bluuebunny/crossref_metadata_2025 huggingface dataset:
(Digital Presentation) Ionic Liquid-Based Electrolytes for Evaluation of Anthraquinone Derivative As Cathode in Zinc Ion Battery
Authors: Merukan Chola Noufal , Nagarale Rajaram Krishna
Published: November 2022

Aqueous zinc ion batteries are a very promisingly emerging class of energy storage devices. They are brought to the attention of the researchers owing to the abundant resourcefulness, user and environmental friendliness, and excellent water compatibility unlike the alkaline and alkaline earth metals. Unfortunately, their research and development are still in the unmatured stage. Few of the inorganic materials, such as oxides of manganese, vanadium, Prussian blue, etc., are some of the inorganic materials evaluated as cathode for zinc batteries. Even though inorganic materials offer high energy density which directly affects the size of the battery, they face some serious constraints of being used for real practical applications. They undergo irreversible structural lattice changes during the cycling process which ultimately deteriorate the battery performance over prolonged cycling. In addition, they face serious dissolution problems, lack of resourcefulness, and environmental non-benignity. In this regard, organic cathodes are interesting candidates because of their flexibility, simple charge storage mechanism, numerous choices of molecular engineering, and high resourcefulness. Herein, we studied the anthraquinone derivative as an organic cathode in ionic liquid electrolytes. Even though aqueous electrolytes are user-friendly, excessive water evaporation occurs with subsequent salt crystallization on the electrode which deteriorates the battery performance. We previously reported on addressing the restriction of water evaporation by choosing ethylene glycol as an electrolyte additive. Since ionic liquid exists as a liquid at room temperature, we selected different types of ILs, ie., imidazole containing different types of alkyl and functionalized alkyl chains as shown in the figure.

This work essentially emphasizes the aqueous zinc battery performance using functionalized ionic liquids as electrolytes with a newly designed anthraquinone-based organic cathode. It has been observed that the zwitterionic electrolyte exhibited comparatively good capacity performance of 156.2 mAhg-1 at 50 mAg-1 current density. The cycling stability, as well as coulombic efficiency, were also found to be much promising. On the whole, user-friendly organic-based electrolyte, as well as organic cathode, converge a new integrated electrode-electrolyte system for zinc ion battery. The detailed battery performance and post-mortem analysis have also been performed which reinvigorate the battery research, for zinc-like multivalent ion-based batteries in particular.

Figure 1
Feasibility Study on Aluminum Under Laser Ablation for Corrosion Resistance in Molten Salt
Authors: Cawley Peggy , Phongikaroon Supathorn
Published: November 2022

Molten salt is a prevalent medium in nuclear technology, especially in both reactors and waste separation (pyroprocessing) routines. Thus, the application dealing with the molten salt requires compatible materials that can withstand its aggressive environment. Research studies have shown that the purity of the molten salt environment can influence corrosion rates. Fission products, moisture, and oxide corrosion contents all distribute into the salt’s impurity and how it reacts within the system. The naturally occurring corrosion creates some protection via incomplete passivation layers; however, these same impurities start instability in the film through localized attacks. Laser ablation treatments in other research fields have proven useful in the improvement of corrosion resistance in various materials. Yet, this approach has not been tested in molten salt towards nuclear engineering applications. Thus, this becomes a motivation for our study to determine the feasibility of using the laser ablation technique on aluminum samples, creating an oxide layer and testing them in a eutectic LiCl-KCl salt at 773 K simulating a pyroprocessing environment. Over the course of the corrosion test, data sets were collected to allow electrochemical analysis – 24 hour rounds of open circuit voltage, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Detailed results will be presented and discussed.
Corrosion Testing in Nitrate Molten Salt Using Rotating Cylindrical Electrode
Authors: Townsend Ty , Chidambaram Dev
Published: November 2022

Molten salts are under consideration as the working fluid in thermal power generation. Nitrate molten salts store vast amounts of energy at high temperature and are an efficient energy production medium. Nitrate molten salts are corrosive to structural materials in these applications. Static corrosion studies may neglect the effects of fluid flow on corrosion and flowing test loops can be expensive and complex. A rotating cylinder electrode (RCE) can simulate the effects of fluid flow on the corrosion of structural materials and are more compact and economical then flow loops. We have developed a rotating cylinder electrode apparatus to study the corrosion of structural metals in flowing molten salts using accelerated electrochemical corrosion testing. In this study, we have evaluated the corrosion behavior in molten nitrate salts and used various surface characterization techniques to compare the results from static corrosion tests. Results and analysis of these studies will be presented.

Acknowledgement:

This research is being performed using funding received from the DOE Office of Nuclear Energy's Nuclear Energy University Programs under awards DE-NE0008889 and DE-NE0008236, and the US Nuclear Regulatory Commission (USNRC) under contract 31310018M0032. Dr. Kenny Osborne and Ms. Nancy Hebron-Isreal serve as the program managers for the DOE and NRC awards, respectively.
Factors Impacting Atmospheric Pitting Morphologies
Authors: Karasz Erin , Montoya Timothy , Taylor Jason , Katona Ryan , Bryan Charles , Schaller Rebecca Filardo
Published: November 2022

Stainless steels exposed to marine and near-marine environments can suffer from localized corrosion due to the appreciable amount of chloride aerosols present. In some cases, this localized corrosion, in the presence of sufficient tensile stress, can lead to stress corrosion cracking (SCC). Spent nuclear fuel (SNF) is currently stored in stainless steel canisters at independent spent fuel storage installation sites (ISFSI), many of which are located in near-marine environments. The possibility of localized corrosion features transitioning to SCC is a potential concern, particularly as the use of the SNF canisters at ISFSIs has been extended beyond their original licensing period.

