bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Digital Presentation) Fundamental Insights into Electrodeposition of Mixed Chromium Metal-Carbide-Oxides from Trivalent Chromium – Formate Electrolytes
Authors: Ankora Maxine , Mamme Mesfin Haile , Lammers Koen , Wijenberg Jacques , de Vooys Arnoud , Terryn Herman Albert , Mol Arjan 
Published: November 2022

Recent restrictions on industrial usage of hexavalent chromium under new REACH legislation have further sparked the development of hexavalent chromium-free chromium plating processes. An industrially important development in this field is Trivalent Chromium Coating Technology (TCCT®), a chromium electroplating technology for packaging steel developed at Tata Steel. In this process, aqueous trivalent chromium electrolytes rather than hexavalent chromium electrolytes are employed for the electrodeposition of metallic chromium. However, to deposit metallic chromium from a trivalent chromium electrolyte, it is necessary to incorporate a complexing agent given the kinetic inertness of aqueous trivalent chromium complexes. Formate plays this role in the TCCT® process yielding coatings comparable to the conventional hexavalent chromium-based process [1-4].
However, understanding the mechanism and kinetics of chromium electrodeposition from this system is quite limited. Fundamental knowledge of the deposition process is key for industrial process optimization. Essential to determining the reaction mechanism and kinetics is the identification of the chemical species involved in the reaction. Using a hybrid multiscale experimental and computational approach, insights into chromium complexation in the bulk electrolytes and how this speciation influences the composition of the deposit have been gained.
Samples electroplated in electrolytes of varied formate concentrations were characterized using X-ray Fluorescence (XRF) spectroscopy and X-ray Photoelectron Spectroscopy (XPS). Results from these analyses show that metallic chromium is only deposited when the electrolyte contains formate ions. In the absence of formate, only oxide and carbide species are deposited. The characterization results also show a current efficiency of the TCCT process of ~ 40%. From observations from surface characterization as well as spectroscopic analysis and density functional theory (DFT) and ab initio molecular dynamics studies (AIMD) of the bulk electrolyte, the coordination and complexation of formate ion in the chromium complex responsible for metallic chromium deposition have also been identified. Voltammetric studies coupled with ex-situ XPS and scanning electron microscopy (SEM) surface characterization also lead to a clear definition of the reaction mechanism of metallic chromium deposition that the incorporation of formate in trivalent chromium electrolytes makes possible.
Study on Thermoelectric Property of Te Wire-Based Organic-Inorganic Hybrid Thermoelectric Composites through Electrochemical Process
Authors: Lee Min-Jeong , Kim In Yea , Kim Chae Yoon , Lim Gi hwan , Kim Jaehun , Kim Dong Hyun , Lim Jae-Hong 
Published: November 2022

Energy demand and importance are increasing with the industrial development and the development of high technology in modern society. However, the global supply of energy is facing problems such as fossil energy depletion and environmental pollution, and research and interest in alternative energy are increasing. Among them, research on thermoelectricity is being actively conducted. The thermoelectric characteristics are represented by the Seebeck coefficient, electrical conductivity, and thermal conductivity at the operating temperature. This is expressed as a thermoelectric performance index (ZT). ZT appears in proportion to the electrical conductivity and Seebeck coefficient, and inversely proportional to the thermal conductivity. Thermoelectric materials are divided into inorganic thermoelectric materials and organic thermoelectric materials, both of which have advantages and disadvantages. The inorganic thermoelectric material has high thermoelectric performance, but it is highly toxic and has low electrical conductivity. On the other hand, organic thermoelectric materials have lower performance than inorganic materials they are easy to obtain and have high electrical conductivity. In this study, organic-inorganic hybrid thermoelectric material was studied by combining the advantages of each material.
In this study, Te nanowires (NWs) were synthesized at 50 Co by galvanic replacement reaction. We used Si (1 0 0) wafer as substrate of NWs. The substrate was degreased with acetone and ethanol. The solution of cadmium(1M), hydrofluoric acid (HF 51.0%, 4.5M) and tellurium dioxide (TeO2, 2mM). After the reaction, the synthesized Te NWs were washed with deionized water and IPA. The prepared Te NWs reacted with solution (silver nitrate in ethylene glycol) for topotactic reaction. After the reaction, the wires are washed several times with ethanol. The hybrid TE was fabricated by coating PEDOT:PSS on Ag-Te NWs with different ethylene glycol (EG) doping.
A composite thermoelectric material was manufactured using Te (inorganic thermoelectric material) and PEDOT:PSS (organic thermoelectric material). Ag-topotactic reaction was conducted to increase the electrical conductivity of NWs. As the EG doping concentration of PEDOT increased, the electrical conductivity because the layer of PEDOT:PSS became thinner and didn’t fill the gap of NWS sufficiently. In conclusion, the Te NWs coated with PEDOT:PSS with 10% EG doping showed the best electrical conductivity and power factor. The more details will be presented.

