Nanoscale imaging of phonon dynamics by electron microscopy.

Spatially resolved vibrational mapping of nanostructures is indispensable to the development and understanding of thermal nanodevices1, modulation of thermal transport2 and novel nanostructured thermoelectric materials3-5. Through the engineering of complex structures, such as alloys, nanostructures and superlattice interfaces, one can significantly alter the propagation of phonons and suppress material thermal conductivity while maintaining electrical conductivity2. There have been no correlative experiments that spatially track the modulation of phonon properties in and around nanostructures due to spatial resolution limitations of conventional optical phonon detection techniques. Here we demonstrate two-dimensional spatial mapping of phonons in a single silicon-germanium (SiGe) quantum dot (QD) using monochromated electron energy loss spectroscopy in the transmission electron microscope. Tracking the variation of the Si optical mode in and around the QD, we observe the nanoscale modification of the composition-induced red shift. We observe non-equilibrium phonons that only exist near the interface and, furthermore, develop a novel technique to differentially map phonon momenta, providing direct evidence that the interplay between diffuse and specular reflection largely depends on the detailed atomistic structure: a major advancement in the field. Our work unveils the non-equilibrium phonon dynamics at nanoscale interfaces and can be used to study actual nanodevices and aid in the understanding of heat dissipation near nanoscale hotspots, which is crucial for future high-performance nanoelectronics.

Single-defect phonons imaged by electron microscopy.

Crystal defects affect the thermal and heat-transport properties of materials by scattering phonons and modifying phonon spectra1-8. To appreciate how imperfections in solids influence thermal conductivity and diffusivity, it is thus essential to understand phonon-defect interactions. Sophisticated theories are available to explore such interactions, but experimental validation is limited because most phonon-detecting spectroscopic methods do not reach the high spatial resolution needed to resolve local vibrational spectra near individual defects. Here we demonstrate that space- and angle-resolved vibrational spectroscopy in a transmission electron microscope makes it possible to map the vibrational spectra of individual crystal defects. We detect a red shift of several millielectronvolts in the energy of acoustic vibration modes near a single stacking fault in cubic silicon carbide, together with substantial changes in their intensity, and find that these changes are confined to within a few nanometres of the stacking fault. These observations illustrate that the capabilities of a state-of-the-art transmission electron microscope open the door to the direct mapping of phonon propagation around defects, which is expected to provide useful guidance for engineering the thermal properties of materials.

Real-space charge-density imaging with sub-ångström resolution by four-dimensional electron microscopy.

The distribution of charge density in materials dictates their chemical bonding, electronic transport, and optical and mechanical properties. Indirectly measuring the charge density of bulk materials is possible through X-ray or electron diffraction techniques by fitting their structure factors1-3, but only if the sample is perfectly homogeneous within the area illuminated by the beam. Meanwhile, scanning tunnelling microscopy and atomic force microscopy enable us to see chemical bonds, but only on the surface4-6. It remains a challenge to resolve charge density in nanostructures and functional materials with imperfect crystalline structures-such as those with defects, interfaces or boundaries at which new physics emerges. Here we describe the development of a real-space imaging technique that can directly map the local charge density of crystalline materials with sub-ångström resolution, using scanning transmission electron microscopy alongside an angle-resolved pixellated fast-electron detector. Using this technique, we image the interfacial charge distribution and ferroelectric polarization in a SrTiO3/BiFeO3 heterojunction in four dimensions, and discover charge accumulation at the interface that is induced by the penetration of the polarization field of BiFeO3. We validate this finding through side-by-side comparison with density functional theory calculations. Our charge-density imaging method advances electron microscopy from detecting atoms to imaging electron distributions, providing a new way of studying local bonding in crystalline solids.

Growth of Highly Oriented (VNbMoTaW)S2 Layers.

