Baichang Li

Manipulating the nanostructure of materials is critical for numerous applications in electronics, magnetics, and photonics. However, conventional methods such as lithography and laser writing require cleanroom facilities or leave residue. We describe an approach to creating atomically sharp line defects in hexagonal boron nitride (hBN) at room temperature by direct optical phonon excitation with a mid-infrared pulsed laser from free space. We term this phenomenon “unzipping” to describe the rapid formation and growth of a crack tens of nanometers wide from a point within the laser-driven region. Formation of these features is attributed to the large atomic displacement and high local bond strain produced by strongly driving the crystal at a natural resonance. This process occurs only via coherent phonon excitation and is highly sensitive to the relative orientation of the crystal axes and the laser polarization. Its cleanliness, directionality, and sharpness enable applications such as polariton cavities, phonon-wave coupling, and in situ flake cleaving.

Ferroelectricity, a spontaneous and reversible electric polarization, is found in certain classes of van der Waals (vdW) materials. The discovery of ferroelectricity in twisted vdW layers provides new opportunities to engineer spatially dependent electric and optical properties associated with the configuration of moiré superlattice domains and the network of domain walls. Here, we employ near-field infrared nano-imaging and nano-photocurrent measurements to study ferroelectricity in minimally twisted WSe₂. The ferroelectric domains are visualized through the imaging of the plasmonic response in a graphene monolayer adjacent to the moiré WSe₂ bilayers. Specifically, we find that the ferroelectric polarization in moiré domains is imprinted on the plasmonic response of the graphene. Complementary nano-photocurrent measurements demonstrate that the optoelectronic properties of graphene are also modulated by the proximal ferroelectric domains. Our approach represents an alternative strategy for studying moiré ferroelectricity at native length scales and opens promising prospects for (opto)electronic devices.

Two-dimensional transition-metal dichalcogenides (TMDs) have attracted tremendous interest due to the unusual electronic and optoelectronic properties of isolated monolayers and the ability to assemble diverse monolayers into complex heterostructures. To understand the intrinsic properties of TMDs and fully realize their potential in applications and fundamental studies, high-purity materials are required. Here, we describe the synthesis of TMD crystals using a two-step flux growth method that eliminates a major potential source of contamination. Detailed characterization of TMDs grown by this two-step method reveals charged and isovalent defects with densities an order of magnitude lower than those in TMDs grown by a single-step flux technique. For WSe₂, we show that increasing the Se/W ratio during growth reduces point defect density, with crystals grown at 100:1 ratio achieving charged and isovalent defect densities below 10¹⁰ and 10¹¹ cm^-2, respectively. Initial temperature-dependent electrical transport measurements of monolayer WSe₂ yield room-temperature hole mobility above 840 cm²/(V s) and low-temperature disorder-limited mobility above 44,000 cm²/(V s). Electrical transport measurements of graphene-WSe₂ heterostructures fabricated from the two-step flux grown WSe₂ also show superior performance: higher graphene mobility, lower charged impurity density, and well-resolved integer quantum Hall states. Finally, we demonstrate that the two-step flux technique can be used to synthesize other TMDs with similar defect densities, including semiconducting 2H-MoSe₂ and 2H-MoTe₂ and semimetallic T_d-WTe₂ and 1T'-MoTe₂.

The optoelectronic and transport properties of two-dimensional transition metal dichalcogenide semiconductors (2D TMDs) are highly susceptible to external perturbation, enabling precise tailoring of material function through postsynthetic modifications. Here, we show that nanoscale inhomogeneities known as nanobubbles can be used for both strain and, less invasively, dielectric tuning of exciton transport in bilayer tungsten disulfide (WSe₂). We use ultrasensitive spatiotemporally resolved optical scattering microscopy to directly image exciton transport, revealing that dielectric nanobubbles are surprisingly efficient at funneling and trapping excitons at room temperature, even though the energies of the bright excitons are negligibly affected. Our observations suggest that exciton funneling in dielectric inhomogeneities is driven by momentum-indirect (dark) excitons whose energies are more sensitive to dielectric perturbations than bright excitons. These results reveal a new pathway to control exciton transport in 2D semiconductors with exceptional spatial and energetic precision using dielectric engineering of dark state energetic landscapes.

