bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enhanced Property Tunability of Doubly Doped Semiconductor Nanomaterials Using the Cluster Seed Method
Authors: Pálmai Marcell , Tomczak Kyle , Snee Preston 
Published: November 2022

Semiconductor Quantum Dots (QDs) have great potential in applications for renewable energy generation due to their size-tunable redox potentials. They may be prepared with different morphologies and coated to create complex heterostructures. Doping of semiconductor nanomaterials is another mechanism to realize property tunability, and doped QDs are playing an increasing role in green energy generation applications. In 2013 our group reported a method to create a batch of doped quantum dots where each particle was embedded with the same number of guest ions, thus circumventing Poisson statistics. This was accomplished by nucleating the QD around an organometallic seed cluster that contains guest ions. As a result, each QD has the same number of dopants, which eliminates problems due to inhomogeneity of the guest ion stoichiometry. These materials were studied using time-resolved X-ray absorption spectroscopy, which allows us to characterize the electronic and coordination structure in both the ground and excited states.
Current research reveals the potential to doubly dope semiconductors using cluster seeding, and that the originating organometallic structure may be represented in the final material product. To this end, ZnCdSe nanowires were prepared in the presence of (MnTe)4 cluster seeds. The results reveal that Mn(2+) has been successfully incorporated into the host matrix, while temperature dependent optical measurements suggest significantly enhanced semiconductor exciton-magnetic dopant interactions in materials prepared by cluster seeding compared to doped control samples. This could be due to ferromagnetic Mn-Mn interactions in the host resulting from enhanced exchange coupling mediated by highly spin-orbit coupled tellurium bridging. Consequently, cluster seeding may be used to "dope the dopants", affording a heretofore unrealized method for developing designer materials with enhanced electronic and optical properties.

Figure 1
(Invited, Digital Presentation) Physical Properties of Silicon-Germanium Nanostructures: Theory and Simulations
Authors: Amato Michele 
Published: November 2022

Silicon germanium nanostructures (SiGe NSs) have acquired today a prominent role in several cutting-edge research topics in nanoscience, thanks to the most recent advances in synthesis, processing and characterization [1-4]. The physical properties of such nanosystems are strictly related not solely to the size of the system (as in pure Si and Ge NSs), but also to the relative composition of Si and Ge atoms as well as to the geometry of Si/Ge interface. The investigation of these materials with experimental techniques is, however, complicated by several factors not always well controlled which can hide the right comprehension of the fundamental properties. In this context first principles theoretical modeling is extraordinarily important as it can complement or augment experimental observations.
Here, I will present an overview of the ab initio computational modeling of various types of SiGe nanosystems (nanowires [5], nanodots [6] and slabs [7-8]). I will outline how by bringing together two similar elements –Si and Ge, neighbors in the periodic table–, a broad variety of new chemical and physical properties emerge, stimulating both fundamental and application-driven research in nanoscience. Indeed, I will show that substituting some of the atoms of a pure Si NS with Ge in configurations of distinct compositions and dimensionalities, can strongly affect some fundamental properties such as band gap, band offsets, work function and impurity doping levels.

Bibliography

[1] M. Amato, M. Palummo, R. Rurali, S. Ossicini, Chem. Rev. 114, 1371 (2014)
[2] I. Berbezier, A. Ronda, Surf. Sci. Rep., 64, 47 (2009)
[3] J.-N Aqua, I. Berbezier, L. Favre, T. Frisch, A. Ronda, Phys. Rep., 522, 52 (2013)
[4] D. J. Paul, Semicond. Sci. Technol. 19, R75–R108 (2004)
[5] M. Amato, S. Ossicini and R. Rurali, Nano Lett. 11, 2, 594-598 (2011)
[6] I. Marri, M. Amato, S. Ossicini, S. Grillo, O. Pulci, Interplay of quantum confinement and strain effects in type I to type II transition in Ge/Si core-shell nanocrystals (submitted, 2022)
[7] I. Marri, M. Amato, M. Bertocchi, A. Ferretti, D. Varsano, S. Ossicini, Phys. Chem. Chem. Phys. 22, 25593-25605 (2020)
[8] S. Pouch, M. Amato, M. Bertocchi, S. Ossicini, N. Chevalier, T. Mélin, J.M. Hartmann, O. Renault, V. Delaye, D. Mariolle, L. Borowik, J. Phys. Chem. C 119, 26776-26782 (2015)
Mechanistic Li-Ion Battery Modeling, What's Next?
Authors: Dubarry Matthieu , Beck David 
Published: November 2022

