Publications

2024

1. easyunfold: A Python package for unfolding electronic band structures

   Bonan Zhu, Seán R. Kavanagh, and David Scanlon

   Journal of Open Source Software, Jan 2024

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   Zhu et al., (2024). easyunfold: A Python package for unfolding electronic band structures. Journal of Open Source Software, 9(93), 5974, https://doi.org/10.21105/joss.05974

2. Discovery of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) as promising thermoelectric materials by computational screening

   Dan Han, Bonan Zhu, Zenghua Cai, and 6 more authors

   Matter, Jan 2024

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   The thermoelectric performance of existing perovskites lags far behind that of state-of-the-art thermoelectric materials such as SnSe. Despite halide perovskites showing promising thermoelectric properties, namely, high Seebeck coefficients and ultralow thermal conductivities, their thermoelectric performance is significantly restricted by low electrical conductivities. Here, we explore new multi-anion antiperovskites X6NFSn2 (X = Ca, Sr, and Ba) via B-site anion mutation in antiperovskite and global structure searches and demonstrate their phase stability by first-principles calculations. Ca6NFSn2 and Sr6NFSn2 exhibit decent Seebeck coefficients and ultralow lattice thermal conductivities (\textless1 W m−1 K−1). Notably, Ca6NFSn2 and Sr6NFSn2 show remarkably larger electrical conductivities compared to the halide perovskite CsSnI3. The combined superior electrical and thermal properties of Ca6NFSn2 and Sr6NFSn2 lead to high thermoelectric figures of merit (ZTs) of ∼1.9 and ∼2.3 at high temperatures. Our exploration of multi-anion antiperovskites X6NFSn2 (X = Ca, Sr) realizes the “phonon-glass, electron-crystal” concept within the antiperovskite structure.

3. How to verify the precision of density-functional-theory implementations via reproducible and universal workflows

   Emanuele Bosoni, Louis Beal, Marnik Bercx, and 42 more authors

   Nature Reviews Physics, Jan 2024

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   Density-functional theory methods and codes adopting periodic boundary conditions are extensively used in condensed matter physics and materials science research. In 2016, their precision (how well properties computed with different codes agree among each other) was systematically assessed on elemental crystals: a first crucial step to evaluate the reliability of such computations. In this Expert Recommendation, we discuss recommendations for verification studies aiming at further testing precision and transferability of density-functional-theory computational approaches and codes. We illustrate such recommendations using a greatly expanded protocol covering the whole periodic table from Z = 1 to 96 and characterizing 10 prototypical cubic compounds for each element: four unaries and six oxides, spanning a wide range of coordination numbers and oxidation states. The primary outcome is a reference dataset of 960 equations of state cross-checked between two all-electron codes, then used to verify and improve nine pseudopotential-based approaches. Finally, we discuss the extent to which the current results for total energies can be reused for different goals.

4. Structure and ionic conduction enhancement mechanisms at CeO2/SrTiO3 heterointerfaces

   Bonan Zhu, Georg Schusteritsch, Weiwei Li, and 4 more authors

   Applied Physics Reviews, Jun 2024

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   Fluorite-perovskite heterointerfaces garner great interest for enhanced ionic conductivity for application in electronic and energy devices. However, the origin of observed enhanced ionic conductivity as well as the details of the atomic structure at these interfaces remain elusive. Here, systematic, multi-stoichiometry computational searches and experimental investigations are performed to obtain stable and exact atomic structures of interfaces between CeO2 and SrTiO3—two archetypes of the corresponding structural families. Local reconstructions take place at the interface because of mismatched lattices. TiO2 terminated SrTiO3 causes a buckled rock salt CeO interface layer to emerge. In contrast, SrO terminated SrTiO3 maintains the fluorite structure at the interface compensated by a partially occupied anion lattice. Moderate enhancement in oxygen diffusion is found along the interface by simulations, yet evidence to support further significant enhancement is lacking. Our findings demonstrate the control of interface termination as an effective pathway to achieve desired device performance.

5. doped: Python toolkit for robust and repeatable charged defect supercell calculations

