Terahertz phonon engineering with van der Waals heterostructures.

Phonon engineering at gigahertz frequencies forms the foundation of microwave acoustic filters1, acousto-optic modulators2 and quantum transducers3,4. Terahertz phonon engineering could lead to acoustic filters and modulators at higher bandwidth and speed, as well as quantum circuits operating at higher temperatures. Despite their potential, methods for engineering terahertz phonons have been limited due to the challenges of achieving the required material control at subnanometre precision and efficient phonon coupling at terahertz frequencies. Here we demonstrate the efficient generation, detection and manipulation of terahertz phonons through precise integration of atomically thin layers in van der Waals heterostructures. We used few-layer graphene as an ultrabroadband phonon transducer that converts femtosecond near-infrared pulses to acoustic-phonon pulses with spectral content up to 3 THz. A monolayer WSe2 is used as a sensor. The high-fidelity readout was enabled by the exciton-phonon coupling and strong light-matter interactions. By combining these capabilities in a single heterostructure and detecting responses to incident mechanical waves, we performed terahertz phononic spectroscopy. Using this platform, we demonstrate high-Q terahertz phononic cavities and show that a WSe2 monolayer embedded in hexagonal boron nitride can efficiently block the transmission of terahertz phonons. By comparing our measurements to a nanomechanical model, we obtained the force constants at the heterointerfaces. Our results could enable terahertz phononic metamaterials for ultrabroadband acoustic filters and modulators and could open new routes for thermal engineering.

Low Resistance Contact to P-Type Monolayer WSe2.

Advanced microelectronics in the future may require semiconducting channel materials beyond silicon. Two-dimensional (2D) semiconductors, with their atomically thin thickness, hold great promise for future electronic devices. One challenge to achieving high-performance 2D semiconductor field effect transistors (FET) is the high contact resistance at the metal-semiconductor interface. In this study, we develop a charge-transfer doping strategy with WSe2/α-RuCl3 heterostructures to achieve low-resistance ohmic contact for p-type monolayer WSe2 transistors. We show that hole doping as high as 3 × 1013 cm-2 can be achieved in the WSe2/α-RuCl3 heterostructure due to its type-III band alignment, resulting in an ohmic contact with resistance of 4 kΩ µm. Based on that, we demonstrate p-type WSe2 transistors with an on-current of 35 µA·µm-1 and an ION/IOFF ratio exceeding 109 at room temperature.

Atomic-scale observation of localized phonons at FeSe/SrTiO3 interface.

In single unit-cell FeSe grown on SrTiO3, the superconductivity transition temperature features a significant enhancement. Local phonon modes at the interface associated with electron-phonon coupling may play an important role in the interface-induced enhancement. However, such phonon modes have eluded direct experimental observations. The complicated atomic structure of the interface brings challenges to obtain the accurate structure-phonon relation knowledge. Here, we achieve direct characterizations of atomic structure and phonon modes at the FeSe/SrTiO3 interface with atomically resolved imaging and electron energy loss spectroscopy in an electron microscope. We find several phonon modes highly localized (~1.3 nm) at the unique double layer Ti-O terminated interface, one of which (~ 83 meV) engages in strong interactions with the electrons in FeSe based on ab initio calculations. This finding of the localized interfacial phonon associated with strong electron-phonon coupling provides new insights into understanding the origin of superconductivity enhancement at the FeSe/SrTiO3 interface.

Nanoscale Localized Phonons at Al2O3 Grain Boundaries.

Nanoscale defects like grain boundaries (GBs) would introduce local phonon modes and affect the bulk materials' thermal, electrical, optical, and mechanical properties. It is highly desirable to correlate the phonon modes and atomic arrangements for individual defects to precisely understand the structure-property relation. Here we investigated the localized phonon modes of Al2O3 GBs by combination of the vibrational electron energy loss spectroscopy (EELS) in scanning transmission electron microscope and density functional perturbation theory (DFPT). The differences between GB and bulk obtained from the vibrational EELS show that the GB exhibited more active vibration at the energy range of <50 meV and >80 meV, and further DFPT results proved the wide distribution of bond lengths at GB are the main factor for the emergence of local phonon modes. This research provides insights into the phonon-defect relation and would be of importance in the design and application of polycrystalline materials.

