Discovery Of New Phases Research Articles

Mechanochemical Synthesis and Magnetic Properties of the Mixed-Valent Binary Silver(I,II) Fluorides, AgI2AgIIF4 and AgIAgIIF3.

Fluoridoargentates(II) represent a fascinating class of silver(II) compounds with structural and magnetic similarities to cuprate superconductors. However, their synthesis is challenging, leaving their properties largely underexplored and hindering the discovery of new phases. This study introduces mechanochemistry as a novel approach for the synthesis of fluoridoargentates(II), avoiding the use of anhydrous HF or elemental fluorine and employing readily available equipment. Notably, ball milling of commercially available precursors successfully produced the long-sought-after first two examples of binary mixed-valent silver(I,II) phases, AgI2AgIIF4 (Ag3F4) and AgIAgIIF3 (Ag2F3). While the AgI2AgIIF4 phase was obtained at room temperature, the AgIAgIIF3 phase is metastable and required milling under cryogenic conditions. Characterization by synchrotron powder X-ray and neutron diffraction revealed that AgI2AgIIF4 crystallizes in the P21/c space group and is isostructural to β-K2AgF4. In this crystal structure, [AgIIF2F4/2]2- distorted octahedral units with 4 + 2 coordination, extend parallel to a-crystallographic axis giving a quasi-one-dimensional canted antiferromagnetic character, as shown by magnetic susceptibility. The triclinic perovskite AgIAgIIF3 phase adopts the P1̅ space group, is isostructural to AgCuF3 and also shows features of a one-dimensional antiferromagnet. This mechanochemical approach, also successfully applied to synthesize β-K2AgF4, is expected to expand the field of silver(II) chemistry, accelerating the search for silver analogs to cuprate superconductors and potentially extending to other cations in unusual oxidation states.

Accelerating Computational Materials Discovery with Machine Learning and Cloud High-Performance Computing: from Large-Scale Screening to Experimental Validation.

High-throughput computational materials discovery has promised significant acceleration of the design and discovery of new materials for many years. Despite a surge in interest and activity, the constraints imposed by large-scale computational resources present a significant bottleneck. Furthermore, examples of very large-scale computational discovery carried out through experimental validation remain scarce, especially for materials with product applicability. Here, we demonstrate how this vision became reality by combining state-of-the-art machine learning (ML) models and traditional physics-based models on cloud high-performance computing (HPC) resources to quickly navigate through more than 32 million candidates and predict around half a million potentially stable materials. By focusing on solid-state electrolytes for battery applications, our discovery pipeline further identified 18 promising candidates with new compositions and rediscovered a decade's worth of collective knowledge in the field as a byproduct. We then synthesized and experimentally characterized the structures and conductivities of our top candidates, the NaxLi3-xYCl6 (0≤ x≤ 3) series, demonstrating the potential of these compounds to serve as solid electrolytes. Additional candidate materials that are currently under experimental investigation could offer more examples of the computational discovery of new phases of Li- and Na-conducting solid electrolytes. The showcased screening of millions of materials candidates highlights the transformative potential of advanced ML and HPC methodologies, propelling materials discovery into a new era of efficiency and innovation.

First-principles spectroscopy of aqueous interfaces using machine-learned electronic and quantum nuclear effects.

Vibrational spectroscopy is a powerful approach to visualising interfacial phenomena. However, extracting structural and dynamical information from vibrational spectra is a challenge that requires first-principles simulations, including non-Condon and quantum nuclear effects. We address this challenge by developing a machine-learning enhanced first-principles framework to speed up predictive modelling of infrared, Raman, and sum-frequency generation spectra. Our approach uses machine learning potentials that encode quantum nuclear effects to generate quantum trajectories using simple molecular dynamics efficiently. In addition, we reformulate bulk and interfacial selection rules to express them unambiguously in terms of the derivatives of polarisation and polarisabilities of the whole system and predict these derivatives efficiently using fully-differentiable machine learning models of dielectric response tensors. We demonstrate our framework's performance by predicting the IR, Raman, and sum-frequency generation spectra of liquid water, ice and the water-air interface by achieving near quantitative agreement with experiments at nearly the same computational efficiency as pure classical methods. Finally, to aid the experimental discovery of new phases of nanoconfined water, we predict the temperature-dependent vibrational spectra of monolayer water across the solid-hexatic-liquid phases transition.