   Seán R. Kavanagh, Alexander G. Squires, Adair Nicolson, and 6 more authors

   Journal of Open Source Software, Jun 2024

2023

1. Highly cyclable voltage control of magnetism in cobalt ferrite nanopillars for memory and neuromorphic applications

   Muireann h-Óra, Aliona Nicolenco, P. Monalisha, and 6 more authors

   APL Materials, May 2023

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   Tuning the properties of magnetic materials by voltage-driven ion migration (magneto-ionics) gives potential for energy-efficient, non-volatile magnetic memory and neuromorphic computing. Here, we report large changes in the magnetic moment at saturation (mS) and coercivity (HC), of 34% and 78%, respectively, in an array of CoFe2O4 (CFO) epitaxial nanopillar electrodes (∼50 nm diameter, ∼70 nm pitch, and 90 nm in height) with an applied voltage of −10 V in a liquid electrolyte cell. Furthermore, a magneto-ionic response faster than 3 s and endurance >2000 cycles are demonstrated. The response time is faster than for other magneto-ionic films of similar thickness, and cyclability is around two orders of magnitude higher than for other oxygen magneto-ionic systems. Using a range of characterization techniques, magnetic switching is shown to arise from the modulation of oxygen content in the CFO. Also, the highly cyclable, self-assembled nanopillar structures were demonstrated to emulate various synaptic behaviors, exhibiting non-volatile, multilevel magnetic states for analog computing and high-density storage. Overall, CFO nanopillar arrays offer the potential to be used as interconnected synapses for advanced neuromorphic computing applications.

2. Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films

   Dong Li, Hongguang Wang, Kaifeng Li, and 16 more authors

   Nature Communications, Jun 2023

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   Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO6 octahedral rotations throughout LaCoO3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO3 films while suggesting potential applications toward low-power spintronic devices.

3. Cation disorder dominates the defect chemistry of high-voltage LiMn 1.5 Ni 0.5 O 4 (LMNO) spinel cathodes

   Jiayi Cen, Bonan Zhu, Seán R. Kavanagh, and 2 more authors

   Journal of Materials Chemistry A, Jun 2023
4. Exploring battery cathode materials in the Li-Ni-O phase diagrams using structure prediction

   Jiayi Cen, Bonan Zhu, and David O. Scanlon

   Journal of Physics: Energy, Jun 2023

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   The Li-Ni-O phase diagram contains several electrochemically active ternary phases. Many compositions and structures in this phase space can easily be altered by (electro-)chemical processes, yielding many more (meta-)stable structures with interesting properties. In this study, we use ab initio random structure searching (AIRSS) to accelerate materials discovery of the Li-Ni-O phase space. We demonstrate that AIRSS can efficiently explore structures (e.g. LiNiO2) displaying dynamic Jahn-Teller effects. A thermodynamically stable Li2Ni2O3 phase which reduces the thermodynamic stability window of LiNiO2 was discovered. AIRSS also encountered many dynamically stable structures close to the convex hull. Therefore, we confirm the presence of metastable Li-Ni-O phases by revealing their structures and properties. This work will allow Li-Ni-O phases to be more easily identified in future experiments and help to combat the challenges in synthesizing Li-Ni-O phases.

5. Developments and further applications of ephemeral data derived potentials

   Pascal T. Salzbrenner, Se Hun Joo, Lewis J. Conway, and 5 more authors

   The Journal of Chemical Physics, Oct 2023

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   Machine-learned interatomic potentials are fast becoming an indispensable tool in computational materials science. One approach is the ephemeral data-derived potential (EDDP), which was designed to accelerate atomistic structure prediction. The EDDP is simple and cost-efficient. It relies on training data generated in small unit cells and is fit using a lightweight neural network, leading to smooth interactions which exhibit the robust transferability essential for structure prediction. Here, we present a variety of applications of EDDPs, enabled by recent developments of the open-source EDDP software. New features include interfaces to phonon and molecular dynamics codes, as well as deployment of the ensemble deviation for estimating the confidence in EDDP predictions. Through case studies ranging from elemental carbon and lead to the binary scandium hydride and the ternary zinc cyanide, we demonstrate that EDDPs can be trained to cover wide ranges of pressures and stoichiometries, and used to evaluate phonons, phase diagrams, superionicity, and thermal expansion. These developments complement continued success in accelerated structure prediction.

6. Accessible chemical space for metal nitride perovskites

   Bastien F. Grosso, Daniel W. Davies, Bonan Zhu, and 2 more authors

   Chemical Science, Aug 2023

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   Building on the extensive exploration of metal oxide and metal halide perovskites, metal nitride perovskites represent a largely unexplored class of materials. We report a multi-tier computational screening of this chemical space. From a pool of 3660 ABN3 compositions covering I–VIII, II–VII, III–VI and IV–V oxidation state combinations, 279 are predicted to be chemically feasible. The ground-state structures of the 25 most promising candidate compositions were explored through enumeration over octahedral tilt systems and global optimisation. We predict 12 dynamically and thermodynamically stable nitride perovskite materials, including YMoN3, YWN3, ZrTaN3, and LaMoN3. These feature significant electric polarisation and low predicted switching electric field, showing similarities with metal oxide perovskites and making them attractive for ferroelectric memory devices.