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Toward "Electrochemical/Materials Processing for Space Engineering" Symp
Authors: Fukunaka Yasuhiro 
Published: November 2022

Several symposium have been hosted such as “Electrochemistry in Space”, 236th ECS Atlanta(2019) and “ISRU”, Call for Papers: ACS Earth and Space Chemistry for Special Issue: Materials of the Universe : the Final Chemical Frontier(2020). However, their scopes are rather shifted to space exploration concept, primarily led by the Space Agency. Those are not geared toward training graduate students for the future space engineering using basic science, especially Space Environmental Utilization Research is not intensively covered. It is our thought that the Electrochemical Society (ECS) shall organize such an interdisciplinary education & research program collaborating with TMS society (Light Metal and Materials Processing Divisions). The research subjects on Space Energy & Resources must be newly stimulated to make recognize and support the field of Electrochemical/Materials Processing, encompassing:
[1] Basic Science with Drop Tower, Rocket & ISS
(for example: Nucleation & Growth of Ice in Space, Gas Electrode Behavior)
[2] Microgravity Research like Protein or Semiconductor Crystallization
[3] Energy Conversion and Storage System for Space Engineering
(Unitized Regenerative FC), LIB, Nuclear Battery)
[4] Sensor System for Rover Eng. & X-ray Astrophysics
[5] Life Supporting System including Desalination Technology and CO2 Reduction
[6] ISRU, Materials Processing/Thermodynamic Measurement with ELF
[7] Computational Chemistry/Interfacial Reaction Dynamics
[8] Ion Transfer through Cell Membrane in Bio-physics
[9] Global Environmental Observation System
[10] Others
Insights into Cu Surface Chemistry Via in-Operando nanoparticle Enhanced Vibrational Spectroscopy and Mass Spectrometry Measurements
Authors: Raciti David , Tackett Brian , Braun Trevor Michael , Hight Walker Angela , Moffat Thomas P 
Published: November 2022

Copper electrodeposition is a central process in the metallization of microelectronics and more recently has found use as an important electrocatalyst in the conversion of CO2 to hydrocarbons. Gaining mechanistic insight into the nature of the respective reactions requires in situ and better still in operando measurements. Herein the utility of shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) and electrochemical mass spectrometry (EC-MS) to study the potential dependent anion adsorption and hydride formation on low index Cu single crystals surface will be detailed. SHINERs enables monitoring of competitive adsorption between Cl- and SO4
2- on Cu(100) and Cu(111) surfaces (Figure 1a). Saturated ordered halide adlayers are formed at potentials slightly below the open circuit potential while moving to more negative values halide is disrupted resulting with the emergence of a sulfate mode near 970 cm-1. In the case of Cu(111) the desorption of the halide adlayer is coupled to the formation of a hydride phase (Figure 1b) as evident in both SHINERS and EC-MS measurements. SHINERS was also employed to examine the adsorbate dynamics associated with superconformal electrodeposition of Cu. Specifically, competitive adsorption between Cl- and sulfonate terminated thiol/disulfide accelerators molecules was examined during Cu deposition on planar and patterned surfaces (Figure 1c). The ability of the nanoparticle reporters to float on the advancing surface is demonstrated and used to probe the additive evolution on the growth front associated with superconformal electrodeposition. This work demonstrates the capabilities of operando electrochemical measurements and their importance in achieving future technological breakthroughs.
Figure 1. Capturing Cu interfacial chemistry with operando SHINERS (a) on a c(2x2)-Cl covered Cu(100) surface, (b) coupling to EC-MS to reveal the existence of hydride on Cu(111) in Cl containing electrolyte and (c) to track accelerator coverage on electrodeposited pattern surfaces.

