bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Achieving Erosion Less Designing Cu- and Isolation-Film Polishing-Rate Selectivity in Cu-Film Chemical Mechanical Planarization
Authors: Park Jea-Gun , Kim Pil-su , Jeon Min-Uk , Jin Hyeong-Ju , Ahn Ho-Jun , Kim Ju-Yeon , Park Jin-Hyung 
Published: December 2024

Design of logic devices has been scaled down up to several nm (i.e., 5, 4, 3, 2, and 1.8 nm). This scale-down has accompanied a rapid scale-down of the Cu-line width, increasing Cu-line pattern density. The Cu-line formation essentially requires Cu-film CMP, producing the detrimental defects such as dishing, erosion, and edge over erosion (E.O.E) after Cu-film CMP. Particularly, erosion and E.O.E intensively depend on the Cu-line width, and Cu-line pattern density, degrading device operating speed and yield. However, erosion and E.O.E have not been reported clearly.
In this study, unlike conventional Cu-film CMP slurries, for achieving erosion- and E.O.E-less in nanoscale Cu-line pattern CMP, 1-step Cu-line CMP process was designed using a Cu bulk CMP slurry performing remarkably high polishing-rate via surface chemical oxidation layer formation using halide oxidant (i.e., H5IO6) and a Cu barrier-metal (BM) slurry conducting hindrance layer formation using inhibitor (i.e., BTA). Using designed Cu bulk and BM slurries with 100-nm-diameter colloidal silica abrasives could achieve erosion-less for the Cu-line pattern density of 5 ~ 55%, but a high amount of E.O.E remained for all Cu-line pattern density after CMP, as shown in Fig. 1. Thus, the dependencies of erosion and EOE on polishing-rate selectivity between Cu- and Isolation-films were investigated for achieving both erosion- and EOE-less. In our presentation, we will prove the mechanism of the selectivity on Cu- and Isolation-film. In addition, we will present the dependencies of the chemical dominant polishing properties (i.e., OH radical, chemical oxidation degree of the Cu- and Isolation-film surface, chemical composition of chemical oxidation, slurry absorption degree, and corrosion potential and current) as well as the mechanical dominant polishing properties (i.e., electrostatic force between abrasives and Cu- and Isolation-film surface) on the inhibitor concentration.

Acknowledgment

This research was supported by the MOTIE(Ministry of Trade, Industry & Energy (1415180388) and KSRC(Korea Semiconductor Research Consortium) (20019474) support program for the development of the future semiconductor device, and by the Brain Korea 21 PLUS Program and the Samsung Electronics’ University R&D program.

Figure 1
Nano- and Mesoporous Structure Formation Probed with in Situ/in Operando Small and Wide-Angle X-Ray Scattering Analysis during Electrodeposition and Dealloying Processes
Authors: Amenitsch Heinz , Wieser Philipp Aldo 
Published: December 2024

Electrochemical formation of nanoporous materials by electrodeposition or dealloying is essential in various fields such as catalysis, energy storage, and sensing due to their high surface areas and controlled pore sizes. Understanding the underlying principles leading to specific morphologies during the electrochemical protocol is of importance for a directed design of desired morphologies. In situ/in operando analysis at the nanoscale, such as grazing incidence small and wide angle X-ray scattering (GISWAXS), is an important tool to understand the pathway of the structure evolution at both the mesostructural and the crystalline levels. Here the development of a versatile electrochemical cell for GISWAXS [1] was essential to be able to investigate such processes.
In this presentation an overview of various projects utilizing GISWAXS is given: (i) dealloying of the binary systems AgAu and CoPd [2]; electrodeposition of (ii) vertical aligned hexagonal Pt films using liquid crystal templating with Brij®56 [3]; and (iii) mesoporous platinum nickel films using Pluronic P123 as structure directing agent, as proposed by [4]. Additionally, some current highlights in the field of electrodeposition of ordered materials will be presented.

M. Bogar, I. Khalakhan, A. Gambitta, Y. Yakovlev, H. Amenitsch, In situ electrochemical grazing incidence small angle X-ray scattering: From the design of an electrochemical cell to an exemplary study of fuel cell catalyst degradation. J. Power Sources. 477, 229030 (2020).