2022

1. Manipulating the metal-to-insulator transition and magnetic properties in manganite thin films via epitaxial strain

   Dong Li, Bonan Zhu, Dirk Backes, and 14 more authors

   Physical Review B, Apr 2022

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   Strain engineering of epitaxial transition metal oxide heterostructures offers an intriguing opportunity to control electronic structures by modifying the interplay between spin, charge, orbital, and lattice degrees of freedom. Here, we demonstrate that the electronic structure, magnetic and transport properties of La0.9Ba0.1MnO3 thin films can be effectively controlled by epitaxial strain. Spectroscopic studies and first-principles calculations reveal that the orbital occupancy in Mn eg orbitals can be switched from the d3z2−r2 orbital to the dx2−y2 orbital by varying the strain from compressive to tensile. The change of orbital occupancy associated with Mn 3d-O 2p hybridization leads to dramatic modulation of the magnetic and electronic properties of strained La0.9Ba0.1MnO3 thin films. Under moderate tensile strain, an emergent ferromagnetic insulating state with an enhanced ferromagnetic Curie temperature of 215 K is achieved. These findings not only deepen our understanding of electronic structures, magnetic and transport properties in the La0.9Ba0.1MnO3 system, but also demonstrate the use of epitaxial strain as an effective knob to tune the electronic structures and related physical properties for potential spintronic device applications.

2. Predicting Lithium Iron Oxysulfides for Battery Cathodes

   Bonan Zhu, and David O. Scanlon

   ACS Applied Energy Materials, Jan 2022

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   Cathode materials that have high specific energies and low manufacturing costs are vital for the scaling up of lithium-ion batteries (LIBs) as energy storage solutions. Fe-based intercalation cathodes are highly attractive because of the low cost and the abundance of raw materials. However, existing Fe-based materials, such as LiFePO4, suffer from low capacity due to the large size of the polyanions. Turning to mixed anion systems can be a promising strategy to achieve higher specific capacity. Recently, antiperovskite-structured oxysulfide Li2FeSO has been synthesized and reported to be electrochemically active. In this work, we perform an extensive computational search for iron-based oxysulfides using ab initio random structure searching (AIRSS). By performing an unbiased sampling of the Li–Fe–S–O chemical space, several oxysulfide phases have been discovered, which are predicted to be less than 50 meV/atom from the convex hull and potentially accessible for synthesis. Among the predicted phases, two anti-Ruddlesden–Popper-structured materials Li2Fe2S2O and Li4Fe3S3O2 have been found to be attractive as they have high theoretical capacities with calculated average voltages of 2.9 and 2.5 V, respectively, and their distances to hull are less than 5 meV/atom. By performing nudged-elastic band calculations, we show that the Li-ion transport in these materials takes place by hopping between the nearest neighboring sites with low activation barriers between 0.3 and 0.5 eV. The richness of materials yet to be synthesized in the Li–Fe–S–O phase field illustrates the great opportunity in these mixed anion systems for energy storage applications and beyond.

2021

1. Materials Informatics Reveals Unexplored Structure Space in Cuprate Superconductors

   Rhys E. A. Goodall, Bonan Zhu, Judith L. MacManus-Driscoll, and 1 more author

   Advanced Functional Materials, Jan 2021

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   High-temperature superconducting cuprates have the potential to be transformative in a wide range of energy applications. In this work, the corpus of historical data about cuprates is analyzed using materials informatics, re-examining how their structures are related to their critical temperatures (Tc). The available data is highly clustered and no single database contains all the features of interest to properly examine trends. To work around these issues a linear calibration approach that allows the utilization of multiple data sources is employed, combining fine resolution data for which the Tc is unknown with coarse resolution data where it is known. The hybrid data set constructed enables the exploration of the trends in Tc with the apical and in-plane copper–oxygen distances. It is shown that large regions of the materials space have yet to be explored. Novel experiments relying on the nano-engineering of the crystal structure may enable the exploration of such new regions. Based on the trends identified it is proposed that single layer Bi-based cuprates are good candidate systems for such experiments.

2. Common workflows for computing material properties using different quantum engines

   Sebastiaan P. Huber, Emanuele Bosoni, Marnik Bercx, and 23 more authors

   npj Computational Materials, Aug 2021

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   The prediction of material properties based on density-functional theory has become routinely common, thanks, in part, to the steady increase in the number and robustness of available simulation packages. This plurality of codes and methods is both a boon and a burden. While providing great opportunities for cross-verification, these packages adopt different methods, algorithms, and paradigms, making it challenging to choose, master, and efficiently use them. We demonstrate how developing common interfaces for workflows that automatically compute material properties greatly simplifies interoperability and cross-verification. We introduce design rules for reusable, code-agnostic, workflow interfaces to compute well-defined material properties, which we implement for eleven quantum engines and use to compute various material properties. Each implementation encodes carefully selected simulation parameters and workflow logic, making the implementer’s expertise of the quantum engine directly available to non-experts. All workflows are made available as open-source and full reproducibility of the workflows is guaranteed through the use of the AiiDA infrastructure.