There is evidence that the likelihood of this transition occurring is dependent on the morphology of corrosion damage. Therefore, it is important to examine factors impacting the corrosion morphology. This work focuses on the effects of environment, surface finish, and stress state.

304L stainless steel u-bends of various surface finishes were deposited with fine droplets of magnesium chloride solution or artificial sea water. They were divided among several exposure environments, cyclic or static in nature. Flat coupons of 304H, 304L, or 316L were finished to the same surface roughnesses and exposed in the cyclic environment. Static exposures were 75% or 40% RH at an elevated temperature while the cyclic environment varied both temperature and relative humidity. The cyclic environment is designed to mimic diurnal cycles experienced on a warm SNF canister after an initial storage (or cooling) period. In the flat coupons, the roughest surface finish developed elongated pits and microcracks formed along the edges of the pits, largely running perpendicular to the grind lines. When viewed in cross-section, pits on the roughest surface finish also appeared to have more severe under-cutting and to be more irregularly shaped. The results of the flat coupons will be compared to the u-bends exposed with various salt types and stress states.

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. SAND2022-4056 A. PNNL-SA-171827
(Invited) Advanced Warning for Intervention in Li-Ion Batteries during Abusive Conditions
Authors: Bates Alex Martin , Gray Lucas , Lamb Joshua , Torres-Castro Loraine
Published: November 2022

Electrification is occurring in large sectors across the world, from electric vehicles to grid energy storage. As a result, battery safety is of paramount concern with electric vehicle fires quickly finding their way to media outlets worldwide. This is especially true when battery fires occur near a home or structure. For this reason, advanced warning of an off normal event is crucial for mitigation or intervention. That is, advanced warning so that we may potentially stop the occurrence of thermal runaway, and thus a battery fire, and/or advanced warning to allow movement of individuals away from a dangerous situation.

This work utilized rapid electrochemical impedance spectroscopy (EIS) and a commercial gas sensing tool to quantify key metrics in early detection of off normal events for battery cells in the pouch format. The time between detection of an off normal event, via EIS response or gas detection, and thermal runaway was determined in a controlled environment, under abusive conditions. The importance of gas sensor proximity to the time between detection and thermal runaway was evaluated. This testing used an array of sensors positioned throughout an abuse testing bay, along with in-operando rapid EIS. Batteries with LFP or NMC cathodes were subjected to two abuse modes, overtemperature and overcharge. The gas composition was verified by FTIR to rule out the possibility of a false positive by some other substance, aside from vented gases, such as adhesive heating. This work gives insight into the ability of EIS and gas sensing to give advanced warning with different battery chemistries and failure modes.

Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and 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.
Kelvin Probe Techniques in Corrosion Science: An Overview of the Latest Developments
Authors: Rohwerder Michael
Published: November 2022

Over the last years, Kelvin probe techniques have found a more and more widespread application in corrosion science. While the pioneering applications by Stratmann et al were focused on investigating corrosion underneath ultra-thin electrolyte layers to cathodic delamination of organic coatings [1, 2], over the last 15 years the Kelvin probe method was shown to be applicable for new applications such as mapping hydrogen activities, measuring hydrogen permeation [3] and even measuring oxygen reduction at buried interfaces [4] or on surfaces just covered by a monolayer of water [5].

In this contribution examples about the latest developments of its application in corrosion science will be presented, from coating delamination to hydrogen in materials.

[1] M. Stratmann, H. Streckel, Corros. Sci., 30 (1990), pp. 681-696

[2] M. Stratmann, H. Streckel, R. Feser, Corros. Sci., 32 (1991), pp. 467-470

[3] S. Evers, M. Rohwerder, Electrochemistry Communications 24 (2012) 85

[4] D. Vijayshankar, T.H. Tran, A. Bashir, S. Evers. M. Rohwerder, Electrochimica Acta 189 (2016) 111-117

[5] X.K. Zhong, M. Schulz, C.H. Wu, M. Rabe, A. Erbe, M. Rohwerder, Chemelectrochem 8(4) (2021) 712-718
Impedance Analysis on Initiation and Growth of Ant-Nest Corrosion of Copper
Authors: Itagaki Masayuki , Makita Aoi , Watanabe Hikari , Shitanda Isao , Hosogi Tetsuro , Ito Shinichi
Published: November 2022

The branched pitting corrosion often occurs on copper tubes used in heat-exchanger units in air-conditioners and leads to leakage of heat-exchanger fluid for several months. Figure 1 shows a photograph of this unique localized corrosion formed by galvanostatic polarization in the laboratory. The morphology is characterized by the fractal structure in which pits of several ten micro-m diameter are formed at copper surface and smaller pores are developed on the pit walls randomly. This localized corrosion has been reported with some names: ant-nest corrosion, formicary corrosion, unusual corrosion, branched pits and pinhole corrosion [1]. It’s well known that the occurrence of this localized corrosion is related to trace phosphorus in copper and presence of low molecular weight carboxylic acid such as formic acid. However, the origin to form branched structure has not been clarified.