Compositional tunability, an indispensable parameter for modifying the properties of materials, can open up new applications for van der Waals (vdW) layered materials such as transition-metal dichalcogenides (TMDCs). To date, multielement alloy TMDC layers are obtained via exfoliation from bulk polycrystalline powders. Here, we demonstrate direct deposition of high-entropy alloy disulfide, (VNbMoTaW)S2, layers with controllable thicknesses on free-standing graphene membranes and on bare and hBN-covered Al2O3(0001) substrates via ultra-high-vacuum reactive dc magnetron sputtering of the VNbMoTaW target in Kr and H2S gas mixtures. Using a combination of density functional theory calculations, Raman spectroscopy, X-ray diffraction, scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy, we determine that the as-deposited layers are single-phase, 2H-structured, and 0001-oriented (V0.10Nb0.16Mo0.19Ta0.28W0.27)S2.44. Our synthesis route is general and applicable for heteroepitaxial growth of a wide variety of TMDC alloys and potentially other multielement alloy vdW compounds with the desired compositions.

Anisotropy-Driven Crystallization of Dimensionally Resolved Quasi-1D Van der Waals Nanostructures.

Unusual behavior in solids emerges from the complex interplay between crystalline order, composition, and dimensionality. In crystals comprising weakly bound one-dimensional (1D) or quasi-1D (q-1D) chains, properties such as charge density waves, topologically protected states, and indirect-to-direct band gap crossovers have been predicted to arise. However, the experimental demonstration of many of these nascent physics in 1D or q-1D van der Waals (vdW) crystals is obscured by the highly anisotropic bonding between the chains, stochasticity of top-down exfoliation, and the lack of synthetic strategies to control bottom-up growth. Herein, we report the directed crystallization of a model q-1D vdW phase, Sb2S3, into dimensionally resolved nanostructures. We demonstrate the uncatalyzed growth of highly crystalline Sb2S3 nanowires, nanoribbons, and quasi-2D nanosheets with thicknesses in the range of 10 to 100 nm from the bottom-up crystallization of [Sb4S6]n chains. We found that dimensionally resolved nanostructures emerge from two distinct chemical vapor growth pathways defined by diverse covalent intrachain and anisotropic vdW interchain interactions and controlled precursor ratios in the vapor phase. At sub-100 nm nanostructure thicknesses, we observe the hardening of phonon modes, blue-shifting of optical band gaps, and the emergence of a new high-energy photoluminescence peak. The directional growth of weakly bound 1D ribbons or chains into well-resolved nanocrystalline morphologies provides opportunities to develop ordered nanostructures and hierarchical assemblies that are suitable for a wide range of optoelectronic and quantum devices.

Curvature-Induced One-Dimensional Phonon Polaritons at Edges of Folded Boron Nitride Sheets.

Generation and manipulation of phonon polaritons are of paramount importance for understanding the interaction between an electromagnetic field and dielectric materials and furthering their application in mid-infrared optical communication. However, the formation of tunable one-dimensional phonon polaritons has been rarely realized in van der Waals layered structures. Here we report the discovery of curvature-induced phonon polaritons localized at the crease of folded hexagonal boron nitrides (h-BNs) with a few atomic layers using monochromated electron energy-loss spectroscopy. Compared to bulk regions, the creased-localized signals undergo an abnormal blue-shift of 1.4 meV. First-principles calculations reveal that the energy shift arises from the optical phonon hardening in the curled region. Interestingly, the curvature-induced phonon polariton can also be controllably achieved via an electron-beam etching approach. This work opens an avenue of tailoring local electromagnetic response and creating unique phonon polariton modes in van der Waals layered materials for diverse applications.

Understanding the Mechanism of Electronic Defect Suppression Enabled by Nonidealities in Atomic Layer Deposition.