3. Perspectives for next generation lithium-ion battery cathode materials

   Samuel G. Booth, Alisyn J. Nedoma, Nirmalesh N. Anthonisamy, and 42 more authors

   APL Materials, Oct 2021

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   Transitioning to electrified transport requires improvements in sustainability, energy density, power density, lifetime, and approved the cost of lithium-ion batteries, with significant opportunities remaining in the development of next-generation cathodes. This presents a highly complex, multiparameter optimization challenge, where developments in cathode chemical design and discovery, theoretical and experimental understanding, structural and morphological control, synthetic approaches, and cost reduction strategies can deliver performance enhancements required in the near- and longer-term. This multifaceted challenge requires an interdisciplinary approach to solve, which has seen the establishment of numerous academic and industrial consortia around the world to focus on cathode development. One such example is the Next Generation Lithium-ion Cathode Materials project, FutureCat, established by the UK’s Faraday Institution for electrochemical energy storage research in 2019, aimed at developing our understanding of existing and newly discovered cathode chemistries. Here, we present our perspective on persistent fundamental challenges, including protective coatings and additives to extend lifetime and improve interfacial ion transport, the design of existing and the discovery of new cathode materials where cation and cation-plus-anion redox-activity can be exploited to increase energy density, the application of earth-abundant elements that could ultimately reduce costs, and the delivery of new electrode topologies resistant to fracture which can extend battery lifetime.

4. Accelerating cathode material discovery through ab initio random structure searching

   Bonan Zhu, Ziheng Lu, Chris J. Pickard, and 1 more author

   APL Materials, Dec 2021

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   The choice of cathode material in Li-ion batteries underpins their overall performance. Discovering new cathode materials is a slow process, and all major commercial cathode materials are still based on those identified in the 1990s. Discovery of materials using high-throughput calculations has attracted great research interest; however, reliance on databases of existing materials begs the question of whether these approaches are applicable for finding truly novel materials. In this work, we demonstrate that ab initio random structure searching (AIRSS), a first-principles structure prediction method that does not rely on any pre-existing data, can locate low energy structures of complex cathode materials efficiently based only on chemical composition. We use AIRSS to explore three Fe-containing polyanion compounds as low-cost cathodes. Using known quaternary LiFePO4 and quinary LiFeSO4F cathodes as examples, we easily reproduce the known polymorphs, in addition to predicting other, hitherto unknown, low energy polymorphs and even finding a new polymorph of LiFeSO4F that is more stable than the known ones. We then explore the phase space for Fe-containing fluoroxalates, predicting a range of redox-active phases that are yet to be experimentally synthesized, demonstrating the suitability of AIRSS as a tool for accelerating the discovery of novel cathode materials.

5. Crystal Structure of Colloidally Prepared Metastable Ag2Se Nanocrystals

   Bryce A. Tappan, Bonan Zhu, Patrick Cottingham, and 3 more authors

   Nano Letters, Jul 2021

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   Structural polymorphism is known for many bulk materials; however, on the nanoscale metastable polymorphs tend to form more readily than in the bulk, and with more structural variety. One such metastable polymorph observed for colloidal Ag2Se nanocrystals has traditionally been referred to as the “tetragonal” phase. While there are reports on the chemistry and properties of this metastable polymorph, its crystal structure, and therefore electronic structure, has yet to be determined. We report that an anti-PbCl2-like structure type (space group P21/n) more accurately describes the powder X-ray diffraction and X-ray total scattering patterns of colloidal Ag2Se nanocrystals prepared by several different methods. Density functional theory (DFT) calculations indicate that this anti-PbCl2-like Ag2Se polymorph is a dynamically stable, narrow-band-gap semiconductor. The anti-PbCl2-like structure of Ag2Se is a low-lying metastable polymorph at 5–25 meV/atom above the ground state, depending on the exchange-correlation functional used.

6. Ab initio random structure searching for battery cathode materials

   Ziheng Lu, Bonan Zhu, Benjamin W. B. Shires, and 2 more authors

   The Journal of Chemical Physics, May 2021

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   Cathodes are critical components of rechargeable batteries. Conventionally, the search for cathode materials relies on experimental trial-and-error and a traversing of existing computational/experimental databases. While these methods have led to the discovery of several commercially viable cathode materials, the chemical space explored so far is limited and many phases will have been overlooked, in particular, those that are metastable. We describe a computational framework for battery cathode exploration based on ab initio random structure searching (AIRSS), an approach that samples local minima on the potential energy surface to identify new crystal structures. We show that by delimiting the search space using a number of constraints, including chemically aware minimum interatomic separations, cell volumes, and space group symmetries, AIRSS can efficiently predict both thermodynamically stable and metastable cathode materials. Specifically, we investigate LiCoO2, LiFePO4, and LixCuyFz to demonstrate the efficiency of the method by rediscovering the known crystal structures of these cathode materials. The effect of parameters, such as minimum separations and symmetries, on the efficiency of the sampling is discussed in detail. The adaptation of the minimum interatomic distances on a species-pair basis, from low-energy optimized structures to efficiently capture the local coordination environment of atoms, is explored. A family of novel cathode materials based on the transition-metal oxalates is proposed. They demonstrate superb energy density, oxygen-redox stability, and lithium diffusion properties. This article serves both as an introduction to the computational framework and as a guide to battery cathode material discovery using AIRSS.