While relatively young, the mechanistic modeling approach has proven extremely versatile and effective for Lithium-ion battery diagnosis and prognosis and it has gained tremendous traction in the past decade. The approach is relying on digital twins built from different matchings of the individual voltage response of each electrode. The digital twins enable quantification of the degradation modes and open the gate for material-based diagnosis and prognosis without the need for complex models. From previous work in our laboratory, the method allowed to conceptually explain counter intuitive concepts such as hidden degradation mechanisms, overdischarge induced capacity, and the sudden apparition of knees.
This presentation will reflect on a decade worth of discussion and validation of several of the key concepts of digital twins for advanced diagnosis and prognosis since the seminal publications in the early 2010s. It will also introduce the next chapter with several new directions to enhance its application to more complex case figures. In the past decade since proposing our version of the framework, it was used to diagnose the degradation of several hundred cells of multiple chemistries and blends. It made possible to explain and predict the apparition of knees with the concept of hidden mechanisms and to emulate the impact of kinetics. The approach also proved useful to investigate overdischarge, overcharge, and to generate big-data with millions of synthetic voltage curves enabling the development of advanced diagnosis and prognosis tools. Looking forward, the approach can still be improved and some new directions will be detailed here with proof-of-concept simulations. This includes the simulation of blended and inhomogeneous electrodes that are destined to play a big role for the diagnosis and prognosis of next generation cells. Moreover, calculations could be done outside of constant current which could allow a much wider field implementation of better diagnosis and prognosis tools for deployed systems.
(Invited) Electrostatic Site Potential in Electrolytes As an Emerging Descriptor for Reversible Metal Electrodes
Authors: Takenaka Norio , Ko Seongjae , Yamada Atsuo 
Published: November 2022

In order to maximize the electrochemical stability of a battery with metal anode, suppressing the side reaction between the metal and the electrolyte is essential. When the deposition potential positions outside of the stability window, optimization of SEI is a general approach to realize kinetic hinderance of side reactions. While another effective approach should be upshifting the deposition potential itself because it makes the side reactions much slower and milder, or even thermodynamic stability could be gained if the potential is upshifted into the stability window of the electrolyte.
It is well known that electrode potentials vary significantly depending on the electrolyte. Typical example can be found in salt concentrated electrolyte, where the metal deposition potential significantly upshifts over 0.5 V upon increasing the concentration. However, the mechanism behind the potential shift has remained unclear.
By careful analyses of the local coordination environment by molecular dynamics simulations and the accurate experimental measurement of the deposition potential, we revealed that the potential shift is primarily determined by electrostatic destabilization of metal cations rather than the simple Nernst-type expression depending on cation activity. The shallow site potential of metal cations is attributable to the dominant coordination to more charge-dispersive, larger size anions rather than to relatively electro-positive solvents, thus decreasing the overall Coulombic energy gain of metal cations. Such simple yet hitherto-overlooked mechanism can be a useful guideline in the development of better electrolytes for reversible metal electrode.
(Invited) Drx and Drx+ As Earth-Abundant Inexpensive Cathodes
Authors: Ceder Gerbrand 
Published: November 2022

Scaling the Li-ion industry to multiple TWh/year will be challenging with NMC-class cathodes because of the cost and resource constraints arising from the use of nickel and/or cobalt. Disordered rocksalt cathodes DRX can be synthesized with almost any transition metal and offer a likely alternative to replace Ni-containing layered cathode materials. Since their invention in 2014 understanding and performance improvement of DRX materials has made significant progress. Materials based on Mn and Ti, which can be synthesized from inexpensive precursors, have shown that specific energies between 650 to 850Wh/kg can be maintained during extended cycling. The ability of these materials to substitute some O by F also provides them with excellent stability even up to high voltage. Since they lose little or no oxygen when highly charged, they are also like to provide high safety.
Rate capability, which early on posed a problem for DRX cathodes, has been improved through multiple strategies, and 200mA/g and higher rates can now be achieved without substantial capacity loss. Because these compounds can be synthesized from standard Mn-oxide and Ti-oxide precursors they have the potential to be a low-cost, resource abundant alternative to NMC class materials.
Isoindigo-Derived Organic Small-Molecules As Long-Lifespan and High-Rate Cathode Materials for Rechargeable Batteries
Authors: Park Jong-Jin , Yoon Seong-Jun , Kim Jinsang , Kwon Ji Eon 
Published: November 2022

