
Published: February 2024

While conventional lithium-ion batteries (LIBs) continue to gain progress through incremental improvements, the presence of organic liquid electrolytes brings about fundamental safety issues as their reactivity and flammability subject LIBs to thermal runaway. [1-4] With higher energy densities and better safety performances, all-solid-state batteries (ASSBs) consisting of a 4 V-class cathode active material (CAM), an inorganic solid-state electrolyte (SE) and a lithium-metal anode are considered the future of energy storage technologies. [5-6] The development of practical ASSBs, however, has met a number of challenges. SEs simultaneously meeting the criteria in conductivity, stability and mechanical properties are yet to be discovered. At the anode, reductive degradation of SE, high interfacial impedance and dendrite formation are the most pressing issues. At the cathode, instabilities due to oxidative degradation of SE, reactivities between SE and CAM as well as the loss of mechanical integrity significantly limit ASSB performance.
In this presentation, we discuss our recent effort in addressing these challenges, including the development of novel halide SEs, design of composite cathode structure that enables direct use of uncoated-LiNi0.8Co0.1Mn0.1O2 CAM, and implement of Li-metal based anodes that enable better interface with the SE. We demonstrate the excellent long-term cycling performance achieved on such cells and illustrate the underlying working mechanism. [7] The importance in proper matching of cathode, SE and anode properties as well as our views on future development of better-performing ASSB cells will be presented.

References

Arbizzani, G. Gabrielli and M. Mastragostino, Journal of Power Sources, 2011, 196, 4801-4805.

Murmann, R. Schmitz, S. Nowak, N. Ignatiev, P. Sartori, I. Cekic-Laskovic and M. Winter, Journal of The Electrochemical Society, 2015, 162, A1738.

Cao, X. Ren, L. Zou, M. H. Engelhard, W. Huang, H. Wang, B. E. Matthews, H. Lee, C. Niu and B. W. Arey, Nature Energy, 2019, 4, 796-805.

Fan, L. Chen, O. Borodin, X. Ji, J. Chen, S. Hou, T. Deng, J. Zheng, C. Yang, S.-C. Liou, K. Amine, K. Xu and C. Wang, Nature Nanotechnology, 2018, 13, 715-722.

Janek and W. G. J. N. E. Zeier, Nature Energy, 2016, 1, 1-4.

Famprikis, P. Canepa, J. A. Dawson, M. S. Islam and C. Masquelier, Nature Materials, 2019, 18, 1278-1291.

Y. Kim, H. Cha, R. Kostecki and G. Chen, ACS Energy Letters 2023, 8, 521.
Non-Equilibrium Plasma Oxidation of Elemental Hg
Authors: Jurov Andrea , Gačnik Jan , Živković Igor , Ribeiro Guevara Sergio , Kotnik Jože , Berisha Sabina , Vijayakumaran Nair Sreekanth , Cvelbar Uros , Horvat Milena 
Published: February 2024

Atmospheric mercury, specifically oxidized mercury (HgII), is the largest anthropogenic pool of mercury in the atmosphere. This type of mercury can accumulate in the food chain after undergoing methylation and entering ecosystems through wet and dry deposition. It is important to evaluate the level of wet and dry deposition, but measurements of atmospheric mercury have been biased due to insufficient consideration of measurement uncertainty and metrological traceability, especially for low ambient concentrations of gaseous HgII species.
To address this issue, a calibration method for HgII species has been presented based on atmospheric pressure non-equilibrium plasma oxidation of Hg0 to HgII. Hg0 is generated by reducing HgII in aqueous solution by SnCl2 and aeration, then oxidized to different HgII species using He plasma with traces of different reactive gases. The non-equilibrium plasma oxidation efficiencies, with corresponding expanded standard uncertainty values, were evaluated using a highly sensitive radiotracer. The efficiencies were found to be 100.5 ± 4.7% (k = 2) for 100 pg of HgO, 96.8 ± 7.3% (k = 2) for 250 pg of HgCl2, and 77.3 ± 9.4% (k = 2) for 250 pg of HgBr2. The presence of HgO, HgCl2, and HgBr2 was confirmed by temperature-programmed desorption quadrupole mass spectrometry (TPD-QMS).
The results demonstrate the potential of non-equilibrium plasma oxidation for reliable calibration of ambient air measurement instrumentation, leading to a better understanding of the sources, transport, and fate of this toxic pollutant in the environment. Knowing the chemistry and composition of atmospheric HgII species is crucial for assessing the extent of dry and wet deposition and mitigating the negative impacts of mercury pollution on human health and the environment.
Preventing Pt Catalysts in PEM Fuel Cells from CO Poisoning by Getting COPROX to Work
Authors: Rolison Debra R. , Novak Travis G. , DeSario Paul A. , Herzog Austin E. , Brintlinger Todd H. , DeBlock Ryan H. , Long Jeffrey W. 
Published: February 2024