2020

1. Magnetic signatures of 120 K superconductivity at interfaces in La2CuO4+δ

   Eun-Mi Choi, Bonan Zhu, Ping Lu, and 4 more authors

   Nanoscale, Feb 2020

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   In self-assembled vertically aligned nanocomposite (VAN) thin films of La2CuO4+δ + LaCuO3, we find from DC magnetic susceptibility measurements, weak signatures of superconductivity at ∼120 K. This compares to a maximum TC of 40 K in bulk La2CuO4+δ. The 120 K signature occurs only when both c-axis and a-axis oriented La2CuO4+δ grains are present in the films. The superconductivity was lost after 3 months of storage but was recovered by annealing in oxygen. From lattice parameter analyses undertaken close to the c/a grain boundaries, it was determined that expansion of the La perovskite block in c-La2CuO4+δ enables the differently oriented grains to join at the interface. This expansion is consistent with the higher TC interfacial region. The work shows a new direction for increasing TC in cuprates – namely careful strain engineering of the crystal structure independently in-plane and out-of-plane.

2. Interface Engineered Room-Temperature Ferromagnetic Insulating State in Ultrathin Manganite Films

   Weiwei Li, Bonan Zhu, Qian He, and 11 more authors

   Advanced Science, Feb 2020

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   Ultrathin epitaxial films of ferromagnetic insulators (FMIs) with Curie temperatures near room temperature are critically needed for use in dissipationless quantum computation and spintronic devices. However, such materials are extremely rare. Here, a room-temperature FMI is achieved in ultrathin La0.9Ba0.1MnO3 films grown on SrTiO3 substrates via an interface proximity effect. Detailed scanning transmission electron microscopy images clearly demonstrate that MnO6 octahedral rotations in La0.9Ba0.1MnO3 close to the interface are strongly suppressed. As determined from in situ X-ray photoemission spectroscopy, O K-edge X-ray absorption spectroscopy, and density functional theory, the realization of the FMI state arises from a reduction of Mn eg bandwidth caused by the quenched MnO6 octahedral rotations. The emerging FMI state in La0.9Ba0.1MnO3 together with necessary coherent interface achieved with the perovskite substrate gives very high potential for future high performance electronic devices.

3. Atomic-Scale Control of Electronic Structure and Ferromagnetic Insulating State in Perovskite Oxide Superlattices by Long-Range Tuning of BO6 Octahedra

   Weiwei Li, Bonan Zhu, Ruixue Zhu, and 11 more authors

   Advanced Functional Materials, Feb 2020

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   Control of BO6 octahedral rotations at the heterointerfaces of dissimilar ABO3 perovskites has emerged as a powerful route for engineering novel physical properties. However, its impact length scale is constrained at 2–6 unit cells close to the interface and the octahedral rotations relax quickly into bulk tilt angles away from interface. Here, a long-range (up to 12 unit cells) suppression of MnO6 octahedral rotations in La0.9Ba0.1MnO3 through the formation of superlattices with SrTiO3 can be achieved. The suppressed MnO6 octahedral rotations strongly modify the magnetic and electronic properties of La0.9Ba0.1MnO3 and hence create a new ferromagnetic insulating state with enhanced Curie temperature of 235 K. The emergent properties in La0.9Ba0.1MnO3 arise from a preferential occupation of the out-of-plane Mn d3z2−r2 orbital and a reduced Mn eg bandwidth, induced by the suppressed octahedral rotations. The realization of long-range tuning of BO6 octahedra via superlattices can be applicable to other strongly correlated perovskites for exploring new emergent quantum phenomena.

