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Phonon dispersion is widely used to elucidate the vibrational properties of materials. As an emerging technique, momentum-resolved vibrational spectroscopy in scanning transmission electron microscopy (STEM) offers an unparalleled approach to explore q-dependent phonon behavior at local structures. In this study, we systematically investigate the phonon dispersion of monolayer graphene across several Brillouin zones (BZs) using momentum-resolved vibrational spectroscopy and find that the optical phonon signals vanish at the {\Gamma} points with indices (hk0) satisfying h+2k=3n (n denoted integers). Theoretical analysis reveals that the observed phenomena arise from the complete destructive interference of the scattered waves from different basis atoms. This observation, corroborated by the study of diamond, should be a general characteristic of materials composed of symmetrically equivalent pairs of the same elements. Moreover, our results emphasize the importance of multiple scattering in interpreting the vibrational signals in bulk materials. We demonstrate that the systematic absences and dynamic effects, which have not been much appreciated before, offer new insights into the experimental assessment of local vibrational properties of materials.

A continuing challenge in atomic resolution microscopy is to identify significant structural motifs and their assembly rules in synthesized materials with limited observations. Here we propose and validate a simple and effective hybrid generative model capable of predicting unseen domain boundaries in a potassium sodium niobate thin film from only a small number of observations, without expensive first-principles calculation. Our results demonstrate that complicated domain boundary structures can arise from simple interpretable local rules, played out probabilistically. We also found new significant tileable boundary motifs and evidence that our system creates domain boundaries with the highest entropy. More broadly, our work shows that simple yet interpretable machine learning models can help us describe and understand the nature and origin of disorder in complex materials.

Two-dimensional (2D) perovskite oxide interfaces are ideal systems where diverse emergent properties can be uncovered.The formation and modification of polaronic properties due to short-range strong charge-lattice interactions of 2D interfaces remains hugely intriguing.Here, we report the direct observation of small-polarons at the LaAlO3/SrTiO3 (LAO/STO) conducting interface using high-resolution spectroscopic ellipsometry.First-principles investigations further reveals that strong coupling between the interfacial electrons and the Ti-lattice result in the formation of localized 2D small polarons.These findings resolve the longstanding issue where the excess experimentally measured interfacial carrier density is significantly lower than theoretically predicted values.The charge-phonon induced lattice distortion further provides an analogue to the superconductive states in magic-angle twisted bilayer graphene attributed to the many-body correlations induced by broken periodic lattice symmetry.Our study sheds light on the multifaceted complexity of broken periodic lattice induced quasi-particle effects and its relationship with superconductivity.

Majorana zero modes (MZMs) obey non-Abelian statistics and are considered building blocks for constructing topological qubits. Iron-based superconductors with topological band structures have emerged as promising hosting materials, since isolated candidate MZMs in the quantum limit have been observed inside the topological vortex cores. However, these materials suffer from issues related to alloying-induced disorder, uncontrolled vortex lattices and a low yield of topological vortices. Here, we report the formation of an ordered and tunable MZM lattice in naturally-strained stoichiometric LiFeAs by scanning tunneling microscopy/spectroscopy (STM/S). We observe biaxial charge density wave (CDW) stripes along the Fe-Fe and As-As directions in the strained regions. The vortices are pinned on the CDW stripes in the As-As direction and form an ordered lattice. We detect more than 90 percent of the vortices to be topological and possess the characteristics of isolated MZMs at the vortex center, forming an ordered MZM lattice with the density and the geometry tunable by an external magnetic field. Remarkably, with decreasing the spacing of neighboring vortices, the MZMs start to couple with each other. Our findings provide a new pathway towards tunable and ordered MZM lattices as a platform for future topological quantum computation.

Interlayer electronic coupling in two-dimensional (2D) materials enables tunable and emergent properties by stacking engineering. However, it also brings significant evolution of electronic structures and attenuation of excitonic effects in 2D semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a novel van der Waals crystal, niobium oxide dichloride, featuring a vanishing interlayer electronic coupling and scalable second harmonic generation intensity of up to three orders higher than that of exciton-resonant monolayer WS2. Importantly, the strong second-order nonlinearity enables correlated parametric photon pair generation, via a spontaneous parametric down-conversion (SPDC) process, in flakes as thin as ~46 nm. To our knowledge, this is the first SPDC source unambiguously demonstrated in 2D layered materials, and the thinnest SPDC source ever reported. Our work opens an avenue towards developing van der Waals material-based ultracompact on-chip SPDC sources, and high-performance photon modulators in both classical and quantum optical technologies.

