Machine Learning-Enabled Tomographic Imaging of Chemical Short-Range Atomic Ordering.

In solids, chemical short-range order (CSRO) refers to the self-organization of atoms of certain species occupying specific crystal sites. CSRO is increasingly being envisaged as a lever to tailor the mechanical and functional properties of materials. Yet quantitative relationships between properties and the morphology, number density, and atomic configurations of CSRO domains remain elusive. Herein, it is showcased how machine learning-enhanced atom probe tomography (APT) can mine the near-atomically resolved APT data and jointly exploit the technique's high elemental sensitivity to provide a 3D quantitative analysis of CSRO in a CoCrNi medium-entropy alloy. Multiple CSRO configurations are revealed, with their formation supported by state-of-the-art Monte-Carlo simulations. Quantitative analysis of these CSROs allows establishing relationships between processing parameters and physical properties. The unambiguous characterization of CSRO will help refine strategies for designing advanced materials by manipulating atomic-scale architectures.

Metavalently bonded tellurides: the essence of improved thermoelectric performance in elemental Te.

Elemental Te is important for semiconductor applications including thermoelectric energy conversion. Introducing dopants such as As, Sb, and Bi has been proven critical for improving its thermoelectric performance. However, the remarkably low solubility of these elements in Te raises questions about the mechanism with which these dopants can improve the thermoelectric properties. Indeed, these dopants overwhelmingly form precipitates rather than dissolve in the Te lattice. To distinguish the role of doping and precipitation on the properties, we have developed a correlative method to locally determine the structure-property relationship for an individual matrix or precipitate. We reveal that the conspicuous enhancement of electrical conductivity and power factor of bulk Te stems from the dopant-induced metavalently bonded telluride precipitates. These precipitates form electrically beneficial interfaces with the Te matrix. A quantum-mechanical-derived map uncovers more candidates for advancing Te thermoelectrics. This unconventional doping scenario adds another recipe to the design options for thermoelectrics and opens interesting pathways for microstructure design.

Direct programming of confined surface phonon polariton resonators with the plasmonic phase-change material In3SbTe2.

Tailoring light-matter interaction is essential to realize nanophotonic components. It can be achieved with surface phonon polaritons (SPhPs), an excitation of photons coupled with phonons of polar crystals, which also occur in 2d materials such as hexagonal boron nitride or anisotropic crystals. Ultra-confined resonances are observed by restricting the SPhPs to cavities. Phase-change materials (PCMs) enable non-volatile programming of these cavities based on a change in the refractive index. Recently, the plasmonic PCM In3SbTe2 (IST) was introduced which can be reversibly switched from an amorphous dielectric state to a crystalline metallic one in the entire infrared to realize numerous nanoantenna geometries. However, reconfiguring SPhP resonators to modify the confined polaritons modes remains elusive. Here, we demonstrate direct programming of confined SPhP resonators by phase-switching IST on top of a polar silicon carbide crystal and investigate the strongly confined resonance modes with scanning near-field optical microscopy. Reconfiguring the size of the resonators themselves result in enhanced mode confinements up to a value of λ / 35 . Finally, unconventional cavity shapes with complex field patterns are explored as well. This study is a first step towards rapid prototyping of reconfigurable SPhP resonators that can be easily transferred to hyperbolic and anisotropic 2d materials.

Tailoring chemical bonds to design unconventional glasses.

Glasses are commonly described as disordered counterparts of the corresponding crystals; both usually share the same short-range order, but glasses lack long-range order. Here, a quantification of chemical bonding in a series of glasses and their corresponding crystals is performed, employing two quantum-chemical bonding descriptors, the number of electrons transferred and shared between adjacent atoms. For popular glasses like SiO2, GeSe2, and GeSe, the quantum-chemical bonding descriptors of the glass and the corresponding crystal hardly differ. This explains why these glasses possess a similar short-range order as their crystals. Unconventional glasses, which differ significantly in their short-range order and optical properties from the corresponding crystals are only found in a distinct region of the map spanned by the two bonding descriptors. This region contains crystals of GeTe, Sb2Te3, and GeSb2Te4, which employ metavalent bonding. Hence, unconventional glasses are only obtained for solids, whose crystals employ theses peculiar bonds.