4. Mapping Materials and Molecules

   Bingqing Cheng, Ryan-Rhys Griffiths, Simon Wengert, and 8 more authors

   Accounts of Chemical Research, Sep 2020

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   ConspectusThe visualization of data is indispensable in scientific research, from the early stages when human insight forms to the final step of communicating results. In computational physics, chemistry and materials science, it can be as simple as making a scatter plot or as straightforward as looking through the snapshots of atomic positions manually. However, as a result of the “big data” revolution, these conventional approaches are often inadequate. The widespread adoption of high-throughput computation for materials discovery and the associated community-wide repositories have given rise to data sets that contain an enormous number of compounds and atomic configurations. A typical data set contains thousands to millions of atomic structures, along with a diverse range of properties such as formation energies, band gaps, or bioactivities.It would thus be desirable to have a data-driven and automated framework for visualizing and analyzing such structural data sets. The key idea is to construct a low-dimensional representation of the data, which facilitates navigation, reveals underlying patterns, and helps to identify data points with unusual attributes. Such data-intensive maps, often employing machine learning methods, are appearing more and more frequently in the literature. However, to the wider community, it is not always transparent how these maps are made and how they should be interpreted. Furthermore, while these maps undoubtedly serve a decorative purpose in academic publications, it is not always apparent what extra information can be garnered from reading or making them.This Account attempts to answer such questions. We start with a concise summary of the theory of representing chemical environments, followed by the introduction of a simple yet practical conceptual approach for generating structure maps in a generic and automated manner. Such analysis and mapping is made nearly effortless by employing the newly developed software tool ASAP. To showcase the applicability to a wide variety of systems in chemistry and materials science, we provide several illustrative examples, including crystalline and amorphous materials, interfaces, and organic molecules. In these examples, the maps not only help to sift through large data sets but also reveal hidden patterns that could be easily missed using conventional analyses.The explosion in the amount of computed information in chemistry and materials science has made visualization into a science in itself. Not only have we benefited from exploiting these visualization methods in previous works, we also believe that the automated mapping of data sets will in turn stimulate further creativity and exploration, as well as ultimately feed back into future advances in the respective fields.

5. Vertical Strain-Driven Antiferromagnetic to Ferromagnetic Phase Transition in EuTiO3 Nanocomposite Thin Films

   Yisong Lin, Eun-Mi Choi, Ping Lu, and 8 more authors

   ACS Applied Materials & Interfaces, Feb 2020

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   Three-dimensional (3D) strain induced in self-assembled vertically aligned nanocomposite (VAN) epitaxial films provides an unrivaled method to induce very large strains in thin films. Here, by growing VAN films of EuTiO3 (ETO)–Eu2O3 (EO) with different EO fractions, the vertical strain was systematically increased in ETO, up to 3.15%, and the Eu–Ti–Eu bond angle along ⟨111⟩ decreased by up to 1°, leading to a weakening of the antiferromagnetic interactions and switching from antiferromagnetic to ferromagnetic behavior. Our work has shown for the first time that Eu–Ti–Eu superexchange interactions play a key role in determining the magnetic ground state of ETO. More broadly, our work serves as an exemplar to show that multifunctionalities in strong spin–lattice coupling perovskite oxides can be uniquely tuned at the atomic scale using simple VAN structures.

6. Nanoengineering room temperature ferroelectricity into orthorhombic SmMnO 3 films

   Eun-Mi Choi, Tuhin Maity, Ahmed Kursumovic, and 9 more authors

   Nature Communications, May 2020

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   Orthorhombic RMnO3 (R = rare-earth cation) compounds are type-II multiferroics induced by inversion-symmetry-breaking of spin order. They hold promise for magneto-electric devices. However, no spontaneous room-temperature ferroic property has been observed to date in orthorhombic RMnO3. Here, using 3D straining in nanocomposite films of (SmMnO3)0.5((Bi,Sm)2O3)0.5, we demonstrate room temperature ferroelectricity and ferromagnetism with TC,FM ~ 90 K, matching exactly with theoretical predictions for the induced strain levels. Large in-plane compressive and out-of-plane tensile strains (−3.6% and +4.9%, respectively) were induced by the stiff (Bi,Sm)2O3 nanopillars embedded. The room temperature electric polarization is comparable to other spin-driven ferroelectric RMnO3 films. Also, while bulk SmMnO3 is antiferromagnetic, ferromagnetism was induced in the composite films. The Mn-O bond angles and lengths determined from density functional theory explain the origin of the ferroelectricity, i.e. modification of the exchange coupling. Our structural tuning method gives a route to designing multiferroics.

7. Real-time in situ optical tracking of oxygen vacancy migration in memristors

   Giuliana Di Martino, Angela Demetriadou, Weiwei Li, and 7 more authors

   Nature Electronics, Nov 2020

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   Resistive switches, which are also known as memristors, are low-power, nanosecond-response devices that are used in a range of memory-centric technologies. Driven by an externally applied potential, the switching mechanism of valence change resistive memories involves the migration, accumulation and rearrangement of oxygen vacancies within a dielectric medium, leading to a change in electrical conductivity. The ability to look inside these devices and understand how morphological changes characterize their function has been vital in their development. However, current technologies are often destructive and invasive. Here, we report a non-destructive optical spectroscopy technique that can detect the motion of a few hundred oxygen vacancies with nanometre-scale sensitivity. Resistive switches are arranged in a nanoparticle-on-mirror geometry to exploit the high optical sensitivity to morphological changes occurring in tightly confined plasmonic hotspots within the switching material. Using this approach, we find that nanoscale oxygen bubbles form at the surface of a strontium titanate memristor film, leading ultimately to device breakdown on cycling.