Probing Hyperbolic Shear Polaritons in ß-Ga2O3 Nanostructures Using STEM-EELS.

Phonon polaritons, quasiparticles arising from strong coupling between electromagnetic waves and optical phonons, have potential for applications in subdiffraction imaging, sensing, thermal conduction enhancement, and spectroscopy signal enhancement. A new class of phonon polaritons in low-symmetry monoclinic crystals, hyperbolic shear polaritons (HShPs), have been verified recently in ß-Ga2O3 by free electron laser (FEL) measurements. However, detailed behaviors of HShPs in ß-Ga2O3 nanostructures still remain unknown. Here, by using monochromatic electron energy loss spectroscopy in conjunction with scanning transmission electron microscopy, the experimental observation of multiple HShPs in ß-Ga2O3 in the mid-infrared (MIR) and far-infrared (FIR) ranges is reported. HShPs in various ß-Ga2O3 nanorods and a ß-Ga2O3 nanodisk are excited. The frequency-dependent rotation and shear effect of HShPs reflect on the distribution of EELS signals. The propagation and reflection of HShPs in nanostructures are clarified by simulations of electric field distribution. These findings suggest that, with its tunable broad spectral HShPs, ß-Ga2O3 is an excellent candidate for nanophotonic applications.

Engineering correlated insulators in bilayer graphene with a remote Coulomb superlattice.

Electron superlattices allow the engineering of correlated and topological quantum phenomena. The recent emergence of moiré superlattices in two-dimensional heterostructures has led to exciting discoveries related to quantum phenomena. However, the requirement for the moiré pattern poses stringent limitations, and its potential cannot be switched on and off. Here, we demonstrate remote engineering and on/off switching of correlated states in bilayer graphene. Employing a remote Coulomb superlattice realized by localized electrons in twisted bilayer WS2, we impose a Coulomb superlattice in the bilayer graphene with period and strength determined by the twisted bilayer WS2. When the remote superlattice is turned off, the two-dimensional electron gas in the bilayer graphene is described by a Fermi liquid. When it is turned on, correlated insulating states at both integer and fractional filling factors emerge. This approach enables in situ control of correlated quantum phenomena in two-dimensional materials hosting a two-dimensional electron gas.

Thermodynamic behavior of correlated electron-hole fluids in van der Waals heterostructures.

Coupled two-dimensional electron-hole bilayers provide a unique platform to study strongly correlated Bose-Fermi mixtures in condensed matter. Electrons and holes in spatially separated layers can bind to form interlayer excitons, composite Bosons expected to support high-temperature exciton condensates. The interlayer excitons can also interact strongly with excess charge carriers when electron and hole densities are unequal. Here, we use optical spectroscopy to quantitatively probe the local thermodynamic properties of strongly correlated electron-hole fluids in MoSe2/hBN/WSe2 heterostructures. We observe a discontinuity in the electron and hole chemical potentials at matched electron and hole densities, a definitive signature of an excitonic insulator ground state. The excitonic insulator is stable up to a Mott density of ~0.8 × 1012 cm-2 and has a thermal ionization temperature of ~70 K. The density dependence of the electron, hole, and exciton chemical potentials reveals strong correlation effects across the phase diagram. Compared with a non-interacting uniform charge distribution, the correlation effects lead to significant attractive exciton-exciton and exciton-charge interactions in the electron-hole fluid. Our work highlights the unique quantum behavior that can emerge in strongly correlated electron-hole systems.

Four-dimensional electron energy-loss spectroscopy.

Recent advances in scanning transmission electron microscopy have enabled atomic-scale focused, coherent, and monochromatic electron probes, achieving nanoscale spatial resolution, meV energy resolution, sufficient momentum resolution, and a wide energy detection range in electron energy-loss spectroscopy (EELS). A four-dimensional EELS (4D-EELS) dataset can be recorded with a slot aperture selecting the specific momentum direction in the diffraction plane and the beam scanning in two spatial dimensions. In this paper, the basic principle of the 4D-EELS technique and a few examples of its application are presented. In addition to parallelly acquired dispersion with energy down to a lattice vibration scale, it can map the real space variation of any EELS spectrum features with a specific momentum transfer and energy loss to study various locally inhomogeneous scattering processes. Furthermore, simple mathematical combinations associating the spectra at different momenta are feasible from the 4D dataset, e.g., the efficient acquisition of a reliable electron magnetic circular dichroism (EMCD) signal is demonstrated. This 4D-EELS technique provides new opportunities to probe the local dispersion and related physical properties at the nanoscale.