Gößler, E. Hengge, M. Bogar, M. Albu, D. Knez, H. Amenitsch, R. Würschum, In Situ Study of Nanoporosity Evolution during Dealloying AgAu and CoPd by Grazing-Incidence Small-Angle X-ray Scattering. J. Phys. Chem. C. 126, 4037–4047 (2022).

P.A. Wieser, D. Moser, B. Gollas., H. Amenitsch, Monitoring of Pore Orientation by in Operando Grazing Incidence Small-Angle X-ray Scattering during Templated Electrodeposition of Mesoporous Pt Films, Acs Appl. Materials and Interfieces 15, 47604-47614 (2023).

K. Eiler, S. Surinach, J. Sort, E. Pellicer, Mesoporous Ni-rich Ni–Pt thin films: Electrodeposition, characterization and performance toward hydrogen evolution reaction in acidic media, Applied Catalysis B, Environmental 265, 118597 (2020).

Fig. 1 (a) Scheme of the experimental setup for monitoring electrodeposition of mesoporous PtNi via in operando GISWAXS. The incoming X-ray beam impinges on the sample at a glancing angle αi
(shown in the zoomed inset into the electrochemical cell). The scattering intensity is recorded simultaneously by two detectors: one in the direct beam, to study the GISAXS pattern during electrodeposition, and the other in the GIWAXS regime to resolve the diffraction pattern. (b) Chronoamperometric data during electrodeposition, performed under constant potentials at - 0.7 V vs AgCl. (c) Exemplary SEM micrograph of resulting mesoporous PtNi film.

Figure 1
Gold and Gold Alloys Electropolishing Using HCl-Glycerol-Ethanol Electrolytes
Authors: Rodriguez Julymar , Doche Marie-Laure , Hihn Jean-Yves 
Published: December 2024

Electropolishing (EP) is an electrochemical process used in the final stage of metal processing to reduce surface roughness and enhance functional, technical, and aesthetical properties. Some of its advantages are the preservation of surface metallurgical properties and the ability of treating complex geometries.
EP is based on a homogeneous dissolution of the surface, driven by a competition between oxidation reactions and dissolution. Compounds such as cyanides and thiourea, which was now classified as a classed 3 carcinogen, can form very stable soluble complex with precious metals like gold and its alloys. Consequently, they have been widely used in the formulation of EP electrolytes for these materials, but their toxicity has led to the research of alternative solutions.
This work presents a study based on a cyanide and thiourea free electrolyte previously reported in the literature for pure gold electropolishing and composed by hydrochloric acid, glycerol, and ethanol1,2. The aim was to give new insights in the involved mechanisms to evaluate the electrochemical behavior and the influence of different parameters on pure gold, and to extend this process to 18k jewelry gold alloys (yellow, rose, red and gray). In the first part of the study, only two of the electrolyte components (HCl-glycerol) were used to study the influence of chloride concentration on pure gold EP. Electrochemical techniques and surface properties analysis were evaluated.
In the second part, the effects of adding ethanol to electrolyte composition and of variating rotation speed were also evaluated on pure gold. The best results were obtained for a HCl 50%vol. - Glycerol 25%vol. - Ethanol 25%vol. electrolyte at a rotation speed of 1000 rpm. This solution was then used to electropolish 18K gold alloys. Mitigated results were obtained for silver-containing alloys (yellow, rose and red), which were not uniformly polished due to the formation of an AgCl film on the surface that partially masks the substrates, whereas better results were obtained with 18K grey gold3.
(1) Peck, W. F.; Nakahara, S. Preparation and Electropolishing of Thin Gold Disc Specimens for Transmission-Electron-Microscope Examinations. Metallography 1978, 11 (3), 347–354. https://doi.org/10.1016/0026-0800(78)90047-2.
(2) Verlinden, J.; Celis, J. P.; Roos, J. R. Passivation-depassivation behaviour of gold in a hcl-glycerol solution and its application to electropolishing. Thin Films Sci. Technol. 1983, 341–346.
(3) Rodriguez J. ; Doche M-L ; Hihn J-Y ; Electropolishing of gold and gold alloys in HCl-glycerol-ethanol electrolytes App. Surf. Sci. Adv. 21(2024) 100604 https://doi.org/10.1016/j.apsadv.2024.100604
(Invited) Mn-Based High-Energy Cathodes for Lithium-Ion Batteries
Authors: Chen Guoying 
Published: December 2024

