bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Effects of Halide Anion Type and Alkyl Chain Length on Hydrogen Bonding in Eutectic Solvent System
Authors: Shen Xiaochen , Sinclair Nicholas Scott , Wainright Jesse S. , Savinell Robert F. 
Published: November 2022

Deep eutectic solvent (DES), formed by the intermolecular hydrogen bonding between its components of an H–bond acceptor (HBA) and an H–bond donor (HBD), has been extensively studied in the area of material synthesis, catalysis, electrochemistry, etc. The properties of DES including melting point, color, density, viscosity, conductivity, etc. are closely related to the H-bond network. Establishing an understanding of the H-bond structure offers an opportunity to fine-tune these properties.
Hence, in this study, we systematically investigated the effects of halide anion type and alkyl chain length on the hydrogen bond network of a series of eutectic solvent systems and attempted to establish an unambiguous H-bond correlation with the conductivity. We varied the halide anion from Cl− to I− (Cl−, Br−, I−) and the alkyl chain length from methyl to butyl (n
c = 1, 2, 4), and performed FTIR and conductivity measurements. Results show that the OH stretching peak exhibits a blue shift with the halide anion varies in the order of Cl−, Br−, I− when compared with the neat ethylene glycol (Figure 1a), indicating an increase in H-bond strength. A similar trend can be found with the increasing alkyl chain length as well. A stronger H-bond network inhibits the mobility of these halide anions in the eutectic system, as a result, the conductivity will decrease as shown in Figure 1b. Further probing the H-bond network with ultrafast spectroscopy is currently underway.

Figure 1. (a) FTIR spectrum of neat EG and TBAX:EG(1:10) sample, X= Cl−, Br−,I−. (b) Trend between the OH stretching peak shift (vs. neat EG) and conductivity of these investigated samples.
Acknowledgememts
This work was supported as part of the Breakthrough Electrolytes for Energy Storage (BEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0019409

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(Invited) Single Atom Co-Catalysts in Photocatalytic H2 Generation
Authors: Schmuki Patrik 
Published: November 2022

Photocatalytic H2 generation has been a highly investigated topic ever since Fujishima und Honda (1972) reported on the use of TiO2 as a solar-illuminated semiconductor for the splitting of water into H2 and O2. Generally, in a fully photocatalytic setting (when photogenerated electron and hole are transferred from a solution-suspended TiO2 nanoparticle to an aqueous electrolyte), a reasonable electron transfer rate can only be established when a noble metal co-catalyst is attached to the TiO2. Mostly this is a Pt nanoparticle that is deposited onto the TiO2 by various reductive treatments.
Over the years numerous efforts have been devoted to the shrinkage of the particle to enhance the usage of the noble metal. Evidently the most extreme case shrinkage is the use of an insulated single atom of Pt. The use of such isolated atoms as a co-catalyst in photocatalysis has in recent years attracted strong interest, not only because the single atom state represents a maximized surface to volume efficiency, but also because single atom reactivity allows for unprecedented reaction pathways.
In the presentation we discuss the use of Pt dispersed and anchored as single atoms on TiO2 nanocrystallites, powders and nanotubes as a co-catalyst in photocatalytic H2 generation.
We discuss various trapping and stabilization approaches of SAs on photocatalysts and report on a SA-Pt photocatalyst with a higher photocatalytic activity than observed for classic arrangements of co-catalyst on the semiconductive substrate. Moreover, we show that a small fraction of the totally deposited Pt that is stably trapped SAs provides virtually all photocatalytic reactivity of a Pt decorated catalyst.
Atomic Layer Deposition of ZnO on the 3D Porous Ni(OH)2 Nanostructure for Supercapacitor Applications
Authors: Ji-Hu Baek , Kwon Se-Hun 
Published: November 2022

