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result(s) for
"Kourkoutis, Lena F."
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Doping evolution of the Mott–Hubbard landscape in infinite-layer nickelates
by
Li, Danfeng
,
Goodge, Berit H.
,
Wang, Bai Yang
in
Applied Physical Sciences
,
electron energy-loss
,
hole doping
2021
The recent observation of superconductivity in Nd0.8Sr0.2NiO₂ has raised fundamental questions about the hierarchy of the underlying electronic structure. Calculations suggest that this system falls in the Mott–Hubbard regime, rather than the charge-transfer configuration of other nickel oxides and the superconducting cuprates. Here, we use state-of-the-art, locally resolved electron energy-loss spectroscopy to directly probe the Mott–Hubbard character of Nd1—x
Sr
x
NiO₂. Upon doping, we observe emergent hybridization reminiscent of the Zhang–Rice singlet via the oxygen-projected states, modification of the Nd 5d states, and the systematic evolution of Ni 3d hybridization and filling. These experimental data provide direct evidence for the multiband electronic structure of the superconducting infinite-layer nickelates, particularly via the effects of hole doping on not only the oxygen but also nickel and rare-earth bands.
Journal Article
Linear-in-temperature resistivity for optimally superconducting (Nd,Sr)NiO2
by
Wang, Bai Yang
,
Goodge, Berit H.
,
Lee, Kyuho
in
639/766/119/1003
,
639/766/119/995
,
Charge transfer
2023
The occurrence of superconductivity in proximity to various strongly correlated phases of matter has drawn extensive focus on their normal state properties, to develop an understanding of the state from which superconductivity emerges
1
–
4
. The recent finding of superconductivity in layered nickelates raises similar interests
5
–
8
. However, transport measurements of doped infinite-layer nickelate thin films have been hampered by materials limitations of these metastable compounds: in particular, a high density of extended defects
9
–
11
. Here, by moving to a substrate (LaAlO
3
)
0.3
(Sr
2
TaAlO
6
)
0.7
that better stabilizes the growth and reduction conditions, we can synthesize the doping series of Nd
1–
x
Sr
x
NiO
2
essentially free from extended defects. In their absence, the normal state resistivity shows a low-temperature upturn in the underdoped regime, linear behaviour near optimal doping and quadratic temperature dependence for overdoping. This is phenomenologically similar to the copper oxides
2
,
12
despite key distinctions—namely, the absence of an insulating parent compound
5
,
6
,
9
,
10
, multiband electronic structure
13
,
14
and a Mott–Hubbard orbital alignment rather than the charge-transfer insulator of the copper oxides
15
,
16
. We further observe an enhancement of superconductivity, both in terms of transition temperature and range of doping. These results indicate a convergence in the electronic properties of both superconducting families as the scale of disorder in the nickelates is reduced.
By moving to a substrate that better stabilizes conditions, the doping series of Nd
1–
x
Sr
x
NiO
2
is synthesized free from extended defects, resulting in enhancement of superconductivity in terms of transition temperature and range of doping.
Journal Article
Charge transport and localization in atomically coherent quantum dot solids
2016
Epitaxial attachment of quantum dots into ordered superlattices enables the synthesis of quasi-two-dimensional materials that theoretically exhibit features such as Dirac cones and topological states, and have major potential for unprecedented optoelectronic devices. Initial studies found that disorder in these structures causes localization of electrons within a few lattice constants, and highlight the critical need for precise structural characterization and systematic assessment of the effects of disorder on transport. Here we fabricated superlattices with the quantum dots registered to within a single atomic bond length (limited by the polydispersity of the quantum dot building blocks), but missing a fraction (20%) of the epitaxial connections. Calculations of the electronic structure including the measured disorder account for the electron localization inferred from transport measurements. The calculations also show that improvement of the epitaxial connections will lead to completely delocalized electrons and may enable the observation of the remarkable properties predicted for these materials.
Variations in the size of the nanocrystals and in the width of their epitaxial connections are shown to significantly affect carrier localization in superlattices formed by the oriented attachment of PbSe nanocrystals.
Journal Article
Organo–organic and organo–mineral interfaces in soil at the nanometer scale
2020
The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo–mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo–organic interfaces in contrast to exclusively organo–mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo–organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo–mineral interface, 88% (72–92%) and 33% (16–53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo–organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.
Historically it has been maintained that soil organic carbon (SOC) is stabilized through interactions with mineral interfaces. Here the authors use cryo-electron microscopy and spectroscopy to show that SOC interactions can also occur between organic forms in patchy, disordered structure.
Journal Article
Designing solid-liquid interphases for sodium batteries
by
Zachman, Michael J.
,
Arias, Tomas A.
,
Tu, Zhengyuan
in
639/301/930/543
,
639/4077/4079/891
,
Anodes
2017
Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid–electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.
The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid–electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.