The vanadium-based kagome superconductor CsV3Sb5 has attracted tremendous attention due to its unexcepted anomalous Hall effect (AHE), charge density waves (CDWs), nematicity, and a pseudogap pair density wave (PDW) coexisting with unconventional strong-coupling superconductivity (SC). The origins of CDWs, unconventional SC, and their correlation with different electronic states in this kagome system are of great significance, but so far, are still under debate. Chemical doping in the kagome layer provides one of the most direct ways to reveal the intrinsic physics, but remains unexplored. Here, we report, for the first time, the synthesis of Ti-substituted CsV3Sb5 single crystals and its rich phase diagram mapping the evolution of intertwining electronic states. The Ti atoms directly substitute for V in the kagome layers. CsV3-xTixSb5 shows two distinct SC phases upon substitution. The Ti slightly-substituted phase displays an unconventional V-shaped SC gap, coexisting with weakening CDW, PDW, AHE, and nematicity. The Ti highly-substituted phase has a U-shaped SC gap concomitant with a short-range rotation symmetry breaking CDW, while long-range CDW, twofold symmetry of in-plane resistivity, AHE, and PDW are absent. Furthermore, we also demonstrate the chemical substitution of V atoms with other elements such as Cr and Nb, showing a different modulation on the SC phase and CDWs. These findings open up a way to synthesise a new family of doped CsV3Sb5 materials, and further representing a new platform for tuning the different correlated electronic states and superconducting pairing in kagome superconductors., Comment: Science Bulletin (2022,in press)

We report the control of Rashba spin-orbit interaction by tuning asymmetric hybridization between Ti-orbitals at the LaAlO3/SrTiO3 interface. This asymmetric orbital hybridization is modulated by introducing a LaFeO3 layer between LaAlO3 and SrTiO3, which alters the Ti-O lattice polarization and traps interfacial charge carriers, resulting in a large Rashba spin-orbit effect at the interface in the absence of an external bias. This observation is verified through high-resolution electron microscopy, magneto-transport and first-principles calculations. Our results open hitherto unexplored avenues of controlling Rashba interaction to design next-generation spin-orbitronics., Comment: Total 30 Pages and 18 figures in the main article including supplementary information

Development of memory devices with ultimate performance has played a key role in innovation of modern electronics. As a mainstream technology nonvolatile memory devices have manifested high capacity and mechanical reliability, however current major bottlenecks include low extinction ratio and slow operational speed. Although substantial effort has been employed to improve their performance, a typical hundreds of micro- or even milli- second write time remains a few orders of magnitude longer than their volatile counterparts. We have demonstrated nonvolatile, floating-gate memory devices based on van der Waals heterostructures with atomically sharp interfaces between different functional elements, and achieved ultrahigh-speed programming/erasing operations verging on an ultimate theoretical limit of nanoseconds with extinction ratio up to 10^10. This extraordinary performance has allowed new device capabilities such as multi-bit storage, thus opening up unforeseen applications in the realm of modern nanoelectronics and offering future fabrication guidelines for device scale-up., Comment: Preprint version, to be published in Nature Nanotechnology (Submitted on August 16th, 2020)

Empowering conventional materials with unexpected magnetoelectric properties is appealing to the multi-functionalization of existing devices and the exploration of future electronics. Recently, owing to its unique effect in modulating a matter's properties, ultra-small dopants, e.g. H, D, and Li, attract enormous attention in creating emergent functionalities, such as superconductivity, and metal-insulator transition. Here, we report an observation of bipolar conduction accompanied by a giant positive magnetoresistance in D-doped metallic Ti oxide (TiOxDy) films. To overcome the challenges in intercalating the D into a crystalline oxide, a series of TiOxDy were formed by sequentially doping Ti with D and surface/interface oxidation. Intriguingly, while the electron mobility of the TiOxDy increases by an order of magnitude larger after doping, the emergent holes also exhibit high mobility. Moreover, the bipolar conduction induces a giant magnetoresistance up to 900% at 6 T, which is ~6 times higher than its conventional phase. Our study paves a way to empower conventional materials in existing electronics and induce novel electronic phases.