We reported an impedance method to analyze the branched (fractal) pore electrode with transmission line model (TLM) [2, 3]. Impedance spectrum of simple cylinder pore electrode on Nyquist plane normally describes straight-line of 45 degree slope in the high frequency range. In the case of electrode with fractal pores, the slope of straight-line decreases depending on the fractal dimension [3]. In this study, we employed this impedance analysis to investigate the initiation and growth of branched pores in ant-nest corrosion of copper.

References:

[1] D. M. Bastidas, V. M. La Iglesia, E. Cano, S. Fajardo, and J. M. Bastidas, J. Electrochem. Soc., 155, C578 (2008).

[2] M. Itagaki, S. Suzuki, I. Shitanda, K. Watanabe, H. Nakazawa, J. Power Sources, 161, 415 (2007).

[3] M. Itagaki, Y. Hatada, I. Shitanda, K. Watanabe, Electrochim. Acta, 55, 6255 (2010).

Figure 1
Corrosion Analysis of Mg/Al2O3 Bio-Degradable Nanolaminate Thin-Films Fabricated Using DC/Pulsed DC Magnetron-Sputtering Technique
Authors: Deshmukh Pratap , Yarmolenko Sergey , Neralla Sudheer , Sankar Jagannathan
Published: November 2022

Multilayered Thin films are effective in controlling the rate of corrosion of magnesium alloys used for bio-implants applications. It’s been proven that corrosion of metallic implants can be delayed by depositing multilayered metal-oxide thin films. In this study, Mg/Al2O3 nanolaminates, along with different metal oxides, were deposited using DC and pulsed DC magnetron sputtering methods at room temperature on glass substrates. Applicability of these metal-oxide nanolaminates to corrosion control was studied by bulk volumetric degradation measurement technique using solutions such as Saline, HANKS and PBS. Mg/Al2O3 films were also studied under different flow conditions by varying flow rates and pore growth rate and degradation process are measured by time-lapsed technique on optical microscope. Effect of the oxide layer thickness, saline flow rate, total pressure, structural characteristics of oxide coatings and sputtering deposition parameters on pore density and corrosion rate was investigated. Pulsed DC magnetron sputtering enables preparation of thin films with control over pore growth and distribution. Results have shown that repeatable pore density and corrosion rate can be achieved through magnetron sputter-deposited Mg/Al2O3 nanolaminates.
(Invited, Digital Presentation) 3D Printing of Flexible and Wearable Supercapacitors
Authors: Sundriyal Poonam
Published: November 2022

Flexible and wearable electronics have recently emerged as a potential solution for next-generation electronics for healthcare, sports, transport, military, soft robotics, artificial intelligence, the internet of things, and other applications. However, these devices are still at a fledgling stage due to the use of traditional manufacturing processes, lack of compatible power supply, poor commercialization capabilities, and integration problems. Here, we present 3D printing approaches for developing batteries and supercapacitors for flexible electronic applications. Such manufacturing techniques can revolutionize the rapidly growing field of flexible and wearable electronics due to their several attributes like; rapid production, simplicity, capability to produce size and shape versatile patterns, computer-aided design, user control, and environmental friendliness.(1-4) Different aspects of 3D printed supercapacitors (such as; device design, ink preparation of electrode/ electrolyte components, rheology control of inks, surface modification to get good print quality, electrochemical performance of printed devices, and flexibility analysis) will be discussed in detail with a focus on future requirements.

References

Sundriyal P, Bhattacharya S. Scalable micro-fabrication of flexible, solid-state, inexpensive, and high-performance planar micro-supercapacitors through inkjet printing. ACS Applied Energy Materials. 2019;2(3):1876-90.

Sundriyal P, Bhattacharya S. Inkjet-printed electrodes on A4 paper substrates for low-cost, disposable, and flexible asymmetric supercapacitors. ACS Applied Materials & Interfaces. 2017;9(44):38507-21.

Sundriyal P, Bhattacharya S, editors. 3-D Printed Electrode Materials for Low-Cost, Flexible, and Stretchable Energy Storage Devices. ECS Meeting Abstracts; 2019: IOP Publishing.

Sundriyal P, Bhattacharya S. Textile-based supercapacitors for flexible and wearable electronic applications. Scientific reports. 2020;10(1):1-15.
(Invited) Ferroelectric Field-Effect Transistors as High-Density, Ultra-fast, Embedded Non-Volatile Memories
Authors: Khan Asif
Published: November 2022