Journal Article
Resolving the polar interface of infinite-layer nickelate thin films
by
Li, Danfeng
,
Kourkoutis, Lena F
,
Wang, Bai Yang
in
Atomic structure
,
Charge density
,
Crystal structure
2023
Nickel-based superconductors provide a long-awaited experimental platform to explore possible cuprate-like superconductivity. Despite similar crystal structure and d electron filling, however, superconductivity in nickelates has thus far only been stabilized in thin-film geometry, raising questions about the polar interface between substrate and thin film. Here we conduct a detailed experimental and theoretical study of the prototypical interface between Nd1−xSrxNiO2 and SrTiO3. Atomic-resolution electron energy loss spectroscopy in the scanning transmission electron microscope reveals the formation of a single intermediate Nd(Ti,Ni)O3 layer. Density functional theory calculations with a Hubbard U term show how the observed structure alleviates the polar discontinuity. We explore the effects of oxygen occupancy, hole doping and cation structure to disentangle the contributions of each for reducing interface charge density. Resolving the non-trivial interface structure will be instructive for future synthesis of nickelate films on other substrates and in vertical heterostructures.Nickelate superconductivity has so far been limited to thin films, raising questions about the role of the polar substrate–film interface. Here the authors utilize advanced characterization techniques to reveal the interfacial atomic structure and its relevance for superconductivity.
Journal Article
Structure and control of charge density waves in two-dimensional 1T-TaS2
2015
The layered transition metal dichalcogenides host a rich collection of charge density wave phases in which both the conduction electrons and the atomic structure display translational symmetry breaking. Manipulating these complex states by purely electronic methods has been a long-sought scientific and technological goal. Here, we show how this can be achieved in 1T-TaS₂ in the 2D limit. We first demonstrate that the intrinsic properties of atomically thin flakes are preserved by encapsulation with hexagonal boron nitride in inert atmosphere. We use this facile assembly method together with transmission electron microscopy and transport measurements to probe the nature of the 2D state and show that its conductance is dominated by discommensurations. The discommensuration structure can be precisely tuned in few-layer samples by an in-plane electric current, allowing continuous electrical control over the discommensuration-melting transition in 2D.
Journal Article
Stabilizing polymer electrolytes in high-voltage lithium batteries
by
Stalin, Sanjuna
,
Zachman, Michael J.
,
Zhao, Qing
in
140/146
,
639/301/299/891
,
639/4077/4079/891
2019
Electrochemical cells that utilize lithium and sodium anodes are under active study for their potential to enable high-energy batteries. Liquid and solid polymer electrolytes based on ether chemistry are among the most promising choices for rechargeable lithium and sodium batteries. However, uncontrolled anionic polymerization of these electrolytes at low anode potentials and oxidative degradation at working potentials of the most interesting cathode chemistries have led to a quite concession in the field that solid-state or flexible batteries based on polymer electrolytes can only be achieved in cells based on low- or moderate-voltage cathodes. Here, we show that cationic chain transfer agents can prevent degradation of ether electrolytes by arresting uncontrolled polymer growth at the anode. We also report that cathode electrolyte interphases composed of preformed anionic polymers and supramolecules provide a fundamental strategy for extending the high voltage stability of ether-based electrolytes to potentials well above conventionally accepted limits.
Here the authors use cationic chain transfer agents to prevent degradation of ether electrolytes by arresting uncontrolled polymer growth at the anode. This work provides a fundamental strategy for extending the high voltage stability of these electrolytes to potentials above conventionally accepted limits.
Journal Article
Fast ion transport at solid–solid interfaces in hybrid battery anodes
by
Zachman, Michael J.
,
Tu, Zhengyuan
,
Choudhury, Snehashis
in
639/301/299
,
639/4077/4079/891
,
639/638/161
2018
Carefully designed solid-electrolyte interphases are required for stable, reversible and efficient electrochemical energy storage in batteries. We report that hybrid battery anodes created by depositing an electrochemically active metal (for example, Sn, In or Si) on a reactive alkali metal electrode by a facile ion-exchange chemistry lead to very high exchange currents and stable long-term performance of electrochemical cells based on Li and Na electrodes. By means of direct visualization and ex situ electrodeposition studies, Sn–Li anodes are shown to be stable at 3 mA cm
−2
and 3 mAh cm
−2
. Prototype full cells in which the hybrid anodes are paired with high-loading LiNi
0.8
Co
0.15
Al
0.05
O
2
(NCA) cathodes are also reported. As a second demonstration, we create and study Sn–Na hybrid anodes and show that they can be cycled stably for more than 1,700 hours with minimal voltage divergence. Charge storage at the hybrid anodes is reported to involve a combination of alloying and electrodeposition reactions.
Solid-electrolyte interphases (SEI) play important roles in battery operations. Here, the authors report hybrid anodes by forming a Sn overlayer on alkali metal electrodes, leading to a robust SEI and consequently improved electrochemical performance.
Journal Article
Emergent layer stacking arrangements in c-axis confined MoTe2
2023
The layer stacking order in 2D materials strongly affects functional properties and holds promise for next-generation electronic devices. In bulk, octahedral MoTe
2
possesses two stacking arrangements, the ferroelectric Weyl semimetal T
d
phase and the higher-order topological insulator 1T′ phase. However, in thin flakes of MoTe
2
, it is unclear if the layer stacking follows the T
d
, 1T′, or an alternative stacking sequence. Here, we use atomic-resolution scanning transmission electron microscopy to directly visualize the MoTe
2
layer stacking. In thin flakes, we observe highly disordered stacking, with nanoscale 1T′ and T
d
domains, as well as alternative stacking arrangements not found in the bulk. We attribute these findings to intrinsic confinement effects on the MoTe
2
stacking-dependent free energy. Our results are important for the understanding of exotic physics displayed in MoTe
2
flakes. More broadly, this work suggests
c
-axis confinement as a method to influence layer stacking in other 2D materials.
The layer stacking order in 2D materials can be used to control functional properties. Here, the authors find a thickness effect, where thin flakes of MoTe
2
display stacking arrangements different from bulk crystals.
Journal Article