The accurate determination of the compositional fluctuations is pivotal in understanding their role in the reduction of efficiency in high indium content $In_{x}Ga_{1-x}N$ light-emitting diodes, the origin of which is still poorly understood. Here we have combined electron energy loss spectroscopy (EELS) imaging at sub-nanometer resolution with multiscale computational models to obtain a statistical distribution of the compositional fluctuations in $In_{x}Ga_{1-x}N$ quantum wells (QWs). Employing a multiscale computational model, we show the tendency of intrinsic compositional fluctuation in $In_{x}Ga_{1-x}N$ QWs at different Indium concentration and in the presence of strain. We have developed a systematic formalism based on the autonomous detection of compositional fluctuation in observed and simulated EELS maps. We have shown a direct comparison between the computationally predicted and experimentally observed compositional fluctuations. We have found that although a random alloy model captures the distribution of compositional fluctuations in relatively low In ($\sim$ 18%) content $In_{x}Ga_{1-x}N$ QWs, there exists a striking deviation from the model in higher In content ($\geq$ 24%) QWs. Our results highlight a distinct behavior in carrier localization driven by compositional fluctuations in the low and high In-content InGaN QWs, which would ultimately affect the performance of LEDs. Furthermore, our robust computational and atomic characterization method can be widely applied to study materials in which nanoscale compositional fluctuations play a significant role on the material performance., Comment: 38 pages, 5 Figures

Hybrid nanoparticles allow exploiting the interplay of confinement, proximity between different materials and interfacial effects. However, to harness their properties an in-depth understanding of their (meta)stability and interfacial characteristics is crucial. This is especially the case of nanosystems based on functional oxides working under reducing conditions, which may severely impact their properties. In this work, the in-situ electron-induced selective reduction of Mn3O4 to MnO is studied in magnetic Fe3O4/Mn3O4 and Mn3O4/Fe3O4 core/shell nanoparticles by means of high-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Such in-situ transformation allows mimicking the actual processes in operando environments. A multi-stage image analysis using geometric phase analysis combined with particle image velocity enables direct monitoring of the relationship between structure, chemical composition and strain relaxation during the Mn3O4 reduction. In the case of Fe3O4/Mn3O4 core/shell the transformation occurs smoothly without the formation of defects. However, for the inverse Mn3O4/Fe3O4 core/shell configuration the electron beam-induced transformation occurs in different stages that include redox reactions and void formation followed by strain field relaxation via formation of defects. This study highlights the relevance of understanding the local dynamics responsible for changes in the particle composition in order to control stability and, ultimately, macroscopic functionality.

Progress in functional materials discovery has been accelerated by advances in high throughput materials synthesis and by the development of high-throughput computation. However, a complementary robust and high throughput structural characterization framework is still lacking. New methods and tools in the field of machine learning suggest that a highly automated high-throughput structural characterization framework based on atomic-level imaging can establish the crucial statistical link between structure and macroscopic properties. Here we develop a machine learning framework towards this goal. Our framework captures local structural features in images with Zernike polynomials, which is demonstrably noise-robust, flexible, and accurate. These features are then classified into readily interpretable structural motifs with a hierarchical active learning scheme powered by a novel unsupervised two-stage relaxed clustering scheme. We have successfully demonstrated the accuracy and efficiency of the proposed methodology by mapping a full spectrum of structural defects, including point defects, line defects, and planar defects in scanning transmission electron microscopy (STEM) images of various 2D materials, with greatly improved separability over existing methods. Our techniques can be easily and flexibly applied to other types of microscopy data with complex features, providing a solid foundation for automatic, multiscale feature analysis with high veracity.