Atomic Layer Deposition (ALD) is a unique vapor-phase non-line-of-sight deposition process, it can provide excellent control over the wall thickness of nanostructures at the sub-angstrom scale and can be used to create highly conformal coatings of dense inorganic film even on the nano-sized templates with high aspect ratios. Due to these inherent merits, it has become an inevitable process in current semiconductor industries. Following the success of ALD in the semiconductor industries, ALD is recently focused because it can efficiently enhance the performance of energy conversion and storage devices.
As a representative example, electrochemical supercapacitors, as one type of novel power device, have attracted universal research interest because of their great potential to be applied in many fields. In particular, pseudocapacitor is recently focused due to its larger capacitance. The electrochemical energy conversion and storage performance of pseudocapacitors depends strongly on the intrinsic properties of the active electrode materials and their surface area. To maximize these performance, various nano-morphologies and transition metal oxides/hydroxides, such as NiO, Co3O4, MnO2, Ni(OH)2 and etc., having a large theoretical capacitance has been extensively investigated. Those psuedocapacitor materials, however, generally showed a high electrical resistivity and it remain unable to achieve high theoretical capacitance in practical applications.
To solve these drawbacks, ultrathin conductive ALD coatings can be considered. As a representative example, we design and fabricate a novel hybrid 3D Ni(OH)2@ZnO nanostructured electrode material with a high surface area and high conductivity using a hydrothermal method and ALD. ALD-ZnO thin films were deposited on the surface of a 3D porous Ni(OH)2 nanostructure. The optimization of ALD-ZnO was performed to achieve a high conductivity and electrochemical performance. And, it was exhibited that this hybrid 3D core-shell structure, which benefits from the synergistic effects of both Ni(OH)2 and ZnO, can result in a much improved supercapacitor performance.
(Invited) Area-Selective Spatial Atomic Layer Deposition of Silicon-Based Materials
Authors: Mameli Alfredo , Karasulu Bora , Shen Jie , Roozeboom Fred 
Published: November 2022

Area-selective atomic layer deposition (AS-ALD) holds great potential for advancing device manufacturing.1 Recently, outstanding progress on this topic has been made in terms of understanding and developing highly selective processes for various material systems; some of these processes have already been transferred into fabs.2

In this work we provide an overview of AS-ALD of silicon-based materials with high selectivity and high throughput, especially silicon oxide and nitride. While the selectivity is mostly governed by the method of choice and the underpinning chemistry, the aspect of high-throughput is ensured by using spatial ALD, which is, in our case, performed at atmospheric pressure.
The processes presented here comprise three steps: selective inhibitor chemisorption, plasma-based spatial ALD and spatial back-etching. Particular focus is given to the choice of inhibitors as the most critical step in enabling high-selectivity. Here, density functional theory (DFT) calculations have been employed to unveil the chemistries governing the selectivity for the two different inhibitors within the same growth system. General guidelines on the inhibitor chemistries are derived by combining experimental and DFT results.
Finally, process details and effect of plasma chemistries on different surfaces are discussed in an effort to expand the selectivity toolbox to other silicon-based materials.
[1] A. Mameli, et al., “Area-Selective Atomic Layer Deposition of SiO2 using acetylacetone as a chemoselective inhibitor in an ABC-type cycle”,
ACS Nano, 11, 9303, 2017.
[2] H.-P. Chen, , et al., “Fully Self-Aligned Via Integration for Interconnect Scaling Beyond 3nm Node”, IEDM 2021, paper 22-1.