Machine learning discovery of new phases in programmable quantum simulator snapshots

Machine learning has recently emerged as a promising approach for studying complex phenomena characterized by rich datasets. In particular, data-centric approaches lead to the possibility of automatically discovering structures in experimental datasets that manual inspection may miss. Here, we introduce an interpretable unsupervised-supervised hybrid machine learning approach, the hybrid-correlation convolutional neural network (hybrid-CCNN), and apply it to experimental data generated using a programmable quantum simulator based on Rydberg atom arrays. Specifically, we apply hybrid-CCNN to discover and identify new quantum phases on square lattices with programmable interactions. The initial unsupervised dimensionality reduction and clustering stage first reveals five distinct quantum phase regions. In a second supervised stage, we refine these phase boundaries and seek insights into the phases by training multiple CCNN classifiers. A learned spatial weighting, introduced to the CCNNs in this work, enables discovery of spatial structure at scales beyond the filter size. The characteristic spatial weightings and snippets of correlations specifically recognized in each phase capture quantum fluctuations in the striated phase and identify a previously undetected boundary-ordered phase as well as motifs of more exotic ordered phases. These observations demonstrate that a combination of programmable quantum simulators with machine learning can be used as a powerful tool for detailed exploration of correlated quantum states of matter.

Differentiating Zr/HfIV Aqueous Polyoxocation Chemistry with Peroxide Ligation.

This work complements our recent discovery of new phases derived from zirconium perchlorate by addition of hydrogen peroxide. Here, we investigate analogous reactions with hafnium perchlorate, which is found to have modifications of the Clearfield-Vaughan tetramer (CVT). For hafnium perchlorate derivatives, we find distorted versions of CVT by X-ray diffraction and study the reaction solutions by SAXS, Raman spectroscopy, and ESI-MS. Furthermore, we investigate mixed Hf-Zr solution and solid phases and find the latter resemble the zirconium family at low Hf concentrations and the hafnium family at higher hafnium contents.

Oxides and the high entropy regime: A new mix for engineering physical properties

AbstractHistorically, the enthalpy is the criterion for oxide materials discovery and design. In this regime, highly controlled thin film epitaxy can be leveraged to manifest bulk and interfacial phases that are non-existent in bulk equilibrium phase diagrams. With the recent discovery of entropy-stabilized oxides, entropy and disorder engineering has been realized as an orthogonal approach. This has led to the nucleation and rapid growth of research on high-entropy oxides – multicomponent oxides where the configurational entropy is large but its contribution to its stabilization need not be significant or is currently unknown. From current research, it is clear that entropy enhances the chemical solubility of species and can realize new stereochemical configurations which has led to the rapid discovery of new phases and compositions. The research has expanded beyond studies to understand the role of entropy in stabilization and realization of new crystal structures to now include physical properties and the roles of local and global disorder. Here, key observations made regarding the dielectric and magnetic properties are reviewed. These materials have recently been observed to display concerted symmetry breaking, metal-insulator transitions, and magnetism, paving the way for engineering of these and potentially other functional phenomena. Excitingly, the disorder in these oxides allows for new interplay between spin, orbital, charge, and lattice degrees of freedom to design the physical behavior. We also provide a perspective on the state of the field and prospects for entropic oxide materials in applications considering their unique characteristics.

Space, matter and topology

An old branch of mathematics, Topology, has opened the road to the discovery of new phases of matter. A hidden topology in the energy spectrum is the key for novel conducting/insulating properties of topological matter.

Retraction Note to: Fundamental Discovery of New Phases and Direct Conversion of Carbon into Diamond and hBN into cBN and Properties

