Electrostatic moiré potential from twisted hexagonal boron nitride layers.

Moiré superlattices host a rich variety of correlated electronic phases. However, the moiré potential is fixed by interlayer coupling, and it is dependent on the nature of carriers and valleys. In contrast, it has been predicted that twisted hexagonal boron nitride (hBN) layers can impose a periodic electrostatic potential capable of engineering the properties of adjacent functional layers. Here, we show that this potential is described by a theory of electric polarization originating from the interfacial charge redistribution, validated by its dependence on supercell sizes and distance from the twisted interfaces. This enables controllability of the potential depth and profile by controlling the twist angles between the two interfaces. Employing this approach, we further demonstrate how the electrostatic potential from a twisted hBN substrate impedes exciton diffusion in semiconductor monolayers, suggesting opportunities for engineering the properties of adjacent functional layers using the surface potential of a twisted hBN substrate.

Evidence for moiré excitons in van der Waals heterostructures.

Recent advances in the isolation and stacking of monolayers of van der Waals materials have provided approaches for the preparation of quantum materials in the ultimate two-dimensional limit1,2. In van der Waals heterostructures formed by stacking two monolayer semiconductors, lattice mismatch or rotational misalignment introduces an in-plane moiré superlattice3. It is widely recognized that the moiré superlattice can modulate the electronic band structure of the material and lead to transport properties such as unconventional superconductivity4 and insulating behaviour driven by correlations5-7; however, the influence of the moiré superlattice on optical properties has not been investigated experimentally. Here we report the observation of multiple interlayer exciton resonances with either positive or negative circularly polarized emission in a molybdenum diselenide/tungsten diselenide (MoSe2/WSe2) heterobilayer with a small twist angle. We attribute these resonances to excitonic ground and excited states confined within the moiré potential. This interpretation is supported by recombination dynamics and by the dependence of these interlayer exciton resonances on twist angle and temperature. These results suggest the feasibility of engineering artificial excitonic crystals using van der Waals heterostructures for nanophotonics and quantum information applications.

Influence of cutoff radius and tip atomic structure on energy barriers encountered during AFM tip sliding on 2D monolayers.

In computational studies using the Lennard-Jones (LJ) potential, the widely adopted 2.5σcutoff radius effectively truncates pairwise interactions across diverse systems (Santraet al2008J. Chem. Phys.129234704, Chen and Gao 2021Friction9502-12, Bolintineanuet al2014Part. Mech.1321-56, Takahiro and Kazuhiro 2010J. Phys.: Conf. Ser.215012123, Zhouet al2016Fuel180718-26, Toxvaerd and Dyre 2011J. Chem. Phys.134081102, Toxvaerd and Dyre 2011J. Chem. Phys.134081102). Here, we assess its adequacy in determining energy barriers encountered by a Si monoatomic tip sliding on various two-dimensional (2D) monolayers, which is crucial for understanding nanoscale friction. Our findings emphasize the necessity of a cutoff radius of at least 3.5σto achieve energy barrier values exceeding 95% accuracy across all studied 2D monolayers. Specifically, 3.5σcorresponds to 12.70 Å in graphene, 12.99 Å in MoS2and 13.25 Å in MoSe2. The barrier values calculated using this cutoff support previous experiments comparing friction between different orientations of graphene and between graphene and MoS2(Almeidaet al2016Sci. Rep.631569, Zhanget al2014Sci. China57663-7). Furthermore, we demonstrate the applicability of the 3.5σcutoff for graphene on an Au substrate and bilayer graphene. Additionally, we investigate how the atomic configuration of the tip influences the energy barrier, finding a nearly threefold increase in the barrier along the zigzag direction of graphene when using a Si(001) tip composed of seven Si atoms compared to a monoatomic Si tip.

Graphene Nanoribbons with Atomically Sharp Edges Produced by AFM Induced Self-Folding.