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(Invited) ALD Coatings for Li-Ion Battery and All-Solid-State Battery Applications
Authors: Kitsche David , Kondrakov Aleksandr , Janek Jürgen , Brezesinski Torsten 
Published: November 2022

Lithium-ion batteries (LIBs) are essential for modern life, and their improvement is crucial for the more widespread adoption of electric vehicles.[1] Layered lithium transition metal oxides, such as LiNixCoyMnzO2 (often referred to as NCM or NMC), are among the most widely used cathode active materials (CAMs) for automotive applications, owing to their technological maturity and high energy density. However, they typically require a surface coating for stabilizing interfaces, both in liquid-electrolyte based LIBs and in solid-state battery (SSB) environments. For the preparation of protective CAM coatings, atomic layer deposition (ALD) stands out with its ability to produce conformal films on complex substrates.
This presentation encompasses several examples of successful improvements in cycling performance of Ni-rich NCM CAMs in LIBs and SSBs by ALD of binary oxides. The low-temperature deposition of AlxOy onto ready-to-use cathode sheets will be discussed.[2] ALD or ALD-related surface protection enables increased stability by suppressing detrimental surface corrosion and metal leaching (side reactions) in LIBs.[2,3] Moreover, we report about the application of ALD coatings to Ni-rich NCM CAMs in SSBs with lithium thiophosphate solid electrolytes. Specifically, the effect that both HfO2 and ZrO2 have on the cell cyclability will be shown, with emphasis placed on the role of post annealing.[4]

[1] Goodenough et al. J. Am. Chem. Soc. 2013, 135, 1167.
[2] Neudeck et al. Sci. Rep. 2019, 9, 5328.
[3] Neudeck et al. Chem. Commun. 2019, 55, 2174.
[4] Kitsche et al. ACS Appl. Energy Mater. 2021, 4, 7338.
(Digital Presentation) Simultaneous Transforming Residual Lithium Compounds and Stabilizing Surface Lattice Oxygen for Ni-Rich Cathode Via Atomic Layer Deposition and Post-Annealing
Authors: Li Jiawei , Yi Ge , Xiang Junren , Shao Huachen , Liu Xiao , Shan Bin , Chen Rong 
Published: November 2022

Unstable surface species such as residual lithium compounds and surface lattice oxygen at charge state are detrimental factors for the battery performance of Ni-rich cathode (LiNixCoyMn1−x−yO2, x ≥ 0.6, NCM), which induce serious side reactions and lead to rapid capacity loss during cycling. With the advantages of sufficient contacts between gas and solid, gas reactants are introduced to reducing residual lithium compounds via gas-solid reactions or building protective coatings to isolate surface lattice oxygen from the electrolyte via gas-phase deposition, which effectively enhances the cycling stability of NCM. Atomic layer deposition (ALD), as a special coating technology, possesses both the nature of the gas-solid reaction and gas-phase deposition. It is significant to investigate the mechanism of ALD in enhancing the cycling stability of NCM.
Here, we report a method to improving the rate capacity and cycling stability of single-crystal NCM via Al2O3 and B2O3 ALD by constructing a highly Li-ions conductive and electrochemical stable surface. The ultrathin coatings are uniformly coated on the surface of NCM. Moreover, surface composition characterizations show the reductions of residual lithium compounds and formations of lithium-containing coatings after the ALD process. By adding a post-annealing process, Al3+ cations and BO3- polyanions doping form on the surface of NCM, which robustly enhanced the stability of surface lattice oxygen of NCM via strong Al-O bond and B-O bond. Moreover, as acidic oxides, B2O3 shows better performance than Al2O3 in reducing residual lithium compounds during the ALD process. Different from Al3+ cations doping occupying the transition metal ions position, BO3- polyanions doping occupies the oxygen ions position, which does not deteriorate the capacity of NCM. Transformation of residual lithium compounds and stabilizing surface lattice oxygen on NCM greatly decrease the formation of LiF and degradation of surface structure, which is the key to the improvement of rate capacity and cycling stability.
(Invited, Digital Presentation) Atomic Layer Deposited Templates for Constructing Functional Metal-Organic Framework Thin Films
Authors: Zhao Junjie 
Published: November 2022