We review the discovery of new phases of carbon (Q-carbon) and BN (Q-BN) and address critical issues related to direct conversion of carbon into diamond and hBN into cBN at ambient temperatures and pressures in air without any need for catalyst and the presence of hydrogen. The Q-carbon and Q-BN are formed as a result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs T) of carbon, and show that by rapid quenching, kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. Similarly, the hBN-cBN-Liquid triple point is shifted from 3500 K/9.5 GPa to as low as 2800 K and atmospheric pressure. It is shown that nanosecond laser heating of amorphous carbon and nanocrystalline BN on sapphire, glass, and polymer substrates can be confined to melt in a super undercooled state. By quenching this super undercooled state, we have created a new state of carbon (Q-carbon) and BN (Q-BN) from which nanocrystals, microcrystals, nanoneedles, microneedles, and thin films are formed depending upon the nucleation and growth times allowed and the presence of growth template. The large-area epitaxial diamond and cBN films are formed, when appropriate planar matching or lattice matching template is provided for growth from super undercooled liquid. The Q-phases have unique atomic structure and bonding characteristics as determined by high-resolution SEM and backscatter diffraction, HRTEM, STEM-Z, EELS, and Raman spectroscopy, and exhibit new and improved mechanical hardness, electrical conductivity, and chemical and physical properties, including room-temperature ferromagnetism and enhanced field emission. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g−1. We have also deposited diamond on cBN by using a novel pulsed laser evaporation of carbon and obtained cBN/diamond composites, where cBN acts as template for diamond growth. Both diamond and cBN grown from super undercooled liquid can be alloyed with both p- and n-type dopants. This process allows carbon to diamond and hBN to cBN conversions and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond and cBN phases.

Discovery of Q-Phases and Direct Coversion of Carbon into Diamond and h-BN into c-BN

Abstract The discovery of new phases of carbon and direct conversion of carbon into diamond and diamond-like materials—at ambient conditions and without a catalyst—is a breakthrough with tremendous potential for electronics and hard-materials applications.

RETRACTED ARTICLE: Fundamental Discovery of New Phases and Direct Conversion of Carbon into Diamond and hBN into cBN and Properties

We review the discovery of new phases of carbon (Q-carbon) and BN (Q-BN) and address critical issues related to direct conversion of carbon into diamond and hBN into cBN at ambient temperatures and pressures in air without any need for catalyst and the presence of hydrogen. The Q-carbon and Q-BN are formed as a result of quenching from super undercooled state by using high-power nanosecond laser pulses. We discuss the equilibrium phase diagram (P vs T) of carbon, and show that by rapid quenching, kinetics can shift thermodynamic graphite/diamond/liquid carbon triple point from 5000 K/12 GPa to super undercooled carbon at atmospheric pressure in air. Similarly, the hBN-cBN-Liquid triple point is shifted from 3500 K/9.5 GPa to as low as 2800 K and atmospheric pressure. It is shown that nanosecond laser heating of amorphous carbon and nanocrystalline BN on sapphire, glass, and polymer substrates can be confined to melt in a super undercooled state. By quenching this super undercooled state, we have created a new state of carbon (Q-carbon) and BN (Q-BN) from which nanocrystals, microcrystals, nanoneedles, microneedles, and thin films are formed depending upon the nucleation and growth times allowed and the presence of growth template. The large-area epitaxial diamond and cBN films are formed, when appropriate planar matching or lattice matching template is provided for growth from super undercooled liquid. The Q-phases have unique atomic structure and bonding characteristics as determined by high-resolution SEM and backscatter diffraction, HRTEM, STEM-Z, EELS, and Raman spectroscopy, and exhibit new and improved mechanical hardness, electrical conductivity, and chemical and physical properties, including room-temperature ferromagnetism and enhanced field emission. The Q-carbon exhibits robust bulk ferromagnetism with estimated Curie temperature of about 500 K and saturation magnetization value of 20 emu g−1. We have also deposited diamond on cBN by using a novel pulsed laser evaporation of carbon and obtained cBN/diamond composites, where cBN acts as template for diamond growth. Both diamond and cBN grown from super undercooled liquid can be alloyed with both p- and n-type dopants. This process allows carbon to diamond and hBN to cBN conversions and formation of useful nanostructures and microstructures at ambient temperatures in air at atmospheric pressure on practical and heat-sensitive substrates in a controlled way without need for any catalysts and hydrogen to stabilize sp3 bonding for diamond and cBN phases.