Proton-exchange membrane fuel cells still require CO-scrubbed H2 feedstreams to sustain long-duration performance. Sufficiently CO-free H2 costs an order of magnitude more than steam refining fossil fuels to generate H2—and until green processes produce the bulk of H2, preferential oxidation of CO from H2-rich feedstreams, also known as COPROX, is a necessity. We design architected catalytic platforms as ultraporous metal nanoparticle–modified oxide aerogels in which a covalently bonded oxide nanoparticulate network (NPs) supports comparably sized catalytic nanoparticles (NPs). The degree of physical and chemical interfacial intimacy stabilizes the more catalytically active low valent state of Cu and the ultraporous catalytic platform demonstrates high activity and on-stream durability for thermal catalysis of CO [1]. We then evaluate the selectivity and activity of this architected catalyst and a related aerogel, Cu/GdxCe1–xO2, for preferential oxidation of CO (COPROX) in H2 feedstreams. The catalysts convert >95% of CO at temperatures that prevent oxidation (consumption) of the H2 fuel (a purification reaction necessary to prevent poisoning of the anode catalysts in H2 fuel cells). The architected Cu/ceria catalysts achieve >95% selectivity vs. H2 and maintain this unprecedented activity for >16 h at 100°C in dry or humidified feedstreams [2,3]. The ability to purify H2 from steam-reformed fuels for use in proton-exchange membrane fuel cells increases power source flexibility as the world transitions to more sustainable, carbon-neutral routes to highly purified H2.
[1] Stabilization of reduced copper on ceria aerogels for CO oxidation. C. L. Pitman, A. M. Pennington, T. H. Brintlinger, D. E. Barlow, L. F. Esparraguera, R. M. Stroud, J. J. Pietron, P. A. DeSario, D. R. Rolison, Nanoscale Adv. 2020, 2, 4547–4556 (10.1039/D0NA00594K).
[2] Preferential oxidation of CO in H2-containing gas. T.G. Novak, D.R. Rolison, P.A. DeSario, US Patent Application, filed Jan 27, 2023 [Navy Case #210,945].
[3] Cu/CeO2 and Cu/Gd-substituted CeO2 aerogels for active, selective, and stable COPROX catalysis. T.G. Novak, P.A. DeSario, T.H. Brintlinger, R.H. DeBlock, J.W. Long, and D.R. Rolison, ACS Sus. Chem. Eng.
2023, 11, 2853–2860 (10.1021/acssuschemeng.2c06158).
Batteries Worth Their Salt: Targeting Next Generation Stationary Storage with Molten Salt Electrolytes
Authors: Spoerke Erik D. , Maraschky Adam M. , Meyerson Melissa L , Percival Stephen J. , Peretti Amanda S. , Gross Martha S. , Small Leo J. 
Published: February 2024

There is an imminent need for batteries capable of meeting the evolving demands of a growing stationary storage landscape, one rich in renewable energy sources and challenged with unprecedented global electrification. Key to our future electrical grid, desirable large-scale, long-duration batteries must not only meet demands for high power and energy density, but they must be safe, cost-effective, and should be sustainably sourced from earth-abundant materials. Here, we will highlight our research and development of low temperature molten salt batteries that employ active materials such as sodium, aluminum, iron, chloride, and iodide. We will demonstrate the promise of our approach through a low-temperature (100°C) molten sodium battery that comprises a molten sodium anode, a solid-state NaSICON ceramic separator, and a low-cost molten metal-halide salt catholyte. These batteries, with remarkable voltages greater than 3.1V, are capable of months of cycling as well as high current charge and discharge behavior, greater than 50mA/cm2. Here, we will not only highlight these performance metrics, but we will describe how we used specialized electrochemical and chemical characterization technique to understand the impacts of molten salt electrolyte composition, electrochemistry, and interfacial interactions on battery performance. By understanding the connections between specific electrochemical phenomena and battery chemistry, we have learned to improve battery performance through tuning of properties, such as molten salt Lewis acidity and current collector composition. This scientifically-motivated battery design approach continues to enable agile innovation and advances to realize the potential of molten salt batteries as a new, impactful stationary storage technology.
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Mechanical Properties of Vcrmn and Vcrmnti High Entropy Alloys
Authors: Sultana Najmin Ara , Mohammed Yousuf S , Baumgart Helmut , Elmustafa Abdelmageed 
Published: February 2024