Metavalent or Hypervalent Bonding: Is There a Chance for Reconciliation?

A family of solids including crystalline phase change materials such as GeTe and Sb2 Te3 , topological insulators like Bi2 Se3, and halide perovskites such as CsPbI3 possesses an unconventional property portfolio that seems incompatible with ionic, metallic, or covalent bonding. Instead, evidence is found for a bonding mechanism characterized by half-filled p-bands and a competition between electron localization and delocalization. Different bonding concepts have recently been suggested based on quantum chemical bonding descriptors which either define the bonds in these solids as electron-deficient (metavalent) or electron-rich (hypervalent). This disagreement raises concerns about the accuracy of quantum-chemical bonding descriptors is showed. Here independent of the approach chosen, electron-deficient bonds govern the materials mentioned above is showed. A detailed analysis of bonding in electron-rich XeF2 and electron-deficient GeTe shows that in both cases p-electrons govern bonding, while s-electrons only play a minor role. Yet, the properties of the electron-deficient crystals are very different from molecular crystals of electron-rich XeF2 or electron-deficient B2 H6 . The unique properties of phase change materials and related solids can be attributed to an extended system of half-filled bonds, providing further arguments as to why a distinct nomenclature such as metavalent bonding is adequate and appropriate for these solids.

Infrared Resonance Tuning of Nanoslit Antennas with Phase-Change Materials.

Phase-change materials (PCMs) have been established as prime candidates for nonvolatile resonance tuning of nanophotonic components based on a large optical contrast between their amorphous and crystalline states. Recently, the plasmonic PCM In3SbTe2 was introduced, which can be switched from an amorphous dielectric state to a crystalline metallic one over the entire infrared spectral range. While locally switching the PCM around metallic nanorod antennas has already been demonstrated, similar tuning of inverse antenna structures (nanoslits) has not yet been investigated. Here, we demonstrate optical resonance tuning of nanoslit antennas with dielectric and plasmonic PCMs. We compare two geometries with fundamentally different resonance tuning mechanisms: tuning the resonance of aluminum slit antennas by change of the refractive index (dielectric PCM Ge3Sb2Te6), and creating slit-like volumes of amorphous In3SbTe2 and modifying the slit geometry directly (plasmonic PCM In3SbTe2). While the tuning range with the plasmonic PCM is about 3.4 µm and only limited by fabrication, the resonances with the dielectric PCM feature a three times larger quality factor compared to resonances obtained with the plasmonic PCM.

Evolution of Short-Range Order of Amorphous GeTe Upon Structural Relaxation Obtained by TEM Diffractometry and RMC Methods.

Glasses frequently reveal structural relaxation that leads to changes in their physical properties including enthalpy, specific volume, and resistivity. Analyzing the short-range order (SRO) obtained from electron diffraction by transmission electron microscopy (TEM) in combination with Reverse-Monte-Carlo (RMC) simulations is shown to provide information on the atomic arrangement. The technique elaborated here features several benefits including reliability, accessibility, and allows for obtaining detailed structural data quickly. This is demonstrated with a detailed view of the structural changes in the as-deposited amorphous phase change material (PCM) GeTe. The data show a significant increase in the average bond angle upon thermal treatment. At the same time the fraction of tetrahedrally coordinated Ge atoms decreases due to an increase in octahedrally distorted and pyramidal motifs. This finding provides further evidence for the atomic processes that govern structural relaxation in amorphous GeTe and other PCMs. A thorough literature review finally unveils possible origins of the large discrepancies reported on the structure of amorphous GeTe.

Two-step phase manipulation by tailoring chemical bonds results in high-performance GeSe thermoelectrics.