Redox-active organic molecules (ROMs) are promising electrode materials for next-generation rechargeable batteries owing to their beneficial advantages of environmental friendliness, natural abundance, low cost, and possible high theoretical capacity. However, they suffer from a serious dissolution problem in organic electrolytes and low electrical conductivity, limiting their practical application. In particular, despite many advantages such as easy synthesis, potential low cost, and convenient processing, small-molecule electrode materials have typically showed far inferior stability and rate performance than polymeric materials.
Herein, two isoindigo-based small molecules, isoindigo (Me-IIG) and thienoisoindigo (Me-TIIG), were synthesized and evaluated as a cathode material in lithium-organic batteries. In a Li coin cell, Me-IIG and Me-TIIG electrode exhibited specific capacity of 156 and 168 mAh g-1 at 1C, corresponding to 84% and 95% of capacity utilization, respectively. The Me-TIIG with better planar molecular geometry than the Me-IIG showed much lower solubility in organic electrolytes with the aid of strong intra- and intermolecular interactions. As a result, the Me-TIIG electrode presented remarkably improved cycling stability, retaining 96% of the initial capacity after 500 cycles at 5C rate. Moreover, Me-TIIG exhibited lower reorganization energy than Me-IIG, which can facilitate a kinetically faster electrochemical pathway, leading to superior rate capability. It should be noted that the Me-TIIG electrode showed excellent rate performance achieving 70% capacity retention at a high rate of 20C.
Regulating Electrochemical Growth of Metals at Rechargeable Battery Electrodes
Authors: Zheng Jingxu , Archer Lynden A. , Checkelsky Joseph 
Published: November 2022

Control of crystallography of thin metal electrodeposit films has recently emerged as key to achieving long operating lifetimes in next-generation electrochemical systems for energy storage. Very recent studies show that the crystallography of metal deposits impacts both morphological evolution and chemical kinetics of the interfaces between metal anodes and electrolytes in a battery. We report that the large crystallographic heterogeneity, e.g., broad orientational distribution, that appears characteristic of commercial metal foils results in rough morphology upon plating/stripping. On this basis, we develop an accumulative roll bonding (ARB) methodology—a severe plastic deformation process—that uses commercial metal foils as input. Zn metal—a promising, low-cost-competitive battery anode material— is used as a first example to interrogate the proposed concept. We demonstrate that the ARB process is highly effective in achieving uniform, mono-domain quality crystallographic control on macroscopic materials. After the ARB process, the Zn grains exhibit a strong (002) texture (i.e. [002]Zn//ND). We report further that the texture transitions from a classical bipolar pattern to a nonclassical unipolar pattern under large nominal strain, almost completely eliminating the orientational heterogeneity of the foil. Evaluated as anodes in aqueous Zn coin cells, the strongly (002)-textured Zn suppresses the rough plating/stripping landscape, promotes uniform, homoepitaxial growth of Zn and remarkably improve the continuous plating/stripping performance by nearly two orders of magnitude under practical conditions (e.g., 4 mAh at 40 mA/cm2). The performance improvements are readily scaled to achieve pouch-type Zn full batteries that deliver exceptional reversibility. The ARB process is thermo-mechanical and can in principle be applied to any metal chemistry to achieve similar crystallographic uniformity, provided the appropriate temperature and accumulated strains are employed to achieve severe levels of plastic deformation. We evaluate this concept using ARB to induce strong texturing phenomena in commercial Li and Na foils, which unlike Zn (HCP) are BCC crystals, and demonstrate its success using morphological and electrochemical analysis of these metals as electrodes. Our simple process for creating strong textures in both hexagonal and cubic metals and illustrating the critical role such built-in crystallography plays underscores potentially transformative opportunities for developing scalable, highly reversible thin metal anodes (e.g. hexagonal Zn, Mg, and cubic Li, Na, Ca, Al) with specific crystal textures for next generation batteries that have practical N:P ratios.
Key References:
Zheng, J., et al.
Advanced Materials
34.1 (2022): 2106867.
Zheng, J., et al.
Nature Energy
6.4 (2021): 398-406.
Zheng, J., et al.
Science Advances
6.25 (2020): eabb1122
Zheng, J., et al.
Science
366.6465 (2019): 645-648.
Electrochemical Reduction of Active Metals in Aqueous Systems: An Electron Withdrawing Ligand Approach to Deposit Highly Adherent Oxide Layers
Authors: Nulwala Hunaid , Zhou Xu 
Published: November 2022