Cation-disordered Li-excess rocksalts (DRX) are promising cathode materials for next-generation lithium-ion batteries utilizing sustainable resources. [1] These compounds are typically Co- and Ni-free, and they offer exceptionally large charge storage capacities by activating the redox reactions of both cationic transition-metals and anionic oxygen in the lattice. [2-4] Recent studies showed that significant performance improvement can be achieved by introducing fluorine substitution. Fluorine was found to improve local structural stability and chemomechanical properties, as well as reduce oxygen gas release, impedance rise and capacity fade. [5-7] However, achieving adequate cycle life remains a formidable barrier in DRX cathodes.
In this presentation, we will show our recent effort in developing stable DRX oxyfluorides based on Mn-redox chemistry. Mn-rich DRX oxyfluoride cathodes consisting of earth-abundant elements will be presented. These materials experience unique local structural transformations upon charge and discharge, leading to dynamic evolution in voltage profile and significant capacity rise during early cycles. Stable cycling can be achieved after the initial activation process. Our understanding in how chemistry can impact local and long-range structures and their evolution during electrochemical cycling will also be presented, as well as the perspectives on future directions in cathode development.

References

Chen D.; Ahn J.; Chen, G. An Overview of Cation-Disordered Lithium-Excess Rocksalt Cathodes. ACS Energy Lett.
2021, 6,

Lee, J.; Urban, A.; Li, X.; Su, D.; Hautier, G.; Ceder, G. Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries. Science
2014, 343, 519.

Yabuuchi, N.; Takeuchi, M.; Nakayama, M.; Shiiba, H.; Ogawa, M.; Nakayama, K.; Ohta, T.; Endo, D.; Ozaki, T.; Inamasu, T.; Sato, K.; Komaba, S., High-Capacity Electrode Materials for Rechargeable Lithium Batteries: Li3NbO4-based System with Cation-Disordered Rocksalt Structure. Natl. Acad. Sci.
2015, 112, 7650.

Chen, D.; Kan, W. H.; Chen, G. Understanding Performance Degradation in Cation-Disordered Rock-Salt Oxide Cathodes. Energy Mater.
2019, 9, 1901255.

Lee, J.; Papp, J. K.; Clément, R. J.; Sallis, S.; Kwon, D.-H.; Shi, T.; Yang, W.; McCloskey, B. D.; Ceder, G. Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials. Commun.
2017, 8, 981.

Lun, Z.; Ouyang, B.; Kitchaev, D. A.; Clément, R. J.; Papp, J. K.; Balasubramanian, M.; Tian, Y.; Lei, T.; Shi, T.; McCloskey, B. D.; Lee, J.; Ceder, G. Improved Cycling Performance of Li-Excess Cation-Disordered Cathode Materials upon Fluorine Substitution. Energy Mater.
2018, 9,1802959.

Ahn, J.; Chen, D.; Chen, G.. A Fluorination Method for Improving Cation-Disordered Rocksalt Cathode Performance. Energy Mater.
2020, 10, 2001671.
Stress-Induced Modification for Interlayers in Lithium Metal Batteries
Authors: Edgerton Brent , Liu Yangliu , Moon Jaron , Warren Roseanne 
Published: December 2024

As solid-state electrolytes (SSE) gain attention in the academic and industrial space, thin film interlayers are increasingly used to enhance wettability and lower interfacial resistance. Gold films, or interlayers, are frequently sputtered on ceramic electrolytes to improve their contact bonding with both anodic and cathodic layers. To-date, adherence between the SSE and current collector without cracks or delamination has been considered sufficient to qualify a “good” interlayer deposition. It is well known in the surface science community, however, that thin films can sustain high levels of residual stress, depending on dose-momentum of the depositing species.
For the first time, this work demonstrates the effects of interlayer residual stress on first and subsequent charge-discharge cycles and formulates a theory identifying the governing physical mechanism. We fabricate Au-Cu electrodes imbued with residual stress (-50 to 160 MPa) and cycle electrodeposited lithium on and off the surface to demonstrate unique morphological, electrochemical, and performance characteristics. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) measurements show that tensile interlayers result in larger, more irregularly shaped lithium structures that have high irreversibility, while compressive interlayers result in small, densely packed lithium structures with minimal solid electrolyte interface (SEI) formation (Figure 1a-d).
We characterize the Au-Cu surface using SEM, nanoindentation, optical spectroscopy (UV-Vis-NIR), and ultraviolet photoelectron spectroscopy (UPS) to relate the physical properties of the interlayer to the electrochemical behavior. The test results show that film stress causes the equilibrium electron energy levels to shift. As the surface becomes more tensile, the contact energy decreases, the color reddens, and the work function increases (Figure 1e-g). This evidences a change in the electronic configuration, leading to distinct thermodynamic behavior in lithium structures. This work demonstrates the high sensitivity of the electrochemical environment to even minor changes in the initial condition of interlayer state and presents a guide for consistent fabrication parameters that maximize the potential interlayer benefits offered by residual stress control.