Ferroelectric field-effect transistors (FEFETs) are receiving significant attention from the microelectronics community for next-generation memory technologies, especially as embedded non-volatile elements for data-centric applications. The main attractive features of FEFETs are that write energy and speed of FEFETs are within an order of magnitude of respective metrics for SRAMs (FEFET ~1 fJ and 1-10 ns vs. SRAM: <1 fJ and <1 ns), all the while requiring a significantly smaller cell size (FEFET 50-60F2 vs. SRAM 120-150F2) and close-to-zero standby leakage power – provided that FEFETs are integrated at the same advanced technology nodes as SRAMs [1]. In this talk, we will discuss the potential path for FEFET toward fulfilling this vision, by addressing the outstanding technological challenges: ultra-fast read-after write, reliability, voltage scaling and variation. To that end, our recent exposition on the trap and reliability physics of FEFETs will highlighted. We will highlight, based on newly developed experimental schemes, how the simultaneous capture and emission of electrons and holes in write cycles occur at the interface and the grain boundaries in the time domain, where in the band-diagram, these traps (acceptors and donors) are located and how exactly they result in the degradation of the read speed and reliability with continued write cycling. Based on these insights, we move on show how engineering the interfacial layer and the ferroelectric grain structure can enable ultra-fast read-after write and write voltage and dramatic improvements in reliability and variation, towards achieving a high-density, ultra-high speed memory technology.

This research is supported by the National Science Foundation, the Defense Advanced Research Program Agency (DARPA), the Semiconductor Research Corporation (SRC) - Global Research Collaboration (GRC) program, the Applications and Systems-Driven Center for Energy-Efficient Integrated Nano Technologies (ASCENT), one of six centers in the Joint University Microelectronics Program (JUMP), a SRC program sponsored by the DARPA, and an Intel Rising Star award.

[1] Mikolajick, T., Schroeder, U. & Slesazeck, S. The past, the present, and the future of ferroelectric memories. IEEE Trans. Electron Devices 67, 1434–1443 (2020).

[2] Asif Islam Khan, Ali Keshavarzi, and Suman Datta. “The future of ferroelectric field-effect transistor technology." Nature Electronics 3.10 (2020): 588-597.
Process Optimization to Reduce Power in HfO2-Based Rram Devices for in-Memory Computing
Authors: Zeinati Aseel , Misra Durga , Triyoso Dina H. , Clark Robert , Tapily Kandabara , Consiglio Steven , Wajda Cory S , Leusink Gert J
Published: November 2022

Recently, HfO2-based resistive random-access memory (RRAM) devices have shown promise as candidates for in-memory computing applications. By engineering the distribution of defects or oxygen vacancies, the switching dielectric can potentially enable low power switching and multi-conductance levels. A higher concentration of oxygen vacancies closer to the top electrode a two-terminal RRAM device with a HfO2/Al2O3 bilayer structure reduces switching energy (1). Introducing excess oxygen vacancies near the top electrode through a hydrogen plasma treatment with a Ru as top electrode reduces the switching power of the device (2).

In this work we study the pulsed SET operation of different HfO2-based RRAM devices for their possible uses as multi-level cells. We have compared two different RRAM devices with HfO2-based dielectrics. Device-A is prepared with hydrogen plasma treatment at mid-point of HfO2 deposition (10nm Ti/50nmTiN/3nm HfO2(plasma treatment) 3nm HfO2/5nm Ru/5nm ALD TiN/ 50nm PVD TiN). Whereas Device-B constitutes a HfO2/Al2O3 bilayer structure (10nm Ti/50nmTiN/7nm HfO2/1nm Al2O3/5nm Ru/5nm ALD TiN/50nm PVD TiN). Both the devices have Ru as the top metal.

Fig. 1 and Fig. 2 show the conductance modulation obtained by applying successive pulse sequences (80 pulses) with increasing the pulse width tp (from 4 𝜇s to 10 ms) every 20 pulses where the pulse height, Vp, remained fixed at 2V during the experiment. A read pulse with voltage Vr=0.1V and pulse width tr=1ms is applied immediately after each pulse. The forming compliance current in Device-A is seven time lower than Device-B. Both devices clearly show promising behavior of multi-level conductance.

Figure 1
(Invited) Computational Insights to Dielectric Hybrid Glasses Under Nanoscale Confinement for Next Generation Devices
Authors: Dauskardt Reinhold H
Published: November 2022

Low and Ultra-k dielectric organosilicate glasses (OSG) are widely used in device interconnect applications such as shallow trench isolation as insulating units. However, the process of gap filling between conducting units has been challenging. One of the challenges is related to the undesired formation of nanovoids in the low-k dielectric material confined inside the trench geometry. Importantly, the effects of such nanoscale device constraints on the structure and mechanical reliability of low-k dielectric hybrid materials are not very well understood. To close this lack of understanding and guide the related experimental efforts we performed molecular dynamics simulations where we explore the role of the molecular structure and connectivity of different low-k dielectric OSG precursors under nanoscale confinement, and predict the resulting elastic and fracture properties. We demonstrated that hyperconnected OSG precursors with aromatic rings, such as the 1,3,5-benzene molecule, pack more homogenously under confinement leading to smaller nanovoids and better mechanical reliability compared to conventionally bridged OSG precursors, such as the ethylene bridged Et-OCS molecule.
(Invited, Digital Presentation) Amoeba-Inspired Electronic Computing System for Combinatorial Optimization
Authors: Kasai Seiya , Aono Masashi
Published: November 2022