In this research, magnetron sputtering is employed to fabricate thin films of high entropy alloys. The target materials are derived from VCrMn and VCrMnTi systems. The focus is to pinpoint suitable candidates for robust and long-lasting beam exit windows in e-beam accelerators. The selection process considers their inherent characteristics, their capacity to dissipate power, and how they respond to irradiation in terms of mechanical traits like hardness, ductility, defect density, and strength.
For the bulk alloy samples of VCrMn and VCrMnTi, a sequence of nanoindentation tests has been executed to evaluate hardness and elastic modulus. The outcomes reveal that both the hardness and modulus are notably greater than those of any individual metal samples. It is anticipated that fabricated alloy films with same compositions will exhibit robust qualities in terms of mechanical properties, including ductility, defect density, and strength. The incorporation of additional titanium (Ti) alloying elements into the high entropy alloys (HEAs) of VCrMn is projected to enhance electron transmission.
The fabricated films have undergone thorough analysis and testing to comprehend their microstructural attributes and chemical composition which involves the utilization of SEM with EDS, FESEM, AFM to investigate microstructural and surface properties of the films. Subsequently, X-ray diffraction has been employed to acquire insights into the morphology and lattice orientation of the films.
Thermal Efficiency Evaluation after Thermocompression of Copper Layer Obtained By Dynamic Hydrogen Bubble
Authors: Schoenleber Jonathan , Janod Goulven , Chachay Lucas , Gigandet Marie-Pierre , Avenas Yvan , Daudin Remi , Missiaen jean-Michel , Bouvard Didier , Khazaka Rabih , Hihn Jean-Yves 
Published: February 2024

With the increase in engines electrification, especially in aircraft future developments, there is a need of extremely high-power converters in the power electric chain, interfacing the electrical network and the electric motors. The COPPERPACK project (COPPER based PACKaging for direct cooled power module ANR-19-CE05-0011) aims to module assembling by thermocompression, which requests the elaboration of thin nanoporous copper films to be placed between chips and metallized ceramic substrates. Different possibilities exist and have been tested all along the project, such as copper-zinc or copper-manganese electrodeposition followed by an anodic dissolution, but the faster and simpler way resides in electroforming deposition made by Dynamic Hydrogen Bubble Template (DHBT) [1]. This process works in unusual potentials and current densities where the competition between hydrogen discharge (commonly avoided) and copper reduction is very high. In this case, this method achieves thick deposits in very short time (few seconds) with high currents allowing a very fast growth of copper around hydrogen bubbles. Pores and ligaments sizes can be controlled by several operating parameters i.e. current densities, temperature, deposit time, chemical additives [2] as well by pulsed currents. Films were tested for chips assembling by thermocompression, and present excellent behavior’s. Several conditions have been tested, in different configurations, varying the size and the height of the chips.
Eventually, this system has been extended to cooling systems, favoring the assembling of copper foams and complex copper shapes, designed for cooling fluid circulation. Once again, the copper layers obtained by DHBT allow to build compact and efficient systems.
[1] Abdel-Karim, R.; El-Raghy, S. Chap 4 in Advanced materials and their applications - micro to nano scale. One Central Press, United Kingdom, pp 69–91, 2017
[2] Shin, H.-C.; Liu, M. Chem. Mater. 2004, 16, 25, 5460–5464 doi.org/10.1021/cm048887b
Light-Induced Platinum Deposition on Silicon-Based Semiconductor Devices
Authors: Fritz Mathias , Hoess Christian Elieser , Deckert Finn-Merlin , Bund Andreas 
Published: February 2024

Metal-semiconductor compounds are used in large numbers in microelectronics and need to be constantly improved. Platinum-silicon semiconductor contacts are often used in sensors and detectors, especially infrared detectors and cameras. Recent developments enable applications in medical technology, such as implanted pressure sensors in the human body.
Currently, platinum coatings on silicon-based semiconductor devices are mostly realized by sputtering techniques or platinum-containing printing pastes with subsequent heat treatment.
This paper will discuss recent results from the authors' lab on light-induced platinum electrodeposition. Special focus will be given to the pre-treatment of the substrates for the subsequent platinum deposition under illumination. In a systematic approach, all influencing parameters were identified and the most influential ones (pre-treatment, current density, electrolyte type, additives, etc.) were incorporated into an experimental plan. The challenges include a homogeneous platinum coating with low contact resistance and good adhesion. Last but not least, the characterization of the layers (with SEM, EDX, laser scanning microscope, etc.) will be discussed.