Spin-Orbit Physics Giving Rise to Novel Phases in Correlated Systems: Iridates and Related Materials

Recently, the effects of spin-orbit coupling (SOC) in correlated materials have become one of the most actively studied subjects in condensed matter physics, as correlations and SOC together can lead to the discovery of new phases. Examples include unconventional magnetism, spin liquids, and strongly correlated topological phases such as topological superconductivity. Among candidate materials, iridium oxides (iridates) have been an excellent playground to uncover such novel phenomena. In this review, we discuss recent progress in iridates and related materials, focusing on the basic concepts, relevant microscopic Hamiltonians, and unusual properties of iridates in perovskite- and honeycomb-based structures. Perspectives on SOC and correlation physics beyond iridates are also discussed.

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

In the course of the recent advances in chemical structure prediction, a straightforward type of diagram to evaluate phase stabilities is presented based on an expedient example. Crystal structures and energetic stabilities of dipnictides NiPn2 (Pn = N, P, As, Sb, Bi) are systematically investigated by first principles calculations within the framework of density functional theory using the generalized gradient approximation to treat exchange and correlation. These dipnictides show remarkable polymorphism that is not yet understood systematically and offers room for the discovery of new phases. Relationships between the concerned structures including the marcasite, the pyrite, the arsenopyrite/CoSb2, and the NiAs2 types are highlighted by means of common structural fragments. Electronic stabilities of experimentally known and related AB2 structure types are presented graphically in so-called stability diagrams. Additionally, competing binary phases are taken into consideration in the diagrams to evaluate the stabilities of the title compounds with respect to decomposition. The main purpose of the stability diagrams is the introduction of an image that enables the estimation of phase stabilities at a single glance. Beyond that, some of the energetically favored structure types can be identified as potential new phases.

Superfluid Phases of 3He in a Periodic Confined Geometry

Predictions and discoveries of new phases of superfluid 3He in confined geometries, as well as novel topological excitations confined to surfaces and edges of near a bounding surface of 3He, are driving the fields of superfluid 3He infused into porous media, as well as the fabrication of sub-micron to nano-scale devices for controlled studies of quantum fluids. In this report we consider superfluid 3He confined in a periodic geometry, specifically a two-dimensional lattice of square, sub-micron-scale boundaries (“posts”) with translational invariance in the third dimension. The equilibrium phase(s) are inhomogeneous and depend on the microscopic boundary conditions imposed by a periodic array of posts. We present results for the order parameter and phase diagram based on strong pair breaking at the boundaries. The ordered phases are obtained by numerically minimizing the Ginzburg-Landau free energy functional. We report results for the weak-coupling limit, appropriate at ambient pressure, as a function of temperature T, lattice spacing L, and post edge dimension, d. For all d in which a superfluid transition occurs, we find a transition from the normal state to a periodic, inhomogeneous “polar” phase with $T_{c_{1}} < T_{c}$ for bulk superfluid 3He. For fixed lattice spacing, L, there is a critical post dimension, d c , above which only the periodic polar phase is stable. For d<d c we find a second, low-temperature phase onsetting at $T_{c_{2}} < T_{c_{1}}$ from the polar phase to a periodic “B-like” phase. The low temperature phase is inhomogeneous, anisotropic and preserves time-reversal symmetry, but unlike the bulk B-phase has only $\mathtt{D}_{\text{4h}}^{\text{L}+\text{S}}$ point symmetry.

Modular high-throughput test stand for versatile screening of thin-film materials libraries

Versatile high-throughput characterization tools are required for the development of new materials using combinatorial techniques. Here, we describe a modular, high-throughput test stand for the screening of thin-film materials libraries, which can carry out automated electrical, magnetic and magnetoresistance measurements in the temperature range of −40 to 300 °C. As a proof of concept, we measured the temperature-dependent resistance of Fe–Pd–Mn ferromagnetic shape-memory alloy materials libraries, revealing reversible martensitic transformations and the associated transformation temperatures. Magneto-optical screening measurements of a materials library identify ferromagnetic samples, whereas resistivity maps support the discovery of new phases. A distance sensor in the same setup allows stress measurements in materials libraries deposited on cantilever arrays. A combination of these methods offers a fast and reliable high-throughput characterization technology for searching for new materials. Using this approach, a composition region has been identified in the Fe–Pd–Mn system that combines ferromagnetism and martensitic transformation.