A single-celled amoeboid organism is known to maximize nutrient acquisition efficiently by deforming its body (Fig. 1(a)). This ability made it possible for the organism to survive in the harsh natural environment over a billion years. Its sophisticated search capability has been demonstrated by means of the amoeba-based computer in which the amoeboid organism is used to search for a solution of the optimization problem [1]. However, from engineering point of view, the deformation speed of the organism is too slow to compute compared to the modern computers. Here, our idea is to artificially represent the amoeba search capability by electronically mimicking the spatiotemporal dynamics of the organism, which is called “electronic amoeba” (Fig. 1(b)) [2]. We have demonstrated that our system can find a reliable and swift solution to the intractable combinatorial optimization problems including maximum cut problem, satisfiability problem (SAT), and traveling salesman problem (TSP) [3]. In this paper, we show the important features of the amoeba dynamics in terms of the solution search and their electronic representations. We also show how to map the problem to the system, which has a great advantage than the currently available optimization computers called Ising machine.

[1] e.g. L. Zhu, S.-J. Kim, M. Hara, and M. Aono, R. Soc. Open Sci. 5, 180396 (2018). [2] S. Kasai, M., Aono & M. Naurse, Appl. Phys. Lett. 103, 163703 (2013). [3] K. Saito, M. Aono & S. Kasai, Sci. Rep. 10, 20772 (2020).

Figure 1
(Invited) Epitaxial Growth of Transition Metal Dichalcogenide Monolayers for Large Area Device Applications
Authors: Redwing Joan M.
Published: November 2022

Wafer-scale epitaxial growth of semiconducting transition metal dichalcogenide (TMD) monolayers such as MoS2, WS2 and WSe2 is of significant interest for device applications to circumvent size limitations associated with the use of exfoliated flakes. Epitaxy is required to achieve single crystal films over large areas via coalescence of TMD domains. Our research has focused on epitaxial growth of 2D semiconducting TMDs on c-plane sapphire substrates using metalorganic chemical vapor deposition (MOCVD). Steps on the miscut sapphire surface serve as preferential sites for nucleation and can be used to induce a preferred crystallographic direction to the TMD domains which enables a reduction in twin boundaries in coalesced films. The step-directed growth is dependent on the surface termination of the sapphire which can be altered through pre-growth annealing in H2 and chalcogen-rich environments. Uniform growth of TMD monolayers with significantly reduced inversion domains is demonstrated on 2” diameter c-plane sapphire substrates enabling large area transfer of monolayers for characterization and device fabrication and testing. Applications for wafer-scale TMD monolayers in nanoelectronics, sensing and photonics will be discussed.
(Energy Technology Division Walter van Schalkwijk Award in Sustainable Energy Technology Address) Low Temperature Water Electrolysis as a Near Term Enabler in Climate Change Mitigation
Authors: Ayers Katherine E. , Capuano Christopher , Carmo Marcelo , Deporcellinis Diana , Dalton Luke , Roemer Andy , Motz Andrew R
Published: November 2022

Generating hydrogen from renewable production methods such as water electrolysis is fundamental to meeting decarbonization goals and mitigating climate change. Regardless of the end market split for hydrogen in ground transportation applications, hydrogen is the major feedstock for industrial chemicals such as ammonia and methanol. The only way to make these processes sustainable is to eliminate carbon dioxide emissions from production of the hydrogen feedstock. Currently, over 95% of this hydrogen is generated from natural gas and other fossil fuels, producing roughly 9 g CO2/g H2. A combination of technologies such as natural gas reforming with carbon capture, utilization and sequestration (CCUS) and water splitting via electrolysis therefore need to be deployed as quickly as possible. In addition, any scheme to convert carbon dioxide to useful chemicals requires a renewable source of hydrogen atoms. So to address both curtailment of ongoing emissions and mitigation of existing CO2 waste streams, renewable hydrogen is a lynchpin for success.

Low temperature electrolysis has commercially deployed for decades, making it one of the only water splitting technologies likely to make an impact in the next 5-10 years. Both liquid alkaline electrolyzers (or alkaline water electrolyzers, AWE) and proton exchange membrane water electrolyzers (PEMWE) have been deployed at >10 MW scale, and many companies are actively working to scale manufacturing to gigawatt capacity. While 2050 goals will likely involve implementation of a broader portfolio of technologies, scaling deployment of existing carbon neutral hydrogen technologies provides the greatest long term benefit by reducing overall emissions earlier. We therefore cannot let “perfect [become] the enemy of good”[1] in terms of waiting for the most efficient, lowest cost solution. At the same time, there are significant improvements that can be made in both AWE and PEMWE products, through advanced materials, processes, and automation. The PEMWE technology in particular can leverage much of the investment in PEM fuel cell research and development, although understanding of electrolysis specific materials and processes in ongoing. This talk will focus on the relationships between material research, process development, and understanding of degradation mechanisms in commercializing reliable technology, and the importance of academia, national labs, and industry to work together in this effort.

[1] Commonly attributed to Voltaire, and others.
Soh Prediction of Li-Ion Batteries with Machine Learning-Based Method
Authors: Choi Jung-goo , Kim Jinwon , Lee Jaeyoung
Published: November 2022

As fossil fuel-driven society has brought environmental pollution and climate crisis, environmentally friendly alternative energy has been in the spotlight. In particular, electric vehicles receive attention as a next-generation transportation method. The most core technology for electric vehicles is the lithium-ion battery and the battery management system (BMS). However, due to the long lifespan of lithium-ion batteries, it is very time-consuming to measure and improve performance over time. In addition, since the batteries are driven under various conditions, it is not easy to measure the SOC and SOH in real-time because there are many variables. With the recent development of prediction technology through machine learning, it has become possible to predict with high accuracy without complex physical knowledge through high-quality data.