In thermoelectrics, phase engineering serves a crucial function in determining the power factor by affecting the band degeneracy. However, for low-symmetry compounds, the mainstream one-step phase manipulation strategy, depending solely on the valley or orbital degeneracy, is inadequate to attain a high density-of-states effective mass and exceptional zT. Here, we employ a distinctive two-step phase manipulation strategy through stepwise tailoring chemical bonds in GeSe. Initially, we amplify the valley degeneracy via CdTe alloying, which elevates the crystal symmetry from a covalently bonded orthorhombic to a metavalently bonded rhombohedral phase by significantly suppressing the Peierls distortion. Subsequently, we incorporate Pb to trigger the convergence of multivalence bands and further enhance the density-of-states effective mass by moderately restraining the Peierls distortion. Additionally, the atypical metavalent bonding in rhombohedral GeSe enables a high Ge vacancy concentration and a small band effective mass, leading to increased carrier concentration and mobility. This weak chemical bond along with strong lattice anharmonicity also reduces lattice thermal conductivity. Consequently, this unique property ensemble contributes to an outstanding zT of 0.9 at 773 K for Ge0.80Pb0.20Se(CdTe)0.25. This work underscores the pivotal role of the two-step phase manipulation by stepwise tailoring of chemical bonds in improving the thermoelectric performance of p-bonded chalcogenides.

Large Mobility Enables Higher Thermoelectric Cooling and Power Generation Performance in n-type AgPb18+xSbTe20 Crystals.

The room-temperature thermoelectric performance of materials underpins their thermoelectric cooling ability. Carrier mobility plays a significant role in the electronic transport property of materials, especially near room temperature, which can be optimized by proper composition control and growing crystals. Here, we grow Pb-compensated AgPb18+xSbTe20 crystals using a vertical Bridgman method. A large weighted mobility of ∼410 cm2 V-1 s-1 is achieved in the AgPb18.4SbTe20 crystal, which is almost 4 times higher than that of the polycrystalline counterpart due to the elimination of grain boundaries and Ag-rich dislocations verified by atom probe tomography, highlighting the significant benefit of growing crystals for low-temperature thermoelectrics. Due to the largely promoted weighted mobility, we achieve a high power factor of ∼37.8 µW cm-1 K-2 and a large figure of merit ZT of ∼0.6 in AgPb18.4SbTe20 crystal at 303 K. We further designed a 7-pair thermoelectric module using this n-type crystal and a commercial p-type (Bi, Sb)2Te3-based material. As a result, a high cooling temperature difference (ΔT) of ∼42.7 K and a power generation efficiency of ∼3.7% are achieved, revealing promising thermoelectric applications for PbTe-based materials near room temperature.

Erratum: Roadmap for phase change materials in photonics and beyond.

[This corrects the article DOI: 10.1016/j.isci.2023.107946.].

Roadmap for phase change materials in photonics and beyond.

Phase Change Materials (PCMs) have demonstrated tremendous potential as a platform for achieving diverse functionalities in active and reconfigurable micro-nanophotonic devices across the electromagnetic spectrum, ranging from terahertz to visible frequencies. This comprehensive roadmap reviews the material and device aspects of PCMs, and their diverse applications in active and reconfigurable micro-nanophotonic devices across the electromagnetic spectrum. It discusses various device configurations and optimization techniques, including deep learning-based metasurface design. The integration of PCMs with Photonic Integrated Circuits and advanced electric-driven PCMs are explored. PCMs hold great promise for multifunctional device development, including applications in non-volatile memory, optical data storage, photonics, energy harvesting, biomedical technology, neuromorphic computing, thermal management, and flexible electronics.

Gibbs Adsorption and Zener Pinning Enable Mechanically Robust High-Performance Bi2 Te3 -Based Thermoelectric Devices.

Bi2 Te3 -based alloys have great market demand in miniaturized thermoelectric (TE) devices for solid-state refrigeration and power generation. However, their poor mechanical properties increase the fabrication cost and decrease the service durability. Here, this work reports on strengthened mechanical robustness in Bi2 Te3 -based alloys due to thermodynamic Gibbs adsorption and kinetic Zener pinning at grain boundaries enabled by MgB2 decomposition. These effects result in much-refined grain size and twofold enhancement of the compressive strength and Vickers hardness in (Bi0.5 Sb1.5 Te3 )0.97 (MgB2 )0.03 compared with that of traditional powder-metallurgy-derived Bi0.5 Sb1.5 Te3 . High mechanical properties enable excellent cutting machinability in the MgB2 -added samples, showing no missing corners or cracks. Moreover, adding MgB2 facilitates the simultaneous optimization of electron and phonon transport for enhancing the TE figure of merit (ZT). By further optimizing the Bi/Sb ratio, the sample (Bi0.4 Sb1.6 Te3 )0.97 (MgB2 )0.03 shows a maximum ZT of ≈1.3 at 350 K and an average ZT of 1.1 within 300-473 K. As a consequence, robust TE devices with an energy conversion efficiency of 4.2% at a temperature difference of 215 K are fabricated. This work paves a new way for enhancing the machinability and durability of TE materials, which is especially promising for miniature devices.