Figure 1
Compressive Stress and Charge Redistribution during CO Adsorption Onto Pt
Authors: Stafford Gery , Schwarz Kathleen , Vinson John , Raciti David 
Published: November 2022

Electroorganic reactions, where energy is either stored or released from chemical bonds within carbon-based molecules, are essential to help achieve a circular carbon-based economy. Central to electrochemical conversion of organic molecules is carbon monoxide (CO), which serves as both an intermediate in electrochemical CO2 reduction to hydrocarbons and electrochemical oxidation in fuel cells that operate via oxygenated hydrocarbons (e.g., ethanol, methanol). For the latter, Pt has been the predominate catalyst of choice, and substantial effort has been spent to identify the mechanistic details for complete oxidation of alcohol-based fuels. With CO conversion serving as an important if not rate-limiting step of the oxidative process, it is critical to understand the state of a catalytic surface when CO is present.
The change in surface stress associated with the adsorption and oxidative stripping of CO on (111)-textured Pt is examined using the wafer curvature method in 0.1 mol/L KHCO3 electrolyte.1 The curvature of the Pt cantilever electrode was monitored as a function of potential in both CO free and CO-saturated electrolyte. Although CO adsorbs as a neutral molecule, significant compressive stress, up to -1.3 N/m, is induced in the Pt. The magnitude of the stress change correlates directly with the CO coverage, and within the detection limits of the stress measurement, is elastically reversible. Density functional theory calculations of a CO bound Pt surface indicate that charge redistribution from the first atomic layer of Pt to subsurface layers account for the observed compressive stress induced by the charge neutral adsorption of CO. A better understanding of adsorbate-induced surface stress is critical for the development of materials platforms for sensing and catalysis.

References

D. Raciti, K.A. Schwarz, J. Vinson, and G.R. Stafford, The Journal of Physical Chemistry C , 126, 4446-4457 (2022).
Dynamic Multi-Dimensional Numerical Transport Study of Lithium-Ion Battery Active Material Microstructures for Automotive Applications
Authors: Lopata Joseph Steven , Garrick Taylor R. , Zeng Yangbing , Shimpalee Sirivatch 
Published: November 2022

Conventional porous electrode battery modeling for a variety of applications makes assumptions to reduce the complexity of the simulation where tradeoffs between computational complexity and electrode detail can be realized without significantly impacting the accuracy of the results. The most common porous electrode battery model is the pseudo-two-dimensional (P2D) model as popularized by Newman and colleagues. These porous electrode battery models typically focus on simulating gradients in two dimensions; the primary dimension through the thickness of the battery cell electrodes and separators, and the secondary dimension in the radial direction of spherical active material particles. The particles are distributed throughout what is assumed to be a homogeneous porous electrode domain. Typically, uniformity in particle size, porosity, and tortuosity is assumed.
In this work, the development of a three-dimensional microstructure (3DMS) lithium-ion battery model will be presented. With the increase in computational resources available in academia and industry, simulation of the microstructure in 3D is possible. Active material domains of both the anode and cathode can be generated stochastically to create microstructures representing the electrodes, with voids surrounding the particle representing the electrolyte. A comparison between the P2D and 3DMS models with sensitivity analysis focused on items that can be probed with microstructure simulations will be discussed and similarities and/or differences in charge/discharge characteristics, overpotentials, and concentration profiles will be presented. The findings from this work will provide a path to simulate at the microstructure level, drive electrode design, and translate the effects of heterogeneity into a homogenous porous electrode model.
(Invited) Iron/Iron Redox Flow Battery Optimisation Studies
Authors: Noack Jens , Wernado Mike , Ortner Jens , Pinkwart Karsten 
Published: November 2022

