Phase-Pure α-Sn Quantum Material on Si Seeded by a 2 nm-Thick Ge Layer.

α-Sn, a new elemental topological quantum material, has drawn substantial attention lately. Unique transport properties and intriguing spintronics applications of α-Sn are demonstrated, resurrecting this material from its notorious "tin pest" infamy. With a diamond cubic crystal structure, group-IV α-Sn holds the potential for integrated topological quantum devices on Si. However, directly growing α-Sn on Si is still challenging due to the ≈20% lattice mismatch. Here, a new method is demonstrated to grow 200 nm-thick α-Sn microstructures on a 2 nm-thick Ge seed layer on Si substrate by physical vapor deposition. In situ Raman spectroscopy reveals that the as-deposited ß-Sn melts upon rapid thermal annealing at 350-450 °C and solidifies to α-Sn after cooling back to room temperature, seeded by heterogeneous nucleation on the Ge layer. Cooling condition and HCl etching are tuned to achieve phase-pure α-Sn microstructures toward quantum devices. Approximately 1 at.% Ge is alloyed into α-Sn due to diffusion from the Ge seed layer, which helps stabilize α-Sn thermodynamically to facilitate device processing. A compressive strain is incorporated into these α-Sn microstructures, making them 3D topological Dirac semimetals for integrated quantum devices on Si.

Time-reversal symmetry breaking superconductivity between twisted cuprate superconductors.

Twisted interfaces between stacked van der Waals (vdW) cuprate crystals present a platform for engineering superconducting order parameters by adjusting stacking angles. Using a cryogenic assembly technique, we construct twisted vdW Josephson junctions (JJs) at atomically sharp interfaces between Bi2Sr2CaCu2O8+x crystals, with quality approaching the limit set by intrinsic JJs. Near 45° twist angle, we observe fractional Shapiro steps and Fraunhofer patterns, consistent with the existence of two degenerate Josephson ground states related by time-reversal symmetry (TRS). By programming the JJ current bias sequence, we controllably break TRS to place the JJ into either of the two ground states, realizing reversible Josephson diodes without external magnetic fields. Our results open a path to engineering topological devices at higher temperatures.

Giant Nonlinear Optical Response via Coherent Stacking of In-Plane Ferroelectric Layers.

Thin ferroelectric materials hold great promise for compact nonvolatile memory and nonlinear optical and optoelectronic devices. Herein, an ultrathin in-plane ferroelectric material that exhibits a giant nonlinear optical effect, group-IV monochalcogenide SnSe, is reported. Nanometer-scale ferroelectric domains with ≈90°/270° twin boundaries or ≈180° domain walls are revealed in physical-vapor-deposited SnSe by lateral piezoresponse force microscopy. Atomic structure characterization reveals both parallel and antiparallel stacking of neighboring van der Waals ferroelectric layers, leading to ferroelectric or antiferroelectric ordering. Ferroelectric domains exhibit giant nonlinear optical activity due to coherent enhancement of second-harmonic fields and the as-resulted second-harmonic generation was observed to be 100 times more intense than monolayer WS2 . This work demonstrates in-plane ferroelectric ordering and giant nonlinear optical activity in SnSe, which paves the way for applications in on-chip nonlinear optical components and nonvolatile memory devices.

3D Nanoscale Mapping of Short-Range Order in GeSn Alloys.

GeSn on Si has attracted much research interest due to its tunable direct bandgap for mid-infrared applications. Recently, short-range order (SRO) in GeSn alloys has been theoretically predicted, which profoundly impacts the band structure. However, characterizing SRO in GeSn is challenging. Guided by physics-informed Poisson statistical analyses of k-nearest neighbors (KNN) in atom probe tomography (APT), a new approach is demonstrated here for 3D nanoscale SRO mapping and semi-quantitative strain mapping in GeSn. For GeSn with ≈14 at. % Sn, the SRO parameters of Sn-Sn 1NN in 10 × 10 × 10 nm3 nanocubes can deviate from that of the random alloys by ±15 %. The relatively large fluctuation of the SRO parameters contributes to band-edge softening observed optically. Sn-Sn 1NN also tends to be more favored toward the surface, less favored under strain relaxation or tensile strain, while almost independent of local Sn composition. An algorithm based on least square fit of atomic positions further verifies this Poisson-KNN statistical method. Compared to existing macroscopic spectroscopy or electron microscopy techniques, this new APT statistical analysis uniquely offers 3D SRO mapping at nanoscale resolution in a relatively large volume with millions of atoms. It can also be extended to investigate SRO in other alloy systems.