The electroplating of active metal in water is extremely challenging. The oxidative reactivity of active metals such as aluminum and zirconium metal leads to a very negative reduction potential. It makes the reduction in the presence of water impossible. Current active metal deposition is performed under inert conditions.
We have utilized a unique ligation approach; we can create aluminum species that remain stable in water and lower the reduction potential for aluminum by 0.5V. This lowering of reduction potential allows us to electrochemically reduce aluminum in water and compete with hydrogen evolution. With this platform we are able to deposit highly adherent layers of aluminum oxide layers on metal surfaces. The aluminum oxide layers are thin, coherent and highly adherent coatings. This aluminum oxide layer can then be chemically adapted to achieve previously inaccessible surface properties. For example, the coating can be made hydrophobic, highly adherent to different polymer coatings and a great tie layer to grow ceramic coatings.
We will be discussing the initial theory in reduction potential and then sharing the results of our work.
(Electrodeposition Division Early Career Investigator Award) Understanding and Controlling Electrodeposition of Li in Solid Electrolytes
Authors: Han Fudong 
Published: November 2022

The successful integration of Li metal anode with solid electrolytes seems to be a must for a high-energy-density solid-state battery. However, Li dendrites tend to form in solid electrolytes during Li plating. The formation of dendrites has been observed in solid electrolytes with various crystal structures from glass, glass-ceramic, poly-crystalline to single-crystalline materials, but the mechanism of such an unexpected dendrite growth remains elusive. In this presentation, I will introduce our understandings of lithium dendrite formation in solid electrolytes based on operando neutron depth profiling characterizations. The results highlight the important role of electronic conduction in solid electrolytes in the formation of isolated Li dendrites in solid electrolytes. I will then present our recent results in understanding the intrinsic value, voltage dependence, and charge carrier of electronic transport in typical lithium solid electrolytes. Lastly, I will introduce corresponding strategies to suppress dendrite formation in solid-state Li metal batteries.

Reference
s
:

[1] F. Han, A. S. Westover, J. Yue, X. Fan, F. Wang, M. Chi, D. N. Leonard, N. J. Dudney, H. Wang, C. Wang, Nature Energy, 4 (2019) 187.
[2] F. Han, J. Yue, X. Zhu, C. Wang, Advanced Energy Materials, 8 (2018) 1703644.
[3] F. Han, J. Yue, C. Chen, N. Zhao, X. Fan, Z. Ma, T. Gao, F. Wang, X. Guo, C. Wang, Joule, 2 (2018) 497.
[4] X. Fan, X. Ji, F. Han, J. Yue, J. Chen, L. Chen, T. Deng, J. Jiang, C. Wang, Science Advances, 4 (2018) eaau9245.
[5] R. Xu, F. Han, X. Fan, J. Tu, C. Wang, Nano Energy, 53 (2018) 958.
[6] Y. Huang, B. Shao, F. Han, Current Opinions in Electrochemistry, 33 (2022) 100933.
[7] Y. Huang, B. Shao, F. Han, Journal of Materials Chemistry A, 10 (2022) 12350.
[8] F. Han, Y. Zhu, X. He, Y. Mo, C. Wang, Advanced Energy Materials, 6 (2016) 1501590.
[9] F. Han, T. Gao, Y. Zhu, K. J. Gaskell, C. Wang, Advanced Materials, 27 (2015) 3473.
Scanning Electrochemical Cell Microscopy: A Tool for Nanoscopic Deposition of Light-Driven Photocatalysts
Authors: Oswald Eva , Gaus Anna-Laurine , Romer Jan , Kund Julian , von Delius Max , Kranz Christine 
Published: November 2022

Single and multi-barrel nanopipettes and nanopipette-based scanning electrochemical probe microscopy techniques like scanning electrochemical cell microscopy (SECCM) have gained significant attention as tools for localized, maskless, three-dimensional surface modifications [1,2]. The nanometer-sized orifices of nanopipettes allow delivering molecules to solution inducing concentration-confined electrodepositions. Also, electroless nanoscale depositions like the fountain pen technique [3] can be achieved by this technique.
In this study, we present the deposition of various cobaloxime-based earth-abundant Co catalysts for light-driven hydrogen evolution reaction (HER) [4]. Arrays of different cobalt(III) complexes were deposited via SECCM and investigated in respect with their HER activity using scanning electrochemical microscopy (SECM) in combination of Pd-microsensors [5] for in situ hydrogen (H2) measurements under illumination. In addition, AFM studies revealed possible degradation of the commercially available neutral benchmark complex [Co(dmgH)2(py)Cl] in these studies. First results will also be presented in respect with the deposition of nanowires via co-deposition of HER catalyst and Ruthenium photosensitizer. First spatially resolved photocatalytic studies at such nanowires, which are characterized by high surface area, will be presented. Also, the influence of the substrate will also be discussed.