Silicon germanium (SiGe) is a multifunctional material considered for quantum computing, neuromorphic devices, and CMOS transistors. However, implementation of SiGe in nanoscale electronic devices necessitates suppression of surface states dominating the electronic properties. The absence of a stable and passive surface oxide for SiGe results in the formation of charge traps at the SiGe-oxide interface induced by GeOx. In an ideal ALD process in which oxide is grown layer by layer, the GeOx formation should be prevented with selective surface oxidation (i.e., formation of an SiOx interface) by controlling the oxidant dose in the first few ALD cycles of the oxide deposition on SiGe. However, in a real ALD process, the interface evolves during the entire ALD oxide deposition due to diffusion of reactant species through the gate oxide. In this work, this diffusion process in nonideal ALD is investigated and exploited: the diffusion through the oxide during ALD is utilized to passivate the interfacial defects by employing ozone as a secondary oxidant. Periodic ozone exposure during gate oxide ALD on SiGe is shown to reduce the integrated trap density (Dit) across the band gap by nearly 1 order of magnitude in Al2O3 (<6 × 1010 cm-2) and in HfO2 (<3.9 × 1011 cm-2) by forming a SiOx-rich interface on SiGe. Depletion of Ge from the interfacial layer (IL) by enhancement of volatile GeOx formation and consequent desorption from the SiGe with ozone insertion during the ALD growth process is confirmed by electron energy loss spectroscopy (STEM-EELS) and hypothesized to be the mechanism for reduction of the interfacial defects. In this work, the nanoscale mechanism for defect suppression at the SiGe-oxide interface is demonstrated, which is engineering of diffusion species in the ALD process due to facile diffusion of reactant species in nonideal ALD.

Vibrational spectroscopy in the electron microscope.

Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample--that is, for 'aloof' spectroscopy that largely avoids radiation damage.

Unexpected Strong Thermally Induced Phonon Energy Shift for Mapping Local Temperature.

Measuring temperature in nanoscale is crucial for the research and development of microelectronic devices. Plasmon resonance has been utilized to map local temperature gradient in metallic materials (Al) due to their large coefficients of thermal expansion. However, most semiconductors (including Si and SiC) possess much smaller coefficients of thermal expansion due to their strong covalent bonding in crystal structure, for which the plasmon-based temperature measurement becomes unreliable. Here, we report an unexpected strong, thermally induced phonon energy shift in SiC by spatially resolved vibrational spectroscopy in transmission electron microscopy with in situ heating, demonstrating that this shift can be applied as a useful tool for measuring nanoscale temperature. When a bulk phonon spectrum is used, the spatial resolution of vibrational spectroscopy can be as high as one nanometer. Molecular dynamics simulations reveal that lattice expansion only contributes a small fraction of phonon energy shift and that vibrant motions away from the bonds are predominate factors. This study gains deeper insight into the understanding of dynamic behaviors of the phonon and provides a new avenue to measure local temperature in nanodevices.

Observation of Strong Polarization Enhancement in Ferroelectric Tunnel Junctions.

Ferroelectric heterostructures, with capability of storing data at ultrahigh densities, could act as the platform for next-generation memories. The development of new device paradigms has been hampered by the long-standing notion of inevitable ferroelectricity suppression under reduced dimensions. Despite recent experimental observation of stable polarized states in ferroelectric ultrathin films, the out-of-plane polarization components in these films are strongly attenuated compared to thicker films, implying a degradation of device performance in electronic miniaturization processes. Here, in a model system of BiFeO3/La0.7Sr0.3MnO3, we report observation of a dramatic out-of-plane polarization enhancement that occurs with decreasing film thickness. Our electron microscopy analysis coupled with phase-field simulations reveals a polarization-enhancement mechanism that is dominated by the accumulation of oxygen vacancies at interfacial layers. The results shed light on the interplay between polarization and defects in nanoscale ferroelectrics and suggest a route to enhance functionality in oxide devices.

Domain Architectures and Grain Boundaries in Chemical Vapor Deposited Highly Anisotropic ReS2 Monolayer Films.