Very high-pressure orogenic garnet peridotites

Mantle-derived garnet peridotites are a minor component in many very high-pressure metamorphic terranes that formed during continental subduction and collision. Some of these mantle rocks contain trace amounts of zircon and micrometer-sized inclusions. The constituent minerals exhibit pre- and postsubduction microstructures, including polymorphic transformation and mineral exsolution. Experimental, mineralogical, petrochemical, and geochronological characterizations using novel techniques with high spatial, temporal, and energy resolutions are resulting in unexpected discoveries of new phases, providing better constraints on deep mantle processes.

Classification and analysis of the non stoichiometry features in the layered lead and thallium cuprates

The numerous and varied non stoichiometry features occuring in the high Tc super- conductors are directly generated by the own nature of the building principles of these structures i.e. the intergrowth of rock salt-type layers and oxygen deficient perovskite slabs. The coexistence of sev- eral cations (sometimes up to six) in the matrix, the possibilities of mixed valencies for some of these cations (Cu-Bi-Tl-Pb-Pr) and the possible occupancy of the crystallographic sites by several cations simultaneously are undoubtly factors susceptible to favor their appearance. Is the acquaintance of these numerous phenomena only a microscopist hobby ? The importance of the microstructural char- acterization has been widely proved in different stages of the superconductor studies: the existence of extended defects can indeed hinder an accurate interpretation of the physical properties, the survey of the structural mechanisms can open the road to the discovery of new phases and can be an essential help in the optimization of these materials. This paper deals with the classification of the phenomena which can be observed and the analysis of the structural mechanisms which are involved in the lead and thallium cuprates; owing to their particular behavior, bismuth cuprates will be only considered as a comparison.

On the Origin of the Structural Modulation in the Bi Cuprates As Derived from 3d-Metal Substituted Phases

ABSTRACTA substitution for Cu by a 3d-metal (Fe, Co, Mn) in the superconducting Bi phases (Bi2Sr2Can−1CunOy; n = 1,2 and 3) has led to the discovery of new phases. These 3d-metal substituted phases are non-superconducting and, in contrast to the Cu-based phases, they exhibit a structural modulation that is commensurate. Single crystal x-ray studies were performed on the Bi2Sr3Fe2Oy, Bi2Sr2CoOy and Bi2Sr2MnOy compounds. A result, in common, is that the modulation is caused by the periodic insertion of a row of oxygen atoms in the Bi layers and this results in a corrugated-like slab structure. The Bi-O layers can be described as composed of alternating rocksalt-type and oxygen deficient perovskite-type blocks. For the Fe (n=2) phase the Bi atoms form ribbons (chains) in the ab plane. This is in contrast to the n=1 Co or Mn phases for which a disorder at the oxygen position is observed. Although the extra oxygen in the Bi-O layer could account for the doping mechanism in the high Tc Bi-phases, cation non-stoichiometry may also beimportant.

Some recent studies on the structural arrangements of lipids in surface layers and interphases

The surface chemistry studies carried out in our laboratory can be traced back to the Department of Colloid Science in Cambridge, England, where one of the present authors spent a year as a student just thirty years ago, working with Prof. (now Sir) E. K. Rideal and Dr. J. H. Sehulman. The original aim was to explore the possibilities of the monolayer technique in the elucidation of the structure of some complex lipid molecules of bacterial origin, viz., phthiocerol (1), the so-called phthioic acid (2), and certain other fatty acids (3). These structure problems were later solved by mass spectrometry (cf. 4) but the monolayer work led to the discovery of new phases in condensed monolayers (5, 6), and the use of the surface phase diagram for the deterruination of the composition of mixtures of fatty acids was demonstrated (7). The relation between the different twodimensional monolayerphases observed and the arrangement of the molecules in the three-dimensional crystal has been the subjeer of discussion (8-10). These problems have been studied in our laboratory in recent years (11). Detailed monolayer studies together with X-ray crystal structure studies have now led to a fairly complete correlation between monolayer states and three-dimensional crystalline arrangements of long-chain molecules. The extension of previous X-ray single crystal structure studies of glycerides carried out in this laboratory (12) to glyceridewater systems (13) has given new infermarion about the phase behavior of such systems. The newly developed electron spectroscopy of nonbinding electrons in the inner shells (14) has recently been applied to Langmuir-Blodgett multi]ayers (15). It seems likely that this technique will become a very important tool in studies of surface layers.