Metal-organic frameworks (MOFs) are a class of porous crystalline materials featuring high surface area, ordered pore structures and amenability for post-synthetic modification. Integrating MOF thin films with various substrate materials could enable applications in separations, heterogeneous catalysis, chemical sensors and electronic devices. However, it is difficult to find a universal approach to deposit uniform and high-quality MOF coatings on a variety of substrate materials. Previous attempts often require surface modification methods that may not be generally applicable.
In this talk, interfacial engineering using atomic layer deposited (ALD) templates will be discussed for forming MOF thin films on various substrates. We found that ALD metal oxides are effective in promoting the heterogeneous nucleation of MOFs and also readily hydrolyzed into hydroxy double salts (HDSs) for rapid transformation to MOFs. With ALD template layers, conformal and functional MOF coatings were integrated on fibers, membranes and laminated structures. Accordingly, we developed a series of MOF-functionalized fibers for adsorption and catalytic degradation of hazardous compounds. Furthermore, we obtained ultra-thin mixed-metal MOF skin layers on porous alumina supports for membrane separation, and achieved large propylene permeance (up to 4.5×10-8 mol·m-2·s-1·Pa-1) and high propylene/propane selectivity over 250. We anticipate that this platform technology will also lead to potential device structures for chemical sensing, energy storage and many other scenarios.
Solution ALD: A Versatility Process for the Growth of Sulfides and Selenides
Authors: Barr Maissa K. S. , Zhao Baolin , Von Grundherr Peter , Koch Vanessa , Charvot Jaroslav , Halik Marcus , Bures Filip , Bachmann Julien 
Published: November 2022

We have proposed and demonstrated a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD), known with gaseous precursors, towards precursors dissolved in a liquid. The technique can also be considered as a generalization of already established methods such as the ‘layer by layer’ growth or the ‘successive ion layer adsorption and reaction’ (SILAR). 'Solution ALD' (sALD) shares the fundamental properties of standard ‘gas ALD’ (gALD), specially the self-limiting growth and the ability to coat conformally deep pores. It has been already shown that it is possible to transfer standard reactions from gALD to sALD such as TiO2 deposition . However, sALD also offers novel opportunities such as overcoming the need for volatile and thermally robust precursors.
To illustrate this, we establish sALD procedures for depositing films of non oxides layers such as Pb-compound deposition, MOF, selenides and sulfides. Those examples highlight how ionic, polar, or high-molecular weight precursors that only exist in the condensed phase are now rendered amenable to being utilized in surface-controlled thin film formation by sALD for depositing materials that would otherwise be more difficult or more expensive to achieve by gALD or hazardous. The deposition was achieved on small (2 cm*1 cm) and large samples (up to 10 cm*10 cm). The ALD behavior has been shown. The influence of the deposition parameters on the morphology, the crystalline structure and the chemical composition has been investigated by scanning electron microscopy, atomic force microscopy, grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. Additionally, the nucleation is studied in function of chemical pretreatment to control the growth and allow selective deposition of SnS, SnSe and Sb2Se3.
This particular ALD process offer the growth of high quality and crystalline layers in middle conditions with the use of low cost and environmental friendly precursors.

Y. Wu, D. Döhler, M. Barr, E Oks,M. Wolf, L. Santinacci and J. Bachmann, Nano Lett.
2015, 15, 6379

J. Fichtner, Y. Wu, J. Hitzenberger, T. Drewello and J. Bachmann, ECS J. Solid State Sci. Technol.
2017, 6, N171
(Digital Presentation)Cu Coordination Environment Modification Via Atomic Layer Infiltration As High Selective CO2RR Catalyst
Authors: Cao Meng , Han Xueyang , Liu Zhang , Ren Haonan , Du Chun , Yang Fan , Shan Bin , Chen Rong 
Published: November 2022