Doping by Design: Enhanced Thermoelectric Performance of GeSe Alloys Through Metavalent Bonding.

Doping is usually the first step to tailor thermoelectrics. It enables precise control of the charge-carrier concentration and concomitant transport properties. Doping should also turn GeSe, which features an intrinsically a low carrier concentration, into a competitive thermoelectric. Yet, elemental doping fails to improve the carrier concentration. In contrast, alloying with Ag-V-VI2 compounds causes a remarkable enhancement of thermoelectric performance. This advance is closely related to a transition in the bonding mechanism, as evidenced by sudden changes in the optical dielectric constant ε∞ , the Born effective charge, the maximum of the optical absorption ε2 (ω), and the bond-breaking behavior. These property changes are indicative of the formation of metavalent bonding (MVB), leading to an octahedral-like atomic arrangement. MVB is accompanied by a thermoelectric-favorable band structure featuring anisotropic bands with small effective masses and a large degeneracy. A quantum-mechanical map, which distinguishes different types of chemical bonding, reveals that orthorhombic GeSe employs covalent bonding, while rhombohedral and cubic GeSe utilize MVB. The transition from covalent to MVB goes along with a pronounced improvement in thermoelectric performance. The failure or success of different dopants can be explained by this concept, which redefines doping rules and provides a "treasure map" to tailor p-bonded chalcogenides.

Metavalent Bonding in Layered Phase-Change Memory Materials.

Metavalent bonding (MVB) is characterized by the competition between electron delocalization as in metallic bonding and electron localization as in covalent or ionic bonding, serving as an essential ingredient in phase-change materials for advanced memory applications. The crystalline phase-change materials exhibits MVB, which stems from the highly aligned p orbitals and results in large dielectric constants. Breaking the alignment of these chemical bonds leads to a drastic reduction in dielectric constants. In this work, it is clarified how MVB develops across the so-called van der Waals-like gaps in layered Sb2 Te3 and Ge-Sb-Te alloys, where coupling of p orbitals is significantly reduced. A type of extended defect involving such gaps in thin films of trigonal Sb2 Te3 is identified by atomic imaging experiments and ab initio simulations. It is shown that this defect has an impact on the structural and optical properties, which is consistent with the presence of non-negligible electron sharing in the gaps. Furthermore, the degree of MVB across the gaps is tailored by applying uniaxial strain, which results in a large variation of dielectric function and reflectivity in the trigonal phase. At last, design strategies are provided for applications utilizing the trigonal phase.

Fast crystallization below the glass transition temperature in hyperquenched systems.

Many phase change materials (PCMs) are found to crystallize without exhibiting a glass transition endotherm upon reheating. In this paper, we review experimental evidence revealing that these PCMs and likely other hyperquenched molecular and metallic systems can crystallize from the glassy state when reheated at a standard rate. Among these evidences, PCMs annealed below the glass transition temperature Tg exhibit slower crystallization kinetics despite an increase in the number of sub-critical nuclei that should promote the crystallization speed. Flash calorimetry uncovers the glass transition endotherm hidden by crystallization and reveals a distinct change in kinetics when crystallization switches from the glassy to the supercooled liquid state. The resulting Tg value also rationalizes the presence of the pre-Tg relaxation exotherm ubiquitous of hyperquenched systems. Finally, the shift in crystallization temperature during annealing exhibits a non-exponential decay that is characteristic of structural relaxation in the glass. Modeling using a modified Turnbull equation for nucleation rate supports the existence of sub-Tg fast crystallization and emphasizes the benefit of a fragile-to-strong transition for PCM applications due to a reduction in crystallization at low temperature (improved data retention) and increasing its speed at high temperature (faster computing).