Layer Hall effect in a 2D topological axion antiferromagnet.

Whereas ferromagnets have been known and used for millennia, antiferromagnets were only discovered in the 1930s1. At large scale, because of the absence of global magnetization, antiferromagnets may seem to behave like any non-magnetic material. At the microscopic level, however, the opposite alignment of spins forms a rich internal structure. In topological antiferromagnets, this internal structure leads to the possibility that the property known as the Berry phase can acquire distinct spatial textures2,3. Here we study this possibility in an antiferromagnetic axion insulator-even-layered, two-dimensional MnBi2Te4-in which spatial degrees of freedom correspond to different layers. We observe a type of Hall effect-the layer Hall effect-in which electrons from the top and bottom layers spontaneously deflect in opposite directions. Specifically, under zero electric field, even-layered MnBi2Te4 shows no anomalous Hall effect. However, applying an electric field leads to the emergence of a large, layer-polarized anomalous Hall effect of about 0.5e2/h (where e is the electron charge and h is Planck's constant). This layer Hall effect uncovers an unusual layer-locked Berry curvature, which serves to characterize the axion insulator state. Moreover, we find that the layer-locked Berry curvature can be manipulated by the axion field formed from the dot product of the electric and magnetic field vectors. Our results offer new pathways to detect and manipulate the internal spatial structure of fully compensated topological antiferromagnets4-9. The layer-locked Berry curvature represents a first step towards spatial engineering of the Berry phase through effects such as layer-specific moiré potential.

Single-Particle Studies Reveal a Nanoscale Mechanism for Elastic, Bright, and Repeatable ZnS:Mn Mechanoluminescence in a Low-Pressure Regime.

Mechanoluminescent materials, which emit light in response to elastic deformation, are demanded for use as in situ stress sensors. ZnS doped with Mn is known to exhibit one of the lowest reported thresholds for appearance of mechanoluminescence, with repeatable light emission under contact pressure <10 MPa. The physical basis for such behavior remains as yet unclear. Here, reliable microscopic detection of mechanoluminescence of single ZnS:Mn microparticles, in combination with nanoscale structural characterization, provides evidence that the mechanoluminescent properties of these particles result from interplay between a non-centrosymmetric crystal lattice and its defects, viz., dislocations and stacking faults. Statistical analysis of the distributions of mechanoluminescence energy release trajectories reveals two distinct mechanisms of excitation: one attributable to a piezo-phototronic effect and the other due to dislocation motion. At pressures below 8.1 MPa, both mechanisms contribute to mechanoluminescent output, with a dominant contribution from the piezo-phototronic mechanism. In contrast, above 8.1 MPa, dislocation motion is the primary excitation source. For the piezo-phototronic mechanism, we propose a specific model that accounts for elastic ZnS:Mn mechanoluminescence under very low pressure. The charged interfaces in stacking faults lead to the presence of filled traps, which otherwise would be empty in the absence of the built-in electric field. Upon application of external stress, local enhancement of the piezoelectric field at the stacking faults' interfaces facilitates release of the trapped carriers and subsequent luminescence. This field enhancement explains how <10 MPa pressure produces thousands of photons.

Aluminosilicate haloes preserve complex life approximately 800 million years ago.