Phonon transition across an isotopic interface.

Isotopic mixtures result in distinct properties of materials such as thermal conductivity and nuclear process. However, the knowledge of isotopic interface remains largely unexplored mainly due to the challenges in atomic-scale isotopic identification. Here, using electron energy-loss spectroscopy in a scanning transmission electron microscope, we reveal momentum-transfer-dependent phonon behavior at the h-10BN/h-11BN isotope heterostructure with sub-unit-cell resolution. We find the phonons' energy changes gradually across the interface, featuring a wide transition regime. Phonons near the Brillouin zone center have a transition regime of ~3.34 nm, whereas phonons at the Brillouin zone boundary have a transition regime of ~1.66 nm. We propose that the isotope-induced charge effect at the interface accounts for the distinct delocalization behavior. Moreover, the variation of phonon energy between atom layers near the interface depends on both of momentum transfer and mass change. This study provides new insights into the isotopic effects in natural materials.

Hyperbolic whispering-gallery phonon polaritons in boron nitride nanotubes.

Light confinement in nanostructures produces an enhanced light-matter interaction that enables a vast range of applications including single-photon sources, nanolasers and nanosensors. In particular, nanocavity-confined polaritons display a strongly enhanced light-matter interaction in the infrared regime. This interaction could be further boosted if polaritonic modes were moulded to form whispering-gallery modes; but scattering losses within nanocavities have so far prevented their observation. Here, we show that hexagonal BN nanotubes act as an atomically smooth nanocavity that can sustain phonon-polariton whispering-gallery modes, owing to their intrinsic hyperbolic dispersion and low scattering losses. Hyperbolic whispering-gallery phonon polaritons on BN nanotubes of ～4 nm radius (sidewall of six atomic layers) are characterized by an ultrasmall nanocavity mode volume (Vm ≈ 10-10λ03 at an optical wavelength λ0 ≈ 6.4 µm) and a Purcell factor (Q/Vm) as high as 1012. We posit that BN nanotubes could become an important material platform for the realization of one-dimensional, ultrastrong light-matter interactions, with exciting implications for compact photonic devices.

Charge Transfer Dynamics in MoSe2/hBN/WSe2 Heterostructures.

Ultrafast charge transfer processes provide a facile way to create interlayer excitons in directly contacted transition metal dichalcogenide (TMD) layers. More sophisticated heterostructures composed of TMD/hBN/TMD enable new ways to control interlayer exciton properties and achieve novel exciton phenomena, such as exciton insulators and condensates, where longer lifetimes are desired. In this work, we experimentally study the charge transfer dynamics in a heterostructure composed of a 1 nm thick hBN spacer between MoSe2 and WSe2 monolayers. We observe the hole transfer from MoSe2 to WSe2 through the hBN barrier with a time constant of 500 ps, which is over 3 orders of magnitude slower than that between TMD layers without a spacer. Furthermore, we observe strong competition between the interlayer charge transfer and intralayer exciton-exciton annihilation processes at high excitation densities. Our work opens possibilities to understand charge transfer pathways in TMD/hBN/TMD heterostructures for the efficient generation and control of interlayer excitons.

Dynamics of Polar Skyrmion Bubbles under Electric Fields.

Room-temperature polar skyrmions, which have been recently discovered in oxide superlattice, have received considerable attention for their potential applications in nanoelectronics owing to their nanometer size, emergent chirality, and negative capacitance. For practical applications, their manipulation using external stimuli is a prerequisite. Herein, we study the dynamics of individual polar skyrmions at the nanoscale via in situ scanning transmission electron microscopy. By monitoring the electric-field-driven creation, annihilation, shrinkage, and expansion of topological structures in real space, we demonstrate the reversible transformation among skyrmion bubbles, elongated skyrmions, and monodomains. The underlying mechanism and interactions are discussed in conjunction with phase-field simulations. The electrical manipulation of nanoscale polar skyrmions allows the tuning of their dielectric permittivity at the atomic scale, and the detailed knowledge of their phase transition behaviors provides fundamentals for their applications in nanoelectronics.