8. Revealing the Structure and Oxygen Transport at Interfaces in Complex Oxide Heterostructures via 17O NMR Spectroscopy

   Michael A. Hope, Bowen Zhang, Bonan Zhu, and 3 more authors

   Chemistry of Materials, Sep 2020

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   Vertically aligned nanocomposite (VAN) films, comprising nanopillars of one phase embedded in a matrix of another, have shown great promise for a range of applications due to their high interfacial areas oriented perpendicular to the substrate. In particular, oxide VANs show enhanced oxide-ion conductivity in directions that are orthogonal to those found in more conventional thin-film heterostructures; however, the structure of the interfaces and its influence on conductivity remain unclear. In this work, 17O NMR spectroscopy is used to study CeO2–SrTiO3 VAN thin films: selective isotopic enrichment is combined with a lift-off technique to remove the substrate, facilitating detection of the 17O NMR signal from single atomic layer interfaces. By performing the isotopic enrichment at variable temperatures, the superior oxide-ion conductivity of the VAN films compared to the bulk materials is shown to arise from enhanced oxygen mobility at this interface; oxygen motion at the interface is further identified from 17O relaxometry experiments. The structure of this interface is solved by calculating the NMR parameters using density functional theory combined with random structure searching, allowing the chemistry underpinning the enhanced oxide-ion transport to be proposed. Finally, a comparison is made with 1% Gd-doped CeO2–SrTiO3 VAN films, for which greater NMR signal can be obtained due to paramagnetic relaxation enhancement, while the relative oxide-ion conductivities of the phases remain similar. These results highlight the information that can be obtained on interfacial structure and dynamics with solid-state NMR spectroscopy, in this and other nanostructured systems, our methodology being generally applicable to overcome sensitivity limitations in thin-film studies.

9. Hyperspectral Imaging of Photonic Cellulose Nanocrystal Films: Structure of Local Defects and Implications for Self-Assembly Pathways

   Bonan Zhu, Villads E. Johansen, Gen Kamita, and 5 more authors

   ACS Nano, Nov 2020

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   Cellulose nanocrystals (CNCs) can spontaneously assemble into chiral nematic films capable of reflecting circularly polarized light in the visible range. As many other photonic materials obtained by bottom-up approaches, CNC films often display defects that greatly impact their visual appearance. Here, we study the optical response of defects in photonic CNC films, coupling optical microscopy with hyperspectral imaging, and we compare it to optical simulations of discontinuous cholesteric structures of increasing complexity. Cross-sectional SEM observations of the film structure guided the choice of simulation parameters and showed excellent agreement with experimental optical patterns. More importantly, it strongly suggests that the last fraction of CNCs to self-assemble, upon solvent evaporation, does not undergo the typical nucleation and growth pathway, but a spinodal decomposition, an alternative self-assembly pathway so far overlooked in cast films and that can have far-reaching consequences on choices of CNC sources and assembly conditions.

10. Efficient light-emitting diodes from mixed-dimensional perovskites on a fluoride interface

    Baodan Zhao, Yaxiao Lian, Linsong Cui, and 12 more authors

    Nature Electronics, Nov 2020

    Abs

    Light-emitting diodes based on halide perovskites have recently reached external quantum efficiencies of over 20%. However, the performance of visible perovskite light-emitting diodes has been hindered by non-radiative recombination losses and limited options for charge-transport materials that are compatible with perovskite deposition. Here, we report efficient, green electroluminescence from mixed-dimensional perovskites deposited on a thin (~1 nm) lithium fluoride layer on an organic semiconductor hole-transport layer. The highly polar dielectric interface acts as an effective template for forming high-quality bromide perovskites on otherwise incompatible hydrophobic charge-transport layers. The control of crystallinity and dimensionality of the perovskite layer is achieved by using tetraphenylphosphonium chloride as an additive, leading to external photoluminescence quantum efficiencies of around 65%. With this approach, we obtain light-emitting diodes with external quantum efficiencies of up to 19.1% at high brightness (\textgreater1,500 cd m−2).

2019

1. 3D strain-induced superconductivity in La2CuO4+δ using a simple vertically aligned nanocomposite approach

   Eun-Mi Choi, Angelo Di Bernardo, Bonan Zhu, and 12 more authors

   Science Advances, Apr 2019

   Abs

   A long-term goal for superconductors is to increase the superconducting transition temperature, TC. In cuprates, TC depends strongly on the out-of-plane Cu-apical oxygen distance and the in-plane Cu-O distance, but there has been little attention paid to tuning them independently. Here, in simply grown, self-assembled, vertically aligned nanocomposite thin films of La2CuO4+δ + LaCuO3, by strongly increasing out-of-plane distances without reducing in-plane distances (three-dimensional strain engineering), we achieve superconductivity up to 50 K in the vertical interface regions, spaced ~50 nm apart. No additional process to supply excess oxygen, e.g., by ozone or high-pressure oxygen annealing, was required, as is normally the case for plain La2CuO4+δ films. Our proof-of-concept work represents an entirely new approach to increasing TC in cuprates or other superconductors. We demonstrate a new way to increase the superconducting TC of cuprates using 3-D strain control in nanocomposite thin films. We demonstrate a new way to increase the superconducting TC of cuprates using 3-D strain control in nanocomposite thin films.