Figure 1
The Effect of Surface pH on Rhenium Electrodeposition
Authors: Ahammed Kamal , Huang Qiang 
Published: December 2024

Electrodeposition is considered as a cost-effective, controllable, scalable, and facile process for material deposition[1] and has been widely used in the device fabrication[2-4]. Electrodeposition of high quality rhenium films with improved morphology is enabled in the so called water-in-salt (WIS) electrolyte, where a superhigh concentration of salt, such as LiCl, is present to deplete the free water molecules, reduce the proton diffusion, and suppress the hydrogen evolution side reactions[5]. Yet, inclusion of oxygen and chlorine is observed for the films deposited from such electrolytes. While Cl incorporation may result from high concentration of LiCl, the presence of oxygen can relate to oxide formation due to surface pH increase expected during electrodeposition. Therefore, understanding the surface pH during deposition might provide insight on the Re deposition mechanism and a guideline to further develop the chemistry and process for improved film property.
This work aims to measure the electrolyte pH at the electrode surface during Re electrodeposition and to determine the effects of salt speciation and deposition potential on the hydrogen evolution. How the surface pH impacts the impurity incorporation will also be investigated. A customized rotating ring disk electrode (RRDE) is utilized to perform the measurement. The Iridium Oxide pH sensing layer is fabricated using electrodeposition method on the Au ring and Re deposition is carried out on the Pt disk. The electrolyte pH during deposition is recorded as the open circuit potential (OCP) on the IrOx ring electrode. The interference of the anions or cations in the solution (other than proton or hydroxide) on the OCP reading is studied and calibrated. In-situ pH change under different solute conditions will be investigated to evaluate the efficacy of salts in suppressing hydrogen evolution. Furthermore, a correlation between surface pH and the incorporation of impurities, especially the oxides, will be studied under different solute environments.

References

Zhang, Q., et al., Electrodeposition in ionic liquids. ChemPhysChem, 2016. 17(3): p. 335-351.

Romankiw, L., Compositional Profiles in Electroplated Permalloy and Copper Permalloy: a Methodology Toward Laminated Permalloy for Thin Film Head Applications. Magnetic Materials, Processes, and Devices, 1991: p. 367-379.

Andricacos, P.C., et al., Damascene copper electroplating for chip interconnections. IBM Journal of Research and Development, 1998. 42(5): p. 567-574.

Moffat, T.P. and D. Josell, Superconformal Electrodeposition for 3-Dimensional Interconnects. Israel Journal of Chemistry, 2010. 50(3): p. 312-320.

Huang, Q. and T.W. Lyons, Electrodeposition of rhenium with suppressed hydrogen evolution from water-in-salt electrolyte. Electrochemistry Communications, 2018. 93: p. 53-56.
Multiscale Modeling Approach to Study the Influence of Bilayer Porous Transport Layers on Oxygen Evolution and PEMWE Performance
Authors: Sepe Mitchell , Shah Dhairya , Cho Hyunseok , Shimpalee Sirivatch 
Published: December 2024