Two-dimensional semiconducting ferroelectrics can enable new technology for low-energy electronic switching. However, conventional ferroelectric materials are usually electrically insulating and suffer from severe depolarization effects when downscaled to atomic thickness. Following recent work, we show that robust ferroelectricity can be obtained from nonferroelectric semiconducting 2H-WSe₂ by creating R-stacked bilayers with broken inversion symmetry. Here, we identify that the phase transition order of this artificial ferroelectric heterostructure is first-order, with a discontinuous jump in the order parameter across the phase transition temperature. The Curie temperature has been experimentally determined as 353 K. Using the Landau-Devonshire theory, we further determine the Curie–Weiss temperatures to be 351.2 K. We additionally demonstrate the robustness of this artificial ferroelectric material using consecutive polarization measurements, where no appreciable deterioration was detected.

Excitons play a dominant role in the optoelectronic properties of atomically thin van der Waals (vdW) semiconductors. These excitons are amenable to on-demand engineering with diverse control knobs, including dielectric screening, interlayer hybridization, and moiré potentials. However, external stimuli frequently yield heterogeneous excitonic responses at the nano- and meso-scales, making their spatial characterization with conventional diffraction-limited optics a formidable task. Here, we use a scattering-type scanning near-field optical microscope (s-SNOM) to acquire exciton spectra in atomically thin transition metal dichalcogenide microcrystals with previously unattainable 20 nm resolution. Our nano-optical data revealed material- and stacking-dependent exciton spectra of MoSe₂, WSe₂, and their heterostructures. Furthermore, we extracted the complex dielectric function of these prototypical vdW semiconductors. s-SNOM hyperspectral images uncovered how the dielectric screening modifies excitons at length scales as short as few nanometers. This work paves the way towards understanding and manipulation of excitons in atomically thin layers at the nanoscale.

Two-dimensional (2D) materials and their in-plane and out-of-plane (i.e., van der Waals, vdW) heterostructures are promising building blocks for next-generation electronic and optoelectronic devices. Since the performance of the devices is strongly dependent on the crystalline quality of the materials and the interface characteristics of the heterostructures, a fast and nondestructive method for distinguishing and characterizing various 2D building blocks is desirable to promote the device integrations. In this work, based on the color space information on 2D materials’ optical microscopy images, an artificial neural network-based deep learning algorithm is developed and applied to identify eight kinds of 2D materials with accuracy well above 90% and a mean value of 96%. More importantly, this data-driven method enables two interesting functionalities: (1) resolving the interface distribution of chemical vapor deposition (CVD) grown in-plane and vdW heterostructures and (2) identifying defect concentrations of CVD-grown 2D semiconductors. The two functionalities can be utilized to quickly identify sample quality and optimize synthesis parameters in the future. Our work improves the characterization efficiency of atomically thin materials and is therefore valuable for their research and applications.

Nickel nanoparticles drive the width of bilayer nanoribbons down to 8 nm, enabling quantum transport at high temperatures.

Chiral Weyl fermions with linear energy-momentum dispersion in the bulk accompanied by Fermi-arc states on the surfaces prompt a host of enticing optical effects. While new Weyl semimetal materials keep emerging, the available optical probes are limited. In particular, isolating bulk and surface electrodynamics in Weyl conductors remains a challenge. We devised an approach to the problem based on near-field photocurrent imaging at the nanoscale and applied this technique to a prototypical Weyl semimetal TaIrTe₄. As a first step, we visualized nano-photocurrent patterns in real space and demonstrated their connection to bulk nonlinear conductivity tensors through extensive modeling augmented with density functional theory calculations. Notably, our nanoscale probe gives access to not only the in-plane but also the out-of-plane electric fields so that it is feasible to interrogate all allowed nonlinear tensors including those that remained dormant in conventional far-field optics. Surface- and bulk-related nonlinear contributions are distinguished through their “symmetry fingerprints” in the photocurrent maps. Robust photocurrents also appear at mirror-symmetry breaking edges of TaIrTe₄ single crystals that we assign to nonlinear conductivity tensors forbidden in the bulk. Nano-photocurrent spectroscopy at the boundary reveals a strong resonance structure absent in the interior of the sample, providing evidence for elusive surface states. Significance Nonlinear optics in topological semimetals is a burgeoning field of research with an expanding list of new materials but limited choice of probes. We devised, modeled, and implemented an approach for investigating nonlinear optics at the nanoscale with a metallic tip. Far-field nonlinear optics are diffraction-limited and probe the in-plane response only. Our tip-based approach circumvents the diffraction limit and provides strong field enhancement for both in-plane and out-of-plane fields. We therefore gain access to complete nonlinear tensors including components not attainable before. One immediate application of our approach is the separation of surface state and bulk nonlinear responses in Weyl semimetals. Applying near-field probes to topological semimetals constitutes a new paradigm of research on nanoscale nonlinearity.