2. Determining interface structures in vertically aligned nanocomposite films

   Bonan Zhu, Georg Schusteritsch, Ping Lu, and 2 more authors

   APL Materials, Jun 2019

   Abs

   Vertically aligned nanocomposite (VAN) films have self-assembled pillar-matrix nanostructures. Owing to their large area-to-volume ratios, interfaces in VAN films are expected to play key roles in inducing functional properties, but our understanding is hindered by limited knowledge about their structures. Motivated by the lack of definitive explanation for the experimentally found enhanced ionic conductivity in Sm-doped-CeO2/SrTiO3 VAN films, we determine the structure at vertical interfaces using random structure searching and explore how it can affect ionic conduction. Interatomic potentials are used to perform the initial searching, followed by first-principles calculations for refinement. Previously unknown structures are found, with lower energy than that of an optimized hand-built model. We find a strongly distorted oxygen sublattice which gives a complex landscape of vacancy energies. The cation lattice remains similar to the bulk phase, but has a localized strain field. The excess energy of the interface is similar to that of high angle grain boundaries in SrTiO3.

2018

1. Voltage control of magnetic single domains in Ni discs on ferroelectric BaTiO3

   M. Ghidini, B. Zhu, R. Mansell, and 10 more authors

   Journal of Physics D: Applied Physics, May 2018

   Abs

   For 1 µm-diameter Ni discs on a BaTiO3 substrate, the local magnetization direction is determined by ferroelectric domain orientation as a consequence of growth strain, such that single-domain discs lie on single ferroelectric domains. On applying a voltage across the substrate, ferroelectric domain switching yields non-volatile magnetization rotations of 90°, while piezoelectric effects that are small and continuous yield non-volatile magnetization reversals that are non-deterministic. This demonstration of magnetization reversal without ferroelectric domain switching implies reduced fatigue, and therefore represents a step towards applications.

2016

1. Highly photoluminescent copper carbene complexes based on prompt rather than delayed fluorescence

   Alexander S. Romanov, Dawei Di, Le Yang, and 7 more authors

   Chemical Communications, May 2016

   Abs

   Linear two-coordinate copper complexes of cyclic (alkyl)(amino)carbenes (CAAC)CuX (X = halide) show photoluminescence with solid-state quantum yields of up to 96%; in contrast to previously reported Cu photoemitters the emission is independent of temperature over the range T = 4–300 K and occurs very efficiently by prompt rather than delayed fluorescence, with lifetimes in the sub-nanosecond range.

2015

1. Magnetoelectric imaging of multiferroic heterostructures (Presentation Recording)

   Massimo Ghidini, Arnaud Lesaine, Bonan Zhu, and 12 more authors

   In Spintronics VIII , Oct 2015

   Abs

   Electrical control of magnetism has been demonstrated in multiferroic compounds and ferromagnetic semiconductors, but electrical switching of a substantial net magnetization at room temperature has not been demonstrated in these materials. This goal has instead been achieved in heterostructures comprising ferromagnetic films in which electrically driven magnetic changes arise due to strain or exchange bias from ferroic substrates, or due to charge effects induced by a gate. However, previous work focused on electrical switching of an in-plane magnetization or involved the assistance of applied magnetic fields. In heterostructures made of juxtaposed ferroelectric and ferromagnetic layers, we have shown electrical control with no applied magnetic field of the perpendicular magnetization of small features [1] and of magnetic stripe domains patterns [2]. Here we investigate Ni81Fe19 films on ferroelectric substrates with and without buffer layers of Cu, whose presence precludes charge-mediated coupling. Ni81Fe19 has virtually zero magnetostriction, but sufficiently thin films show large magnetostriction, and thus, on increasing film thickness through the threshold for zero magnetostriction, we have seeked the crossover from charge- to strain-mediated coupling. We will then show that strain associated with the motion of 90°- ferroelectric domain walls in a BaTiO3 substrate, can switch the magnetization of an array of overlying single-domain Ni dots. [1] M. Ghidini, R. Pellicelli, J. L. Prieto, X. Moya, J. Soussi, J. Briscoe, S. Dunn and N. D. Mathur, Nature Communications 4 (2013) 1453. [2] M. Ghidini, F.Maccherozzi, X. Moya, L. C. Phillips, W.Yan, J. Soussi, N. Métallier, M.Vickers, , N. -J.Steinke, R. Mansell, C. H. W. Barnes, S. S. Dhesi, and N. D. Mathur, Adv. Mater.doi: 10.1002/adma.201404799 (2015).