Mudstone-hosted microfossils are a major component of the Proterozoic fossil record, particularly dominating the record of early eukaryotic life. Early organisms possessed no biomineralized parts to resist decay and controls on their fossilization in mudstones are poorly understood. Consequently, the Proterozoic fossil record is compromised-we do not know whether changing temporal/spatial patterns of microfossil occurrences reflect evolution or the distribution of favourable fossilization conditions. We investigated fossilization within the approximately 1000 Ma Lakhanda Group (Russia) and the approximately 800 Ma Svanbergfjellet and Wynniatt formations (Svalbard and Arctic Canada). Vertical sections of microfossils and surrounding matrices were extracted from thin sections by focused ion beam milling. Elemental mapping and synchrotron-based infrared microspectroscopy revealed that microfossils are surrounded by haloes rich in aluminium, probably hosted in kaolinite. Kaolinite has been implicated in Cambrian Burgess Shale-type (BST) fossilization and is known to slow the growth of degraders. The Neoproterozoic mudstone microfossil record may be biased to tropical settings conducive to kaolinite formation. These deposits lack metazoan fossils even though they share fossilization conditions with younger BST deposits that are capable of preserving non-mineralizing metazoans. Thus metazoans, at least those typically preserved in BST deposits, were probably absent from sedimentary environments before approximately 800 Ma.

Aggregated nanoparticles: Sample preparation and analysis by atom probe tomography.

Atom probe tomography (APT) allows measurement of the three-dimensional structure and composition of materials, but specific sample preparation procedures are required for challenging materials such as aggregates of nanoparticles. Indeed, the presence of porosity within the specimen affects both the stability of the sample and the accuracy of the data. Here, aggregates of nanoparticles were transferred onto a micromanipulator tip and embedded via electron-beam-assisted deposition of Pt. Successive FIB-millings and Pt-depositions are needed to create suitable APT tips. The 3D reconstruction reveals the presence of 15-20 nm nanoparticles, and mass-spectral analysis shows the absence of trace elements within the catalyst, thus serving as quality control for the synthesis of nanoparticles with specific compositions.

Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination.

Shifting electrochemical oxygen reduction towards 2e- pathway to hydrogen peroxide (H2O2), instead of the traditional 4e- to water, becomes increasingly important as a green method for H2O2 generation. Here, through a flexible control of oxygen reduction pathways on different transition metal single atom coordination in carbon nanotube, we discovered Fe-C-O as an efficient H2O2 catalyst, with an unprecedented onset of 0.822 V versus reversible hydrogen electrode in 0.1 M KOH to deliver 0.1 mA cm-2 H2O2 current, and a high H2O2 selectivity of above 95% in both alkaline and neutral pH. A wide range tuning of 2e-/4e- ORR pathways was achieved via different metal centers or neighboring metalloid coordination. Density functional theory calculations indicate that the Fe-C-O motifs, in a sharp contrast to the well-known Fe-C-N for 4e-, are responsible for the H2O2 pathway. This iron single atom catalyst demonstrated an effective water disinfection as a representative application.

A Novel Bone Substitute with High Bioactivity, Strength, and Porosity for Repairing Large and Load-Bearing Bone Defects.

Achieving adequate healing in large or load-bearing bone defects is highly challenging even with surgical intervention. The clinical standard of repairing bone defects using autografts or allografts has many drawbacks. A bioactive ceramic scaffold, strontium-hardystonite-gahnite or "Sr-HT-Gahnite" (a multi-component, calcium silicate-based ceramic) is developed, which when 3D-printed combines high strength with outstanding bone regeneration ability. In this study, the performance of purely synthetic, 3D-printed Sr-HT-Gahnite scaffolds is assessed in repairing large and load-bearing bone defects. The scaffolds are implanted into critical-sized segmental defects in sheep tibia for 3 and 12 months, with bone autografts used for comparison. The scaffolds induce substantial bone formation and defect bridging after 12 months, as indicated by X-ray, micro-computed tomography, and histological and biomechanical analyses. Detailed analysis of the bone-scaffold interface using focused ion beam scanning electron microscopy and multiphoton microscopy shows scaffold degradation and maturation of the newly formed bone. In silico modeling of strain energy distribution in the scaffolds reveal the importance of surgical fixation and mechanical loading on long-term bone regeneration. The clinical application of 3D-printed Sr-HT-Gahnite scaffolds as a synthetic bone substitute can potentially improve the repair of challenging bone defects and overcome the limitations of bone graft transplantation.