Valley pseudospin in two-dimensional (2D) transition-metal dichalcogenides (TMDs) allows optical control of spin-valley polarization and intervalley quantum coherence. Defect states in TMDs give rise to new exciton features and theoretically exhibit spin-valley polarization; however, experimental achievement of this phenomenon remains challenges. Here, we report unambiguous valley pseudospin of defect-bound localized excitons in CVD-grown monolayer MoS2; enhanced valley Zeeman splitting with an effective g-factor of -6.2 is observed. Our results reveal that all five d-orbitals and the increased effective electron mass contribute to the band shift of defect states, demonstrating a new physics of the magnetic responses of defect-bound localized excitons, strikingly different from that of A excitons. Our work paves the way for the manipulation of the spin-valley degrees of freedom through defects toward valleytronic devices.

Two-dimensional (2D) magnets with intrinsic ferromagnetic/antiferromagnetic (FM/AFM) ordering are highly desirable for future spintronics devices. However, the synthesis of 2D magnetic crystals, especially the direct growth on SiO2/Si substrate, is just in its infancy. Here, we report a chemical vapor deposition (CVD)-based rational growth approach for the synthesis of ultrathin FeTe crystals with controlled structural and magnetic phases. By precisely optimizing the growth temperature (Tgrowth), FeTe nanoplates with either layered tetragonal or non-layered hexagonal phase can be controlled with high-quality. The two controllable phases lead to square and triangular morphologies with a thickness down to 3.6 and 2.8 nm, respectively. More importantly, transport measurements reveal that tetragonal FeTe is antiferromagnetic with a Neel temperature (TN) about 71.8 K, while hexagonal FeTe is ferromagnetic with a Curie temperature (TC) around 220 K. Theoretical calculations indicate that the ferromagnetic order in hexagonal FeTe is originated from a concomitant lattice distortion and the spin-lattice coupling. This study represents a major step forward in the CVD growth of 2D magnetic materials on SiO2/Si substrates and highlights on their potential applications in the future spintronic devices., Comment: 15 pages, 5 figures

Scanning transmission electron microscopy (STEM) has advanced rapidly in the last decade thanks to the ability to correct the major aberrations of the probe forming lens. Now atomic-sized beams are routine, even at accelerating voltages as low as 40 kV, allowing knock-on damage to be minimized in beam sensitive materials. The aberration-corrected probes can contain sufficient current for high quality, simultaneous, imaging and analysis in multiple modes. Atomic positions can be mapped with picometer precision, revealing ferroelectric domain structures, composition can be mapped by energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) and charge transfer can be tracked unit cell by unit cell using the EELS fine structure. Furthermore, dynamics of point defects can be investigated through rapid acquisition of multiple image scans. Today STEM has become an indispensable tool for analytical science at the atomic level, providing a whole new level of insights into the complex interplays that control materials properties.

Identifying the point defects in 2D materials is important for many applications. Recent studies have proposed that W vacancies are the predominant point defect in 2D WSe2, in contrast to theoretical studies, which predict that chalcogen vacancies are the most likely intrinsic point defects in transition metal dichalcogenide semiconductors. We show using first principles calculations, scanning tunneling microscopy (STM) and scanning transmission electron microscopy experiments, that W vacancies are not present in our CVD-grown 2D WSe2. We predict that O-passivated Se vacancies (O_Se) and O interstitials (Oins) are present in 2D WSe2, because of facile O2 dissociation at Se vacancies, or due to the presence of WO3 precursors in CVD growth. These defects give STM images in good agreement with experiment. The optical properties of point defects in 2D WSe2 are important because single photon emission (SPE) from 2D WSe2 has been observed experimentally. While strain gradients funnel the exciton in real space, point defects are necessary for the localization of the exciton at length scales that enable photons to be emitted one at a time. Using state-of-the-art GW-Bethe-Salpeter-equation calculations, we predict that only Oins defects give localized excitons within the energy range of SPE in previous experiments, making them a likely source of previously observed SPE. No other point defects (O_Se, Se vacancies, W vacancies and Se_W antisites) give localized excitons in the same energy range. Our predictions suggest ways to realize SPE in related 2D materials and point experimentalists toward other energy ranges for SPE in 2D WSe2.