References:

Oswald, K. Palanisamy, C. Kranz, Curr. Op.
Electrochem. 34, 100965 (2022).

Hengsteler et al., Nano Lett. 21, 9093 (2021).

-H. Kim, N. Moldovan, H.D. Espinosa, Small 1, 632, (2005).

Oswald et al., Chem. Eur. J. 27, 16896 (2021) and corrigendum (2022); doi:10.1002/chem.2022008809.

Kund et al., ChemElectroChem 9, e202200071 (2022)

Funding by the German Science Foundation (DFG) – project number 364549901 – TRR 234 (projects B7, C4).
(Digital Presentation) Electrodeposition of Re on Aerosol Jet Printed Metal Seed Layers on Flexible Substrates
Authors: Tsui Lok-kun , Ahammed Kamal , Sui Yongkun , Weigel Emily A , Huang Qiang , Lavin Judi 
Published: November 2022

Quantum computers (QCs) are expected to run advanced algorithms to solve currently intractable challenges in chemistry simulations, cryptography, medicine, and finance.[1] The Josephson Junction based qubits that power a quantum computer must reside in a cryogenically cooled chamber at 10 mK. Communications with this chip is currently carried out with a chandelier of rigid cables.[2] A flexible cable containing superconducting interconnect lines could in principle simplify the design of QC interconnects and lead to improvement in qubit density and efficiency. We have previously demonstrated the use of aerosol jet printing (AJP) for the patterning of electrodeposited Cu and Ni [3]. We have also recently reported on the development of a water-in-salt method to electrodeposit superconducting Re on evaporated Au on Si substrates. These Re components have a critical temperature above 4.2 K, which makes the superconductivity easily accessible with liquid He cooling[4].
We report for the first time the metallization of flexible Kapton substrates with printed Au and Ag nanoparticle inks by aerosol jet printing as the seed for superconductor electrodeposition. Electrodeposition of Re onto the printed structures was performed using the water-in-salt method. ASTM D3359 tests demonstrated that Au has superior adhesion to Kapton, while the Ag seed does not survive rhenium deposition, potentially due to the high internal stress of Re. Further, improved adhesion was demonstrated when Kapton substrates were roughened with 1200 grit sandpaper. Electrodeposited Re on AJP Au seed layer on flexible Kapton substrates, as shown in Figure 1, demonstrated a superconducting transition temperature of 6K. In addition, electrodeposited Re on Au survived 200 cycles of flexure testing under >30 MPa load and 1.2% strain. These efforts demonstrate the proof-of-principle for patterning of superconducting interconnects for the further development of QCs.

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. SAND2022-11522 A

References

[1] F. Bova, A. Goldfarb, and R.G. Melko “Commercial Applications of Quantum Computing.” EPJ Quantum Tech. (2021) 8:2.
[2] S. Krinner, S. Storz, P. Kurpiers, P. Magnard, J. Heinsoo, R. Keller, J. Lütolf, C. Eichler & A. Wallraff. “Engineering cryogenic setups for 100-qubit scale superconducting circuit systems.” EPJ Quantum Tech. (2019) 6:2.
[3] L. K. Tsui, S. C. Kayser, S. A. Strong, and J. M. Lavin, “High Resolution Aerosol Jet Printed Components with Electrodeposition-Enhanced Conductance.” ECS J. Solid State Sci. Tech. (2021). 10, 047001.
[4] W. D. Sides, E. Hassani, D. P. Pappas, Y. Hu, T. S. Oh, Q. Huang “Grain growth and superconductivity of rhenium electrodeposited from water-in-salt electrolytes.” J. App. Phys. (2020). 127, 085301.
Figure 1. (a) Photograph of a well adhered Re on Au sample. (b) Superconducting transition data for Re on printed Au on Kapton.

Figure 1