Recent studies have shown that vapor phase synthesis of structurally isotropic two-dimensional (2D) MoS2 and WS2 produces well-defined domains with clean grain boundaries (GBs). This is anticipated to be vastly different for 2D anisotropic materials like ReS2 mainly due to large anisotropy in interfacial energy imposed by its distorted 1T crystal structure and formation of signature Re-chains along [010] b-axis direction. Here, we provide first insight on domain architecture on chemical vapor deposited (CVD) ReS2 domains using high-resolution scanning transmission electron microscopy, angle-resolved nano-Raman spectroscopy, reflectivity, and atomic force microscopy measurements. Results provide ways to achieve crystalline anisotropy in CVD ReS2, establish domain architecture of high symmetry ReS2 flakes, and determine Re-chain orientation within subdomains. Results also provide a first atomic resolution look at ReS2 GBs, and surprisingly we find that cluster and vacancy defects, formed by collusion of Re-chains at the GBs, dramatically impact the crystal structure by changing the Re-chain direction and rotating Re-chains 180° along their b-axis. Overall results not only shed first light on domain architecture and structure of anisotropic 2D systems but also allow one to attain much desired crystalline anisotropy in CVD grown ReS2 for the first time for tangible applications in photonics and optoelectronics where direction-dependent dichroic and linearly polarized material properties are required.

Structure and segregation of dopant-defect complexes at grain boundaries in nanocrystalline doped ceria.

Grain boundaries (GBs) dictate vital properties of nanocrystalline doped ceria. Thus, to understand and predict its properties, knowledge of the interaction between dopant-defect complexes and GBs is crucial. Here, we report atomistic simulations, corroborated with first principles calculations, elucidating the fundamental dopant-defect interactions at model GBs in gadolinium-doped and manganese-doped ceria. Gadolinium and manganese are aliovalent dopants, accommodated in ceria via a dopant-defect complex. While the behavior of isolated dopants and vacancies is expected to depend on the local atomic structure at GBs, the added structural complexity associated with dopant-defect complexes is found to have key implications on GB segregation. Compared to the grain interior, energies of different dopant-defect arrangements vary significantly at the GBs. As opposed to bulk, the stability of oxygen vacancy is found to be sensitive to the dopant arrangement at GBs. Manganese exhibits a stronger propensity for segregation to GBs than gadolinium, revealing that accommodation of dopant-defect clusters depends on the nature of dopants. Segregation strength is found to depend on the GB character, a result qualitatively supported by our experimental observations based on scanning transmission electron microscopy. The present results indicate that segregation energies, availability of favorable sites, and overall stronger binding of dopant-defect complexes would influence ionic conductivity across GBs in nanocrystalline doped ceria. Our comprehensive investigation emphasizes the critical role of dopant-defect interactions at GBs in governing functional properties in fluorite-structured ionic conductors.

Nanoparticle-directed bimodal crystallization of the quasi-1D van der Waals phase, Bi4I4.

Anisotropy often yields unexpected structures and properties in the solid state. In van der Waals (vdW) solids comprised of 1D or quasi-1D (q-1D) building blocks, anisotropy in both intra- and inter-chain directions results in an abundance of crystalline packing motifs and drastically altered physical states. Among these, structurally and chemically complex 1D/q-1D vdW solids that display topologically protected states, unique optical properties, and enhanced electrical transport properties in 1D are sought after owing to their potential as building blocks for next-generation quantum devices that approach the sub-nanometer regime. Yet, the access to such facet- and edge-specific physical states is still limited by the stochastic nature of micromechanical exfoliation. Here, we demonstrate that the representative Bi4I4 phase, an established pnictohalide q-1D vdW topological insulator in the bulk, can be crystallized from the vapor phase either into well-defined nanowires or quasi-2D nanosheets. We find that gold nanoparticles (Au NPs) on the growth substrate, in conjunction with the highly anisotropic structure of Bi4I4 common to many q-1D vdW crystals, direct the dimensionality of high-purity Bi4I4 nanostructures. Systematic variation of Au NP diameters, Bi : I precursor ratios, and growth-deposition temperatures reveal that Au NPs generally act as nucleation sites for vapor-solid (VS) growth of Bi4I4 nanowires. Strikingly, post-synthesis analyses of the elemental composition of 20 nm Au NPs on the substrate surface show an equisotichiometric 1 : 1 ratio of Bi to I within the Au NP that triggers the vapor-liquid-solid (VLS) growth of [001]-oriented quasi-2D nanosheets comprised of laterally-ordered [Bi4I4]n chains along the perpendicular [100] direction. We rationalize the observed bimodal growth pathways and the morphologically distinct nanostructures based on crystallization habits and orientations of the nanostructures, Bi : I ratios in the resulting Au NPs post-synthesis, and the orientation of stereochemically active Bi lone pairs between adjacent chains. We anticipate that these growth pathways are adaptable to the synthesis of emergent halide- and chalcogen-based 1D vdW nanocrystals with diverse physical and quantum properties.