Carbon dioxide (CO2) is the most notorious greenhouse gas, released by both natural and artificial processes. In an ideal scenario, the production and consumption of CO2 should be balanced so that the concentration of CO2 in atmosphere remains constant to maintain environmental stability. Unfortunately, with the intensification of human industrial activities, this balance has gradually been disrupted, leading to more CO2 production and making global warming a pressing issue. With carbon neutrality gaining increasing attention, electrochemical CO2 reduction reaction (CO2RR) has emerged as a research orientation which converts CO2 to value-added products while storing renewable energy. Cu-based electrocatalysts have been studied extensively for the CO2RR into hydrocarbons in aqueous solutions under environmental conditions. However, they frequently endure low Faradaic Efficiency (FE) and selectivity of specific single product. Particularly, precise construction of Cu micro-environment is of great challenge for the design and fabrication of excellent Cu-based CO2RR catalysts.
Atomic layer infiltration (ALI) allows gas phase precursors to penetrate and diffuse into porous substrates through their nanoporous structures and to grow within the subsurface. Aiming at systematically regulating the Cu metal site micro-environment, porous HKUST-1 containing paddle-wheel Cu coordination nodes was chosen as a template and modified with ALI technique in this work. Various metals were introduced into HKUST-1 using ALI method to construct bimetallic sites which tended to produce CO, HCOOH and other products with high FEs. Density Functional Theory (DFT) calculations prove the modification with metals by ALI enhances the adsorption enthalpy of CO2 and alters the bonding interaction between reaction intermediates and adsorption center, thereby changing the reaction pathways. MOF conversion technique based on atomic layer deposition (ALD) will be utilized to fabricate HKUST-1 thin film in our future work, which allows nanometer precision of catalyst loading to balance active-site density with mass/charge transfer. The proposed ALI and ALD techniques elucidate the reliance of CO2RR selectivity on the Cu micro-environment and provide a platform for regulating Cu or other metal-base electrocatalyst coordination environment to facilitate high selectivity of CO2RR in the future
Enhancing Lithium-Ion Battery Aging Simulations By Coupling a High-Resolution, 3D, Grain-Scale Electromechanical Model to a Single Particle Model
Authors: Allen Jeffery M. , Weddle Peter J , Usseglio-Viretta Francois L. E. , Verma Ankit , Colclasure Andrew M. , Smith Kandler 
Published: November 2022

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. Unfortunately, this requires simulation of thousands of charge/discharge cycles, which can be rather time consuming depending on the fidelity of the simulation. The purpose of this talk is to discuss a new modeling framework that couples a high-resolution, continuous damage model (CDM) to a single particle model (SPM) resulting in a good combination of speed and fidelity.
In previous work, a 3D, continuum-level chemo-mechanical model was developed to investigate cracking within a single cathode particle comprised of hundreds to thousands of randomly oriented grains. The CDM predicted that particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains were misaligned, they expanded different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. The model predicted that small particles with large grains develop significantly less damage than larger particles with small grains. Finally, the model predicted most of the chemo-mechanical damage accumulates in the first charge after formation. This chemo-mechanical “damage saturation” effect indicated that initial particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced. This led to a need for simulating fatigue-like mechanism that degrade the battery over longer time scales.
In order to reach the time scales, need to resolve fatigue-like degradation, the CDM needs to be complemented by a faster model. Therefore, recent efforts have been focused on using results from the CDM to inform parameters within the SPM. These parameters are homogenization factors that are associated with diffusion, particle radius, and/or exchange current density. By coupling the CDM to the SPM, the aging simulation is broken up into two domains: short-term and long-term degradation. The short-term degradation occurs over a single cycle and is handled by the CDM due of its high fidelity, but relatively expensive computational cost. Such mechanism include break-in crack caused by mismatches in grain orientation. The long-term degradation occurs over tens of cycles and is handled by the SPM due it’s computational efficiency. Most of the fatigue-like mechanism fall into this category.
The eventual goal of this modeling framework is to upscale to a psudo-2D model allowing for full electrode simulation, which are informed by high-fidelity grain-scale simulations.

Figure 1