The anomalous Hall effect, observed in conducting ferromagnets with broken time-reversal symmetry, offers the possibility to couple spin and orbital degrees of freedom of electrons in ferromagnets. In addition to charge, the anomalous Hall effect also leads to spin accumulation at the surfaces perpendicular to both the current and magnetization direction. Here we experimentally demonstrate that the spin accumulation, subsequent spin backflow, and spin-charge conversion can give rise to a different type of spin current related magnetoresistance, dubbed here as the anomalous Hall magnetoresistance, which has the same angular dependence as the recently discovered spin Hall magnetoresistance. The anomalous Hall magnetoresistance is observed in four types of samples: co-sputtered (Fe1-xMnx)0.6Pt0.4, Fe1-xMnx and Pt multilayer, Fe1-xMnx with x = 0.17 to 0.65 and Fe, and analyzed using the drift-diffusion model. Our results provide an alternative route to study charge-spin conversion in ferromagnets and to exploit it for potential spintronic applications.

We have synthesized two Nb@C composites with an order of magnitude difference in the density of single-atom niobium substituted into graphitic layers. The concentration and sites of single-atom Nb are identified using aberration-corrected scanning transmission electron microscopy and density functional theory. Comparing the complex permittivity spectra show that the representative dielectric resonance at ~16 GHz originates from the intrinsic polarization of single-atom Nb sites, confirmed by theoretical simulations. The single-atom dielectric resonance represents the physical limit of the electromagnetic response of condensed matter, and thus might open up a new avenue for designing electromagnetic wave absorption materials. Single-atom resonance also has important implications in understanding the correlation between the macroscopic dielectric behaviors and the atomic-scale structural origin.

Iron-based superconductors (FBS) comprise several families of compounds having the same atomic building blocks for superconductivity, but large discrepancies among their physical properties. A longstanding goal in the field has been to decipher the key underlying factors controlling TC and the various doping mechanisms. In FBS materials this is complicated immensely by the different crystal and magnetic structures exhibited by the different families. In this paper, using aberration-corrected scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS), we observe a universal behavior in the hole concentration and magnetic moment across different families. All the parent materials have the same total number of electrons in the Fe 3d bands; however, the local Fe magnetic moment varies due to different orbital occupancy. Although the common understanding has been that both long-range and local magnetic moments decrease with doping, we find that, near the onset of superconductivity, the local magnetic moment increases and shows a dome-like maximum near optimal doping, where no ordered magnetic moment is present. In addition, we address a longstanding debate concerning how Co substitutions induces superconductivity in the 122 arsenide family, showing that the 3d band filling increases a function of doping. These new microscopic insights into the properties of FBS demonstrate the importance of spin fluctuations for the superconducting state, reveal changes in orbital occupancy among different families of FBS, and confirm charge doping as one of the mechanisms responsible for superconductivity in 122 arsenides.

Here we study the electronic properties of cuprate/manganite interfaces. By means of atomic resolution electron microscopy and spectroscopy, we produce a subnanometer scale map of the transition metal oxidation state profile across the interface between the high $T_c$ superconductor YBa$_2$Cu$_3$O$_{7-\delta}$ and the colossal magnetoresistance compound (La,Ca)MnO$_3$. A net transfer of electrons from manganite to cuprate with a peculiar non-monotonic charge profile is observed. Model calculations rationalize the profile in terms of the competition between standard charge transfer tendencies (due to band mismatch), strong chemical bonding effects across the interface, and Cu substitution into the Mn lattice, with different characteristic length scales., Comment: 11+7 pages, 3+2 figures

We report on the first demonstration of p-type doping in large area few-layer films of (0001)-oriented chemical vapor deposited (CVD) MoS2. Niobium was found to act as an efficient acceptor up to relatively high density in MoS2 films. For a hole density of 4 x 1020 cm-3 Hall mobility of 8.5 cm2V-1s-1 was determined, which matches well with the theoretically expected values. XRD and Raman characterization indicate that the film had good out-of-plane crystalline quality. Absorption measurements showed that the doped sample had similar characteristics to high-quality undoped samples, with a clear absorption edge at 1.8 eV. This demonstration of p-doping in large area epitaxial MoS2 could help in realizing a wide variety of electrical and opto-electronic devices based on layered metal dichalcogenides.