Encapsulation of crystalline and amorphous Sb2S3 within carbon and boron nitride nanotubes.

The recent rediscovery of 1D and quasi-1D (q-1D) van der Waals (vdW) crystals has laid foundation for the realization of emergent electronic, optical, and quantum-confined physical phenomena in both bulk and at the nanoscale. Of these, the highly anisotropic q-1D vdW crystal structure and the visible-light optical/optoelectronic properties of antimony trisulfide (Sb2S3) have led to its widespread consideration as a promising building block for photovoltaic and non-volatile phase change devices. However, while these applications will greatly benefit from well-defined and sub-nanometer-thick q-1D structures, little has been known about feasible synthetic routes that can access single covalent chains of Sb2S3. In this work, we explore how encapsulation in single or multi-walled carbon nanotubes (SWCNTs or MWCNTs) and visible-range transparent boron nitride nanotubes (BNNTs) influences the growth and phase of Sb2S3 nanostructures. We demonstrate that nanotubes with smaller diameters had a more pronounced effect in the crystallographic growth direction and orientation of Sb2S3 nanostructures, promoting the crystallization of the guest structures along the long-axis [010]-direction. As such, we were able to reliably access well-ordered few to single covalent chains of Sb2S3 when synthesized within defect-free SWCNTs with sub-2 nm inner diameters. Intriguingly, we found that the degree of crystalline order of Sb2S3 nanostructures was strongly influenced by the presence of defects and discontinuities along the Sb2S3-nanotube interface. We show that amorphous nanowire domains of Sb2S3 form around defect sites in larger, multi-walled nanotubes that manifest inner wall defects and discontinuities, suggesting a means to manipulate the crystallization dynamics of confined sub-10 nm-thick Sb2S3 nanostructures within nanotubes. Lastly, we show that ultranarrow amorphous Sb2S3 can impart functionality onto isolable BNNTs with photocurrent generation in the pA range which, alongside the dispersibility of the Sb2S3@BNNTs, could be leveraged to easily fabricate photoresistors only a few nm in width. Altogether, our results serve to solidify the understanding of how q-1D vdW pnictogen chalcogenides crystallize within confined synthetic platforms and are a step towards realizing functional materials from ensembles of encapsulated heterostructures.

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals.

Interfacing organic molecular groups with well-defined inorganic lattices, especially in low dimensions, enables synthetic routes for the rational manipulation of both their local or extended lattice structures and physical properties. While appreciably studied in two-dimensional systems, the influence of surface organic substituents on many known and emergent one-dimensional (1D) and quasi-1D (q-1D) crystals has remained underexplored. Herein, we demonstrate the surface functionalization of bulk and nanoscale Chevrel-like q-1D ionic crystals using In2Mo6Te6, a predicted q-1D Dirac semimetal, as the model phase. Using a series of alkyl ammonium (-NR4+; R = H, methyl, ethyl, butyl, and octyl) substituents with varying chain lengths, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction with longer chain substituents. Additionally, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction as the alkyl chain substituents become longer using a combination of powder X-ray diffraction and Raman experiments. Beyond the structural modulation that the substituted groups can impose on the lattice, we also found that the substitution of ammonium-based groups on the surface of the nanocrystals resulted in selective suspension in aqueous (NH4+-functionalized) or organic solvents (NOc4+-functionalized), imparted fluorescent character (Rhodamine B-functionalized), and modulated the electrical conductivity of the nanocrystal ensemble. Altogether, our results underscore the potential of organic-inorganic interfacing strategies to tune the structural and physical properties of rediscovered Chevrel-type q-1D ionic solids and open opportunities for the development of surface-addressable building blocks for hybrid electronic and optoelectronic devices at the nanoscale.