Effects of Material-Tissue Interactions on Bone Regeneration Outcomes Using Baghdadite Implants in a Large Animal Model.

Extensive bone loss due to trauma or disease leads to impaired healing. Current bone grafts and substitutes have major drawbacks that limit their effectiveness for treating large bone defects. A number of bone substitutes in development are undergoing preclinical testing, but few studies specifically investigate the in vivo material-tissue interactions that provide an important indicator to long-term implant safety and efficacy. This study is the first of its kind to specifically investigate in vivo material-tissue interactions at the bone-implant interface. Baghdadite scaffolds implanted in critical-sized segmental defects in sheep tibia for 26 weeks are analyzed by focused ion beam scanning electron microscopy, multiphoton microscopy, and histology. The scaffolds are seen to induce extensive bone formation that directly abut the implant surfaces with no evidence of chronic inflammation or fibrous capsule formation. Bone remodeling is influenced by slow in vivo degradation around and within the implant, causing portions of the implant to be incorporated into the newly formed bone. These findings have important implications for predicting the long-term effects of baghdadite ceramics in promoting defect healing, and support the translation of baghdadite scaffolds as a new generation of bone graft substitutes with improved properties for the repair of large bone defects.

Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases.

Many application-relevant properties of nanoporous metals critically depend on their multiscale architecture. For example, the intrinsically high step-edge density of curved surfaces at the nanoscale provides highly reactive sites for catalysis, whereas the macroscale pore and grain morphology determines the macroscopic properties, such as mass transport, electrical conductivity, or mechanical properties. In this work, we systematically study the effects of alloy composition and dealloying conditions on the multiscale morphology of nanoporous copper (np-Cu) made from various commercial Zn-Cu precursor alloys. Using a combination of X-ray diffraction, electron backscatter diffraction, and focused ion beam cross-sectional analysis, our results reveal that the macroscopic grain structure of the starting alloy surprisingly survives the dealloying process, despite a change in crystal structure from body-centered cubic (Zn-Cu starting alloy) to face-centered cubic (Cu). The nanoscale structure can be controlled by the acid used for dealloying with HCl leading to a larger and more faceted ligament morphology compared to that of H3PO4. Anhydrous ethanol dehydrogenation was used as a probe reaction to test the effect of the nanoscale ligament morphology on the apparent activation energy of the reaction.

Highly tensile-strained Ge/InAlAs nanocomposites.

Self-assembled nanocomposites have been extensively investigated due to the novel properties that can emerge when multiple material phases are combined. Growth of epitaxial nanocomposites using lattice-mismatched constituents also enables strain-engineering, which can be used to further enhance material properties. Here, we report self-assembled growth of highly tensile-strained Ge/In0.52Al0.48As (InAlAs) nanocomposites by using spontaneous phase separation. Transmission electron microscopy shows a high density of single-crystalline germanium nanostructures coherently embedded in InAlAs without extended defects, and Raman spectroscopy reveals a 3.8% biaxial tensile strain in the germanium nanostructures. We also show that the strain in the germanium nanostructures can be tuned to 5.3% by altering the lattice constant of the matrix material, illustrating the versatility of epitaxial nanocomposites for strain engineering. Photoluminescence and electroluminescence results are then discussed to illustrate the potential for realizing devices based on this nanocomposite material.

Methylammonium Bismuth Iodide as a Lead-Free, Stable Hybrid Organic-Inorganic Solar Absorber.