In this study, machine learning technology was applied by utilizing charge/discharge data of lithium ion batteries. The measured values in the initial charge/discharge cycles were selected as independent variable, and the number of cycles remaining until the end of the life was selected as a dependent variable, and then a regression algorithm was applied. After that, model tuning was performed to increase accuracy by reducing overfitting of the data. This study used machine learning technology to predict the SOH of a lithium ion battery with high accuracy with only the initial cycles, thereby contributing to real-time data of BMS and raising the time efficiency of the study.
(Invited, Digital Presentation) ML-Based Fast on-Chip Transient Thermal Simulation for Heterogeneous 2.5D/3D IC Designs
Authors: Chang Norman
Published: November 2022

Large 3DIC designs with multiple chips require

several iterations of transient thermal analysis particularly for

fine-grain on-chip dynamic thermal management. This requires

a fast thermal analysis technology as opposed to traditional

CFD/FEA based methods which have severe runtime/capacity

limitations for large chips (e.g., 2cmx2cm) in 3DIC while

generating fine grained (e.g., 10umx10um) transient thermal

response. The fast transient thermal analysis is based on the idea

of combining the global, intermediate, and local transient

response curves generated from an ML-predictor. The local,

intermediate, and global transient response curves are scaled

based on the far-field and near-field transient decay surface

components respectively, computed using the trained ML decay

surface predictor, followed by linear superposition of the curves

for each power value in the transient power profile to generate

the effective transient response curve. The runtime for

generating thermal results for a large chip is in the order of

minutes, compared to several hours/days while using CFD/FEA

based tools with good accuracy correlation. The fast transient

thermal solver is implemented on distributed ML computing

platform for parallel computation of transient thermal inference

model.
Cu Deposition on AAO Substrate for Interposer Applications
Authors: Kim Chae Yoon , Kim In Yea , Kim Dong Hyun , Lim Gi hwan , Lee Min-Jeong , Kim Jaehun , Lim Jae-Hong
Published: November 2022

In recent days, the demand for high-performance devices has increased in the semiconductor industry. These devices require integrated circuits to test out their performance. For this purpose, interposer with both vertical and horizontal copper circuits which offers advanced connections is used. Interposer consists of a substrate material and metal circuits. Common substrate materials for the interposer are silicon and glass. Whereas anodized aluminum oxide (AAO) has less current leakage than silicon substrate, which results in no need for the insulation, and has a vertically self-aligned nanopore structure though wet etching process, which enables high density holes with less cost. AAO was proposed as a substrate material for interposer.

AAO substrate was fabricated using 0.3M oxalic acid solution, followed by fabricating through-hole of AAO. For the interconnection, copper layer was deposited on the surface and hole of AAO substrate by electroless and electrochemical techniques sequentially. Sol-gel catalyst was adopted followed by heat treatment, instead of Sn/Pd catalyzation, to increase the adhesion property and breakdown voltage. Fabricated AAO is a circle shape with 4.8 cm diameter and average pore size is about 98 nm. Cu electroless deposition was performed on AAO with and without through-holes. Thin Cu layer was deposited without voids. The adhesion was measured by SCRATCH TESTER PRO, J&L Tech, Korea, showing first crack around 1.5 N to 2 N. Pulse electrodeposition with surfactant was used to fill the trough-hole of AAO substrate for through-AAO interconnects. The more details will be presented.

Figure 1
(Invited) Towards the Physical Reliability of 3D-Integrated Systems: Broadband Dielectric Spectroscopic (BDS) Studies of Material Evolution and Reliability in Integrated Systems
Authors: Amoah Papa K. , Sunday Christopher E , Okoro Chukwudi , Ahn Jungjoon , You Lin , Veksler Dmitry , Kopanski Joseph , Obeng Yaw
Published: November 2022

In this talk, we present an overview of our current research focus in developing non-destructive metrology for monitoring reliability issues in 3D-integrated electronic systems. Working closely with the semiconductor industry, we have been looking at various performance limiting phenomena in 3D-interconnects, the associated dielectrics, and advanced packaging for integrated circuits.

The talk will identify some common reliability concerns, and identify some metrology gaps, for 3-D integrated systems. We will introduce a suite of microwave-based Broadband Dielectric Spectroscopic (BDS) techniques and show how these non-destructive metrologies can serve as early warning monitors for reliability issues. These techniques are based on the application of high frequency microwaves, to probe impedance changes due to material and structural changes in integrated circuits under various external stress. For example, we will also discuss the combination of BDS with scanning probe infrastructure to create the Scanning Microwave Microscopy (SMM) technique, which has been used to detect buried artifacts and characterize metallic contacts. We further illustrate the capabilities of the BDS-based techniques with case studies of three potential reliability issues in 3D IC.