With the current push for an alternative to traditional fuel-based transportation, hydrogen has the potential to be a viable replacement. Hydrogen has been proposed as a fuel replacement in internal combustion engines, or as fuel in a fuel cell powered automotive vehicle. Before hydrogen can be used in any type of transportation, it must first be produced. Proton Exchange Membrane Water Electrolyzers (PEMWE) produce hydrogen through an oxygen evolution reaction. A key component to PEMWE operation is the porous transport layer (PTL). Specifically, the PTL on the anode side must provide transport pathways for water to access the catalyst layer, while simultaneously removing oxygen.
In this work, a multiscale modeling approach is used to study the effect of a bilayer PTL, which is a PTL with an added mesoporous layer (MPL), on oxygen evolution and PEMWE performance. A previously developed image processing technique was expanded to generate bilayer PTLs from Xray Tomography scans. This process generates each sample a one combined geometry, which removes the need for interface communication. Due to the improvements in imaging techniques, the ability to mesh complex structures with this technique is possible. Each sample was generated with a 2:1 PTL to MPL ratio, with the total thickness around 400 ums. Porosity and pore size distributions were calculated during the image processing step. First a micro scale model that uses the Finite Volume Method, accompanied with a volume of fluid model, was used to predict permeability and simulate simultaneous two-phase flow of liquid water and oxygen gas. Oxygen evolution, growth, and structure interaction were observed. Results showed that the bilayer structure removes oxygen faster than single layer PTLs. Physical properties calculated using the micro scale model were used to inform a macro scale model of a PEMWE using the Finite Volume Method. The macro scale model predicted performance curves for each bilayer sample. Results showed that the bilayer samples exhibited improved performance as high current densities. Findings from this work show that a bilayer PTL geometry has potential to improve PEMWE performance.
Metallic Glass Nanoparticles Synthesized via Flash Joule Heating for High Performance Catalysis
Authors: Wang Hang , Ma Yuanyuan , Fan Xue , Maclean Stephen A. , Makowski Nathan , Lipton Jason , Meng Juan , Rohr Jason A. , Li Mo , Taylor Andre 
Published: December 2024

Metallic glasses (MGs) are a class of amorphous metal materials with remarkable properties. By leveraging an abundance of uncoordinated active sites that can serve as catalytic regions, MGs can have high catalytic activity and long-term stability as compared to their crystalline counterparts. Conventional synthesis methods cannot produce nanosized MGs with precise control over composition, phase, and morphology. This work presents flash Joule heating (FJH) as a novel one-step approach to synthesize fully amorphous MG nanoparticles while enabling unprecedented control over these critical parameters. The rapid heating (up to 2505 K/s) and ultrafast cooling rates (up to 1485 K/s) in FJH surpass the critical rates required for glass formation in metal-phosphide alloys like Pd-P, Pd-Ni-P, and Pd-Cu-P, preventing crystallization. Characterization techniques such as SAED, XRD, and XPS have confirmed the amorphous nature and metallic states of the nanoparticles.
Remarkably, FJH allowed precise tuning of ternary alloy compositions spanning wide ranges from Pd-rich to Ni/Cu-rich regimes, closely matching designed precursor ratios. The technique significantly expanded the glass formation region compared to conventional methods, accessing previously unattainable compositions like binary Pd3P. Moreover, FJH enabled control over particle size from 2.33±0.83 nm to 36.5±10.1 nm with narrow distributions by optimizing precursors, thermal profiles, and alloy chemistries. Incorporation of multiple elements facilitated smaller nanoparticle formation due to enhanced entropy, reduced melting points, and decreased surface tension.
The amorphous MG nanoparticles exhibited outstanding electrocatalytic performance and remarkable stability superiorities over their crystalline counterparts. For the oxygen evolution reaction, Pd-Ni-P MGs displayed ultra-low onset potentials ~300 mV below pure Pd and retained stable activity over 60 hours, contrasting rapid deactivation of crystalline samples of the same composition within 1 hour. PdCoP MGs for methanol oxidation showed high reaction rates and resilience against activity decline during accelerated durability testing, unlike rapidly decaying crystalline variants. This FJH synthesis approach unlocks new opportunities to realize the full potential of MGs by expanding the compositional space of alloy systems with precise control over MG properties, unlocking potential future transformative catalysts.
Figure 1: Schematics for (a) a traditional heating-cooling process and (b) the FJH process. (c) Illustration of temperature vs. time diagram of supercooled liquid alloys and glass transformation.(d) Ternary phase diagrams of the Pd-Ni-P and Pd-Cu-P systems.

Figure 1