Methylammonium lead halide (MAPbX3 ) perovskites exhibit exceptional carrier transport properties. But their commercial deployment as solar absorbers is currently limited by their intrinsic instability in the presence of humidity and their lead content. Guided by our theoretical predictions, we explored the potential of methylammonium bismuth iodide (MBI) as a solar absorber through detailed materials characterization. We synthesized phase-pure MBI by solution and vapor processing. In contrast to MAPbX3, MBI is air stable, forming a surface layer that does not increase the recombination rate. We found that MBI luminesces at room temperature, with the vapor-processed films exhibiting superior photoluminescence (PL) decay times that are promising for photovoltaic applications. The thermodynamic, electronic, and structural features of MBI that are amenable to these properties are also present in other hybrid ternary bismuth halide compounds. Through MBI, we demonstrate a lead-free and stable alternative to MAPbX3 that has a similar electronic structure and nanosecond lifetimes.

Room-temperature sub-band gap optoelectronic response of hyperdoped silicon.

Room-temperature infrared sub-band gap photoresponse in silicon is of interest for telecommunications, imaging and solid-state energy conversion. Attempts to induce infrared response in silicon largely centred on combining the modification of its electronic structure via controlled defect formation (for example, vacancies and dislocations) with waveguide coupling, or integration with foreign materials. Impurity-mediated sub-band gap photoresponse in silicon is an alternative to these methods but it has only been studied at low temperature. Here we demonstrate impurity-mediated room-temperature sub-band gap photoresponse in single-crystal silicon-based planar photodiodes. A rapid and repeatable laser-based hyperdoping method incorporates supersaturated gold dopant concentrations on the order of 10(20) cm(-3) into a single-crystal surface layer ~150 nm thin. We demonstrate room-temperature silicon spectral response extending to wavelengths as long as 2,200 nm, with response increasing monotonically with supersaturated gold dopant concentration. This hyperdoping approach offers a possible path to tunable, broadband infrared imaging using silicon at room temperature.

Resolving the growth of 3D colloidal nanoparticle superlattices by real-time small-angle X-ray scattering.

The kinetics and intricate interactions governing the growth of 3D single nanoparticle (NP) superlattices (SLs, SNSLs) and binary NP SLs (BNSLs) in solution are understood by combining controlled solvent evaporation and in situ, real-time small-angle X-ray scattering (SAXS). For the iron oxide (magnetite) NP SLs studied here, the larger the NP, the farther apart are the NPs when the SNSLs begin to precipitate and the closer they are after ordering. This is explained by a model of NP assembly using van der Waals interactions between magnetite cores in hydrocarbons with a ∼21 zJ Hamaker constant. When forming BNSLs of two different sized NPs, the NPs that are in excess of that needed to achieve the final BNSL stoichiometry are expelled during the BNSL formation, and these expelled NPs can form SNSLs. The long-range ordering of these SNSLs and the BNSLs can occur faster than the NP expulsion.

Raman analysis of mode softening in nanoparticle CeO(2-δ) and Au-CeO(2-δ) during CO oxidation.

Oxygen vacancy levels are monitored during the oxidation of CO by CeO(2-δ) nanorods and Au-CeO(2-δ) nanorods, nanocubes, and nanopolyhedra by using Raman scattering. The first-order CeO(2) F(2g) peak near 460 cm(-1) decreases when this reaction is fast (fast reduction and relatively slow reoxidation of the surface), because of the lattice expansion that occurs when Ce(3+) replaces Ce(4+) during oxygen vacancy creation. This shift correlates with reactivity for CO oxidation. Increases in the oxygen deficit δ as large as ~0.04 are measured relative to conditions when the ceria is not reduced.

Formation of thick, large-area nanoparticle superlattices in lithographically defined geometries.

Superlattices of colloidal nanocrystals hold the promise of new nanomaterials with tunable properties. The positioning and size of these structures are often poorly controlled after self-assembly from the solution phase, making studies of their properties difficult. We report the fabrication of approximately 100 layer thick, three-dimensional superlattices on a substrate with controlled lateral placement. This novel fabrication technique generates long-range order over the micrometer scale and controlled placement by employing lithographic patterning and microfluidic flow.