Due to the steadily increasing growth of renewable energies, the importance of stationary energy storage systems is growing significantly. A potentially very cheap alternative to lithium-ion and vanadium redox flow batteries are iron/iron redox flow batteries. Iron is an extremely inexpensive active material, thus enabling cheap energy storage solutions and perhaps batteries with very low investment costs while maintaining low toxicity and aggressiveness due to the moderate pH and relatively low potential of the positive electrode. An iron(II) salt solution serves as the initial solution and is oxidized to iron(III) at the positive electrode and reduced to elemental iron at the negative electrode during the charging process.
One of the biggest problems is the formation of hydrogen at the iron electrode during the charging process at low pH values and the precipitation of iron(II) hydroxides from slightly acidic pH values [[i]]. When operating this type of battery, the negative electrode must be kept within a narrow pH window where no precipitation occurs and as little hydrogen as possible is evolved, which in turn significantly reduces battery life and efficiency.
As part of a feasibility, different iron/iron redox flow batteries were constructed and their electrochemical properties were investigated. One of the most important components of the battery was the recombination cell, which allows hydrogen evolution to be reversed, thus significantly increasing the number of cycles. Different substrates for iron deposition were investigated, different membranes as well as different charging and discharging parameters of the battery. With the recombination cell, it was possible to complete up to one hundred cycles with long cycle times of 1 h charging time, and to calculate and compare efficiencies and other performance values. A kynol fabric achieved the best performance and all membranes investigated showed potential applications. An optimized battery achieved up to 70% energy efficiency at 12.5 mA/cm² and max. 47 mW/cm² power density at 75 mA/cm².

[i] [1]L. W. Hruska, J. Electrochem. Soc. 1981, 128, 18.

Figure 1
(Invited) Plasma-Based Thin Film Technology in Fabrication of Nano- to Giga-Sized Electronics
Authors: Kuo Yue 
Published: November 2022

This talk is presented to honor Professor Noel Buckley who has made many important contributions in compound semiconductors, copper thin film deposition, batteries, and other topics critical to the manufacture of modern optoelectronics. He is also a good friend, colleague, and collaborator for 3 decades.
Plasma technology has been broadly used in the mass production of modern electronics varying from nano-sized devices in ICs to giga-dimension flat panel displays. It is especially critical to the preparation of thin films with well-controlled properties, geometry, and reliability. In this talk, the speaker shall discuss the recent development of plasma thin film deposition, etching, and reaction in his laboratory for the manufacture of electronic and optoelectronic products.

Room-temperature plasma-based copper etch processes for sub 0.5 μm geometry patterns ICs and large-area direct-view TFT LCDs

Sputter deposited sub 1 nm EOT high-k gate dielectrics, nanocrystals embedded high-k dielectric nonvolatile memories, and solid-state incandescent light emitting devices (SSI-LEDs)

Plasma oxidation of copper as a self-aligned passivation film
(Invited) Fluorination and No-Carrier-Added Radio-Fluorination of Organic Molecules Using Cation Pool Technique
Authors: Balandeh Mehrdad , Sadeghi Saman 
Published: November 2022

Positron emission tomography (PET) is a molecular imaging method is being employed in preclinical and clinical studies such as oncology or diagnosis of certain diffuse brain diseases. The growth of PET as a powerful method in biomedical research, needs development of more efficient methods for developing the positron-emitting radiotracers. The fluorine radioactive isotope (18F) has a short half-life of 110 min, making it as an ideal PET radiotracer. 18F labeling of electron rich moieties such as aromatic molecules is highly desirable due to their high biostability.
In 1990 Yoshida and co-workers developed the cation pool method which stabilized carbamate cationic intermediates generated during a two electron oxidation followed by deprotonation that takes place in the anodic compartment of a two compartment cell under low temperatures.1 The method allows for rapid reactions with nucleophiles that may be unstable during electrolysis and can be added to the reaction mixture at the end of electrolysis to form the final product.
Here, we report on the extension of the cation pool method for the application of electrochemical fluorination and radio-fluorination of methyl (phenylthio)acetate. Electrochemical fluorination and no-carrier-added radio-fluorination were successfully achieved using the cation pool method. The cation pool method has tremendous potential for radiofluorination experiments. The excess concentration of cations may provide an efficient reaction mechanism for late-stage fluorination under low fluoride concentrations encountered in radiochemistry. Furthermore, radiochemical yield, which is reduced by decay of the radioisotope, can benefit from a rapid late-stage fluorination reaction. The cation pool can be prepared prior to cyclotron production of 18F isotope, thereby, providing a rapid late-stage fluorination reaction, maximizing radiochemical yield by minimizing decay through a rapid reaction of the previously prepared cations with 18F-fluoride.
Synthesis parameters such as temperature, supporting electrolyte concentration and type, and precursor concentration were studied and optimized. Optimum reaction yield was obtained at -20 °C. The products were characterized using gas chromatography–mass spectrometry (GC-MS), nuclear magnetic resonance (NMR), radio-thin-layer chromatography (radio-TLC) and high-performance liquid chromatography (HPLC).