Strong charge carrier scattering at grain boundaries of PbTe caused by the collapse of metavalent bonding.

Grain boundaries (GBs) play a significant role in controlling the transport of mass, heat and charge. To unravel the mechanisms underpinning the charge carrier scattering at GBs, correlative microscopy combined with local transport measurements is realized. For the PbTe material, the strength of carrier scattering at GBs depends on its misorientation angle. A concomitant change in the barrier height is observed, significantly increasing from low- to high-angle GBs. Atom probe tomography measurements reveal a disruption of metavalent bonding (MVB) at the dislocation cores of low-angle GBs, as evidenced by the abrupt change in bond-rupture behavior. In contrast, MVB is completely destroyed at high-angle GBs, presumably due to the increased Peierls distortion. The collapse of MVB is accompanied by a breakdown of the dielectric screening, which explains the enlarged GB barrier height. These findings correlate charge carrier scattering with bonding locally, promising new avenues for the design of advanced functional materials.

Revisiting the Nature of Chemical Bonding in Chalcogenides to Explain and Design their Properties.

Quantum chemical bonding descriptors have recently been utilized to design materials with tailored properties. Their usage to facilitate a quantitative description of bonding in chalcogenides as well as the transition between different bonding mechanisms is reviewed. More importantly, these descriptors can also be employed as property predictors for several important material characteristics, including optical and transport properties. Hence, these quantum chemical bonding descriptors can be utilized to tailor material properties of chalcogenides relevant for thermoelectrics, photovoltaics, and phase-change memories. Relating material properties to bonding mechanisms also shows that there is a class of materials, which are characterized by unconventional properties such as a pronounced anharmonicity, a large chemical bond polarizability, and strong optical absorption. This unusual property portfolio is attributed to a novel bonding mechanism, fundamentally different from ionic, metallic, and covalent bonding, which is called "metavalent." In the concluding section, a number of promising research directions are sketched, which explore the nature of the property changes upon changing bonding mechanism and extend the concept of quantum chemical property predictors to more complex compounds.

Highly tunable ß-relaxation enables the tailoring of crystallization in phase-change materials.

In glasses, secondary (ß-) relaxations are the predominant source of atomic dynamics. Recently, they have been discovered in covalently bonded glasses, i.e., amorphous phase-change materials (PCMs). However, it is unclear what the mechanism of ß-relaxations is in covalent systems and how they are related to crystallization behaviors of PCMs that are crucial properties for non-volatile memories and neuromorphic applications. Here we show direct evidence that crystallization is strongly linked to ß-relaxations. We find that the ß-relaxation in Ge15Sb85 possesses a high tunability, which enables a manipulation of crystallization kinetics by an order of magnitude. In-situ synchrotron X-ray scattering, dielectric functions, and ab-initio calculations indicate that the weakened ß-relaxation intensity stems from a local reinforcement of Peierls-like distortions, which increases the rigidity of the bonding network and decreases the dynamic heterogeneity. Our findings offer a conceptually new approach to tuning the crystallization of PCMs based on manipulating the ß-relaxations.

Classification of properties and their relation to chemical bonding: Essential steps toward the inverse design of functional materials.

To design advanced functional materials, different concepts are currently pursued, including machine learning and high-throughput calculations. Here, a different approach is presented, which uses the innate structure of the multidimensional property space. Clustering algorithms confirm the intricate structure of property space and relate the different property classes to different chemical bonding mechanisms. For the inorganic compounds studied here, four different property classes are identified and related to ionic, metallic, covalent, and recently identified metavalent bonding. These different bonding mechanisms can be quantified by two quantum chemical bonding descriptors, the number of electrons transferred and the number of electrons shared between adjacent atoms. Hence, we can link these bonding descriptors to the corresponding property portfolio, turning bonding descriptors into property predictors. The close relationship between material properties and quantum chemical bonding descriptors can be used for an inverse material design, identifying particularly promising materials based on a set of target functionalities.