We conclude with a forward look at the future metrology and standards needs 3-D interconnects and the associated advanced packaging.
(Invited) Surface Chemistry Control in Advanced Plasma Processes
Authors: Ventzek Peter , Sridhar Shyam , Chen Ya-Ming , Longo Roberto , Hartmann Gregory , Zhao Jianping , Shinagawa Jun , Chen Zhiying
Published: November 2022

Atomic scale control in fabrication steps for advanced logic and memory manufacture is critical not only for manufacturing viability of widely disparate structures but also functionality of complex devices. Different approaches ranging from the use of “tighter” process control options to leveraging self-limiting cyclic processing have been explored to achieve atomic scale control utilizing seemingly unwieldy plasmas. Process technology is married to plasma as the most capable methods of delivering area selective etch or low temperature selective deposition. A hindrance for advancing the control of plasma modified surfaces is that plasmas modify surfaces resulting in non-ideal states. Current process engineering can accommodate less-than-ideal surfaces; however, even in the best case, managing non-idealities introduces significant complexity. The use of first principles in-situ diagnostics and simulation together provides a path towards increased understanding of plasma-surface interactions and atomic scale control of the surface and sub-surface. Physisorption-mediated plasma processes are useful to illustrate the combination of quantum chemistry and in-situ diagnostics as the etch precursor is delivered to the surface in an unfragmented state. The presentation will include examples of how this system can be used to gain an understanding of the sensitivity of processes to different types of surfaces. It will conclude with forward looking content related to the de-cluttering of plasma processes using new learning concepts.
Enabling High Aspect Ratio 3D NAND Scaling through Deposition and Etch Co-Optimization (DECO)
Authors: Shen Meihua , Hoang John , Chi Hao , Routzahn Aaron , Church Jonathan , Subramonium Pramod Subramonium , Puthenkovilakam Ragesh , Reddy Sirish Reddy , Bhadauriya Sonal , Roberts Sloan , Lill Thorsten , Kamarthy Gowri
Published: November 2022

Over the past decade, the demands for 3D NAND flash memory devices have been increased tremendously due to ever growing digital economics in consumer electronics, data centers, IOT, healthcare and automotive industries. The growth is further accelerated during the recent Covid period. The industry was able to keep up the scaling roadmap by stacking more memory cell in vertical direction to realize higher bit density at reducing cost per Gig-bit.

Unlike devices scaling via feature size reduction, 3D NAND flash vertical stack scaling puts challenges mostly on film deposition and etch. Among many steps, high aspect ratio (HAR) ONON channel hole formation modules remained the most critical steps. Forming billions of perfect channel holes from top to bottom without distortion and twisting is the grand challenge. Besides individual etch and deposition module optimization, deposition and etch Co-optimization (DECO) could provide new opportunities. In this paper, we will present a summary of the recent progress in the approaches and the benefits of DECO as potential pathways to overcome the HAR ONON patterning. We will discuss the ONON Tier Optimization for profile control to reduce the top bowing and enlarge the bottom CD. We will introduce a sacrificial liner approach to prevent top CD enlargement at deeper etch depth. We will also discuss new mask materials for better etch selectivity and profile control to enable the scaling roadmap.
(Digital Presentation) Importance of Electrified Interfaces in Researchable Metal Anode Batteries: Ionic Liquid Electrolyte Composition and Electrode Preconditioning
Authors: Rakov Dmitrii
Published: November 2022

Electrode/electrolyte interface is an important part of many electrochemical systems, as its local structure, so called electric double layer (EDL), defines mechanism of charge transfer and stability of the device. Alkaline metal anodes possess high theoretical capacity due to ability of metal-ions to pack in the dense crystal structure, however, their application is rather limited due to formation of dendrites from non-uniform metal deposition and/or poor quality of the interphase. Experimentally, it was found that variation of ionic liquid (IL) electrolyte composition (salt concentration, presence of cosolvent) and applied current density for the formation cycling, i.e., cycling to activate electrode surface before utilisation, significantly affect dendritic growth and stability of metal anode. This presentation aims to show the molecular level relationships between interfacial structure, value of metal deposition potential and the interphase formation with ionic liquid electrolyte of different compositions (salt concentration, presence of cosolvent). Each electrolyte composition results in a particular interfacial metal-ion solvation environment which controls the reductive stability, metal-ion deposition potential, and ultimately the composition and properties the solid-electrolyte interphase (SEI). The latter is dependent on the EDL composition such as the IL cation/metal cation-IL anion ratio or the presence of other surface active additives. Based on this work, our group at Deakin University developed a theoretical framework to choose an optimum current density for the formation cycling of lithium/sodium metal anodes with ionic liquid electrolytes of different composition (salt concentration, presence of cosolvent). Details of these findings are published in following literature [1, 2].

References

1. Rakov Dmitrii A., Chen F, Ferdousi SA, Li H, Pathirana T, Simonov AN, Howlett PC, Atkin R, Forsyth M. Engineering high-energy-density sodium battery anodes for improved cycling with superconcentrated ionic-liquid electrolytes. Nature materials. 2020 May 4:1-6.