Studying Plasmon Dispersion of MXene for Enhanced Electromagnetic Absorption.

2D metal carbides and nitrides (MXene) are promising candidates for electromagnetic (EM) shielding, saturable absorption, thermal therapy, and photocatalysis owing to their excellent EM absorption. The plasmon resonances in metallic MXene micro/nanostructures may play an important role in enhancing the EM absorption; however, their contribution has not been determined due to the lack of a precise understanding of its plasmon behavior. Here, the use of high-spatial-resolution electron energy-loss spectroscopy to measure the plasmon dispersion of MXene films with different thicknesses is reported, enabling accurate analysis of the EM absorption of complex MXene structures in a wide frequency range via a theoretical model. The EM absorption of MXene can be excited at the desired frequency by controlling the momentum (e.g., the sizes of the nanoflakes for EM excitation) as the strength can be enhanced by increasing the layer number and the interlayer distance in MXene. For example, a 3 nm interlayer distance can nearly double the plasmon-enhanced EM absorption in MXene nanostructures. These findings can guide the design of advanced ultrathin EM absorption materials for a broad range of applications.

Atomic-scale probing of heterointerface phonon bridges in nitride semiconductor.

Interface phonon modes that are generated by several atomic layers at the heterointerface play a major role in the interface thermal conductance for nanoscale high-power devices such as nitride-based high-electron-mobility transistors and light-emitting diodes. Here we measure the local phonon spectra across AlN/Si and AlN/Al interfaces using atomically resolved vibrational electron energy-loss spectroscopy in a scanning transmission electron microscope. At the AlN/Si interface, we observe various interface phonon modes, of which the extended and localized modes act as bridges to connect the bulk AlN modes and bulk Si modes and are expected to boost the phonon transport, thus substantially contributing to interface thermal conductance. In comparison, no such phonon bridge is observed at the AlN/Al interface, for which partially extended modes dominate the interface thermal conductivity. This work provides valuable insights into understanding the interfacial thermal transport in nitride semiconductors and useful guidance for thermal management via interface engineering.

Measuring phonon dispersion at an interface.

The breakdown of translational symmetry at heterointerfaces leads to the emergence of new phonon modes localized at the interface1. These modes have an essential role in thermal and electrical transport properties in devices, especially in miniature ones wherein the interface may dominate the entire response of the device2. Although related theoretical work began decades ago1,3-5, experimental research is totally absent owing to challenges in achieving the combined spatial, momentum and spectral resolutions required to probe localized modes. Here, using the four-dimensional electron energy-loss spectroscopy technique, we directly measure both the local vibrational spectra and the interface phonon dispersion relation for an epitaxial cubic boron nitride/diamond heterointerface. In addition to bulk phonon modes, we observe modes localized at the interface and modes isolated from the interface. These features appear only within approximately one nanometre around the interface. The localized modes observed here are predicted to substantially affect the interface thermal conductance and electron mobility. Our findings provide insights into lattice dynamics at heterointerfaces, and the demonstrated experimental technique should be useful in thermal management, electrical engineering and topological phononics.

Anisotropic moiré optical transitions in twisted monolayer/bilayer phosphorene heterostructures.

Moiré superlattices of van der Waals heterostructures provide a powerful way to engineer electronic structures of two-dimensional materials. Many novel quantum phenomena have emerged in graphene and transition metal dichalcogenide moiré systems. Twisted phosphorene offers another attractive system to explore moiré physics because phosphorene features an anisotropic rectangular lattice, different from isotropic hexagonal lattices previously reported. Here we report emerging anisotropic moiré optical transitions in twisted monolayer/bilayer phosphorenes. The optical resonances in phosphorene moiré superlattice depend sensitively on twist angle and are completely different from those in the constitute monolayer and bilayer phosphorene even for a twist angle as large as 19°. Our calculations reveal that the Γ-point direct bandgap and the rectangular lattice of phosphorene give rise to the remarkably strong moiré physics in large-twist-angle phosphorene heterostructures. This work highlights fresh opportunities to explore moiré physics in phosphorene and other van der Waals heterostructures with different lattice configurations.