References

Yoshida, J. et al. Direct Oxidative Carbon−Carbon Bond Formation Using the “Cation Pool” Method. 1. Generation of Iminium Cation Pools and Their Reaction with Carbon Nucleophiles. J. Am. Chem. Soc.
121, 9546–9549 (1999).
Direct Patterning of ZnO Deposition By Atomic-Layer Additive Manufacturing Using a Safe and Economical Precursor
Authors: Barr Maissa K. S. , Stefanovic Sonja , Gheshlaghi Negar , Zanders David , Devi Anjana , Bachmann Julien 
Published: November 2022

AS-ALD has the potential to overcome many of the challenges the semiconductor industry is facing by enabling self-aligned fabrication, instead of lithography’s cost, resit, equipment. Main challenges in AS-ALD are the need for pre-patterned substrates, defects outside of the desired growing area resulting from insufficient selectivity, and limited selection of substrate materials that allow deposition. [1, 2]
To overcome these challenges, we chose for the first time the novelty of direct patterning with an AL-3D printer, also called atomic layer additive manufacturing (ALAM). 3D-printing is a flexible and efficient tool for reducing the cost and time spend for designing and manufacturing. AL-3D in principle functions similar to conventional g-ALD and the special design of nozzle led in producing direct patterning. All the commercially available precursors which have been used in g-ALD are compatible with our invented equipment and not only we can produce the same films conveniently but also this device allows us to use new precursors e.g. Zn(DMP)2 opening a new chemistry window. We have already deposited different materials TiO2, Pt, SiO2, Al2O3 successfully using TTIP, (MeCp)PtMe3, APTES, TMA as precursor. The ZnO process is very well behaved in ALD community as a diethylzinc (ZnEt2) precursor’s very high vapor pressure and its very high reactivity to water. Our attempts at reducing the amount of vapor delivered were successful in part but the results were not sufficiently reproducible, therefore we turned to the use of a new zinc precursor instead.
In this work we focus on the new precursor Zn(DMP)2 instead of ZnEt2 for ZnO deposition. The Zn(DMP)2 has a very low vapor pressure, the ethyl groups are complemented by dimethylamino substituents that stabilize central zinc ion and thereby render the molecule less reactive to water. Our characterization results shows the deposited ZnO films with our new precursor has same structure and composition as with ZnEt2 with a constant growth rate of 1.0 Å per cycle. the crystals are oriented in a roughly isotropic manner.
After testing Zn(DMP)2 in classical ALD we achieved to print homogeneous patterns with well-defined edges and uniform thicknesses among the whole pattern. The rough particulate deposits indicative of uncontrolled CVD-mode deposition obtained with the ZnEt2 + water reaction are completely absent of lines obtained from the Zn(DMP)2 + water reaction. Furthermore, we fabricate a metal oxide transistor MOSFET to demonstrate the practical applications of the device.

Clark; K. Tapily; K.-H. Yu; T. Hakamata; S. Consiglio; D. O´Meara; C. Wajda; J. Smith; G. Leusink; Perspective: New Process Technologies Required for Future Device and Scaling. APL Mater. 2018, 6, 05203

Fang; J. C. Ho, Area-Selective Atomic Layer Deposition: Conformal Coating, Subnanometer Thickness Control, and Smart Positioning. ACS Nano 2015, 9 (9), 8651-8654.