2. Dmitrii Rakov, Meisam Hasanpoor, Artem Baskin, John W. Lawson, Fangfang Chen, Pavel V. Cherepanov, Alexandr N. Simonov, Patrick C. Howlett, Maria Forsyth. Stable and Efficient Lithium Metal Anode Cycling Through Understanding the Effects of Electrolyte Composition and Electrode Preconditioning, Chemistry of Materials, 2022, 34, 1, 165–177, https://doi.org/10.1021/acs.chemmater.1c02981
(Invited, Digital Presentation) Eco-Friendly and Sustainable Ammonia Production with Atmospheric Pressure Rotating Gliding Arc Discharge
Authors: Iqbal Muzammil
Published: November 2022

Increasing fossil-free global energy demands have motivated the scientific community to investigate new clean and sustainable techniques that can meet global energy demands. The production of green and sustainable fuel, such as ammonia, from base molecules like water and nitrogen using electricity from renewable sources shows great potential to solve energy issues. Non-thermal atmospheric pressure plasma-based ammonia synthesis has great potential for carbon-free fertilizer production powered by renewable electricity. We developed an atmospheric pressure rotating gliding arc discharge reactor coupled with a catalyst for a higher ammonia production rate. Here we reported two-step ammonia production, including 1) facile production of NOx and hydrogen from nitrogen discharge in water, and 2) highly selective catalytic reduction of NOx to ammonia in the presence of hydrogen. The studied plasma technique offers ~0.84 % ammonia concentration with ~95 % selectivity and a 120 µmol/s production rate by integrating a catalytic reduction system with plasma. Compared with previous studies on ammonia synthesis from nitrogen, the remarkable ammonia yield (300–400-fold higher). These promising results provide a breakthrough in the transition toward sustainable and environmentally friendly ammonia production.
Confocal Fluorescence Microscopy to Probe in Operando electrochemical Conversion
Authors: Graf Anton Marius , Cochard Thomas , Amini Kiana , Rubinstein Shmuel , Aziz Michael
Published: November 2022

The development of electrochemical devices, such as flow batteries, fuel cells and electrolysers, is critical for the transition to a sustainable economy. Given the critical role of porous electrodes in the performance of these devices, understanding their structure-function relationship is crucial. Although porous electrodes with many different internal structures have been utilized, there is no clear consensus as to what features lead to what aspects of electrode performance. Transport in porous electrodes is commonly approximated by mean-field theories, which assumes a homogenous, Darcy-like permeability in the porous structure. Recent findings have challenged the suitability of these assumptions by revealing extreme heterogeneities in the electrolyte transport, on commercially relevant length scales exceeding the electrode pore size by an order of magnitude. [1]

In this study, we introduce a new analytical method for electrochemical flow devices: 4D Confocal Optical Fluorescence Microscopy. This non-invasive in-situ analytical technique distinguishes between oxidized and reduced molecular species by their fluorescence spectra and maps out 3D molecular concentration fields with single-digit micron resolution (Figure 1). 3D movies, correlated with macroscopic chronoamperometry, add time as a fourth dimension. Thus, electrochemical conversion and species advection and diffusion can be monitored at heretofore unprecedented resolution, giving us new routes to understanding local phenomena in porous electrodes. We demonstrate this method by monitoring the reversible electrolytic reduction of 2,7 anthraquinone disulfonate (AQDS) to its corresponding hydroquinone, H2AQDS, in aqueous electrolyte in a transparent electrochemical cell. We monitor changes in the concentration field as a response to the variation of applied potential and current in real time. We correlate the fluorescence intensity of a particular band of wavelengths to the electrolyte state of charge. Furthermore, high sensitivity to non-linear optical effects enables us to capture the reversible formation of a dimer, specific to the AQDS/H2AQDS system, quantitatively in an operating battery.

This new high-resolution 4D technique of characterizing operando electrochemical devices is expected to provide insight into the relationship between electrode microstructure and electrochemical performance features.

Literature cited:

[1] A.A. Wong, S.M. Rubinstein and M.J. Aziz, “Direct visualization of electrochemical reactions and heterogeneous transport within porous electrodes in operando by fluorescence microscopy” Cell Reports Phys. Sci.
2021, 100388; https://doi.org/10.1016/j.xcrp.2021.100388

Figure 1
(Keynote) Colloidal Quantum Shells: An Emerging Class of 2D Semiconductors
Authors: Zamkov Mikhail
Published: November 2022

Low-dimensional colloidal semiconductors are inexpensive to process and offer a broad spectrum of attractive quantum-mechanical properties. The notorious problem of these nanostructures lies in their limited performance under high energetic loads, when more than one exciton per particle is created. Multiple excitons undergo fast Auger recombination, causing efficiently roll-off in energy-intensive applications, including high-brightness LEDs, X-ray scintillators, and solar cells. This presentation will discuss an emerging type of low-dimensional semiconductors, known as colloidal quantum shells that allow avoiding such multi-exciton (MX) energy losses. The geometry of quantum shells benefits from the spatial separation of multiple excitons, which leads to extraordinary improvements to MX lifetimes and MX quantum yield. We will compare quantum shells with other nanoscale geometries in three categories: Auger suppression, multi-exciton level structure, and solution-processed film conductivity, highlighting the potential benefits quantum shells can contribute to various applications. Theoretical analysis discussing the role of the quantum shell geometry in suppressing Auger recombination will also be presented.