Four-dimensional vibrational spectroscopy for nanoscale mapping of phonon dispersion in BN nanotubes.

Directly mapping local phonon dispersion in individual nanostructures can advance our understanding of their thermal, optical, and mechanical properties. However, this requires high detection sensitivity and combined spatial, energy and momentum resolutions, thus has been elusive. Here, we demonstrate a four-dimensional electron energy loss spectroscopy technique, and present position-dependent phonon dispersion measurements in individual boron nitride nanotubes. By scanning the electron beam in real space while monitoring both the energy loss and the momentum transfer, we are able to reveal position- and momentum-dependent lattice vibrations at nanometer scale. Our measurements show that the phonon dispersion of multi-walled nanotubes is locally close to hexagonal-boron nitride crystals. Interestingly, acoustic phonons are sensitive to defect scattering, while optical modes are insensitive to small voids. This work not only provides insights into vibrational properties of boron nitride nanotubes, but also demonstrates potential of the developed technique in nanoscale phonon dispersion measurements.

Direct observation of highly confined phonon polaritons in suspended monolayer hexagonal boron nitride.

Phonon polaritons enable light confinement at deep subwavelength scales, with potential technological applications, such as subdiffraction imaging, sensing and engineering of spontaneous emission. However, the trade-off between the degree of confinement and the excitation efficiency of phonon polaritons prevents direct observation of these modes in monolayer hexagonal boron nitride (h-BN), where they are expected to reach ultrahigh confinement. Here, we use monochromatic electron energy-loss spectroscopy (about 7.5 meV energy resolution) in a scanning transmission electron microscope to measure phonon polaritons in monolayer h-BN, directly demonstrating the existence of these modes as the phonon Reststrahlen band (RS) disappears. We find phonon polaritons in monolayer h-BN to exhibit high confinement (>487 times smaller wavelength than that of light in free space) and ultraslow group velocity down to about 10-5c. The large momentum compensation provided by electron beams additionally allows us to excite phonon polaritons over nearly the entire RS band of multilayer h-BN. These results open up a broad range of opportunities for the engineering of metasurfaces and strongly enhanced light-matter interactions.

Broad-Spectral-Range Sustainability and Controllable Excitation of Hyperbolic Phonon Polaritons in α-MoO3.

Hyperbolic phonon polaritons (HPhPs) in orthorhombic-phase molybdenum trioxide (α-MoO3 ) show in-plane hyperbolicity, great wavelength compression, and ultralong lifetime, therefore holding great potential in nanophotonic applications. However, its polaritonic response in the far-infrared (FIR) range remains unexplored due to challenges in experimental characterization. Here, monochromated electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) is used to probe HPhPs in α-MoO3 in both mid-infrared (MIR) and FIR frequencies and correlate their behaviors with microstructures and orientations. It is found that low structural symmetry leads to various phonon modes and multiple Reststrahlen bands (RBs) over a broad spectral range (over 70 meV) and in different directions (55-63 meV and 119-125 meV along the b-axis, 68-106 meV along the c-axis, and 101-121 meV along the a-axis). These HPhPs can be selectively excited by controlling the direction of swift electrons. These findings provide new opportunities in nanophotonic and optoelectronic applications, such as directed light propagation, hyperlenses, and heat transfer.

Manipulation of surface phonon polaritons in SiC nanorods.

Surface phonon polaritons (SPhPs) are potentially very attractive for subwavelength control and manipulation of light at the infrared to terahertz wavelengths. Probing their propagation behavior in nanostructures is crucial to guide rational device design. Here, aided by monochromatic scanning transmission electron microscopy-electron energy loss spectroscopy technique, we measure the dispersion relation of SPhPs in individual SiC nanorods and reveal the effects of size and shape. We find that the SPhPs can be modulated by the geometric shape and size of SiC nanorods. The energy of SPhPs shows red-shift with decreasing radius and the surface optical phonon is mainly concentrated on the surface with large radius. Therefore, the fields can be precisely confined in specific positions by varying the size of the nanorod, allowing effective tuning at nanometer scale. The findings of this work are in agreement with dielectric response theory and numerical simulation, and provide novel strategies for manipulating light in polar dielectrics through shape and size control, enabling the design of novel nanoscale phonon-photonic devices.