The ability to create graphene nanoribbons with atomically sharp edges is important for various graphene applications because these edges significantly influence the overall electronic properties and support unique magnetic edge states. The discovery of graphene self-folding induced by traveling wave excitation through atomic force microscope scanning under a normal force of less than 15 nN is reported. Most remarkably, the crystallographic direction of self-folding may be either along a chosen direction defined by the scan line or along the zigzag or armchair direction in the presence of a pre-existing crack in the vicinity. The crystalline direction of the atomically sharp edge is confirmed via careful lateral force microscopy measurements. Multilayer nanoribbons with lateral dimensions of a few tens of nanometers are realized on the same graphene sheet with different folding types (e.g., z-type or double parallel). Molecular dynamics simulations reveal the folding dynamics and suggest a monotonic increase of the folded area with the applied normal force. This method may be extended to other 2D van der Waals materials and lead to nanostructures that exhibit novel edge properties without the chemical instability that typically hinders applications of etched or patterned graphene nanostructures.

Elastic coupling between layers in two-dimensional materials.

Two-dimensional materials, such as graphene and MoS2, are films of a few atomic layers in thickness with strong in-plane bonds and weak interactions between the layers. The in-plane elasticity has been widely studied in bending experiments where a suspended film is deformed substantially; however, little is known about the films' elastic modulus perpendicular to the planes, as the measurement of the out-of-plane elasticity of supported 2D films requires indentation depths smaller than the films' interlayer distance. Here, we report on sub-ångström-resolution indentation measurements of the perpendicular-to-the-plane elasticity of 2D materials. Our indentation data, combined with semi-analytical models and density functional theory, are then used to study the perpendicular elasticity of few-layer-thick graphene and graphene oxide films. We find that the perpendicular Young's modulus of graphene oxide films reaches a maximum when one complete water layer is intercalated between the graphitic planes. This non-destructive methodology can map interlayer coupling and intercalation in 2D films.

Room-temperature metastability of multilayer graphene oxide films.

Graphene oxide potentially has multiple applications. The chemistry of graphene oxide and its response to external stimuli such as temperature and light are not well understood and only approximately controlled. This understanding is crucial to enable future applications of this material. Here, a combined experimental and density functional theory study shows that multilayer graphene oxide produced by oxidizing epitaxial graphene through the Hummers method is a metastable material whose structure and chemistry evolve at room temperature with a characteristic relaxation time of about one month. At the quasi-equilibrium, graphene oxide reaches a nearly stable reduced O/C ratio, and exhibits a structure deprived of epoxide groups and enriched in hydroxyl groups. Our calculations show that the structural and chemical changes are driven by the availability of hydrogen in the oxidized graphitic sheets, which favours the reduction of epoxide groups and the formation of water molecules.

Manipulating coupling between a single semiconductor quantum dot and single gold nanoparticle.

Using atomic force microscopy nanomanipulation, we position a single Au nanoparticle near a CdSe/ZnS quantum dot to construct a hybrid nanostructure with variable geometry. The coupling between the two particles is varied in a systematic and reversible manner. The photoluminescence lifetime and blinking of the same quantum dot are measured before and after assembly of the structure. In some hybrid structures, the total lifetime is reduced from about 30 ns to well below 1 ns. This dramatic change in lifetime is accompanied by the disappearance of blinking as the nonradiative energy transfer from the CdSe/ZnS quantum dot to the Au nanoparticle becomes the dominant decay channel. Both total lifetime and photoluminescence intensity changes are well described by simple analytical calculations.

Accurate Atomic-Scale Imaging of Two-Dimensional Lattices Using Atomic Force Microscopy in Ambient Conditions.

To facilitate the rapid development of van der Waals materials and heterostructures, scanning probe methods capable of nondestructively visualizing atomic lattices and moiré superlattices are highly desirable. Lateral force microscopy (LFM), which measures nanoscale friction based on the commonly available atomic force microscopy (AFM), can be used for imaging a wide range of two-dimensional (2D) materials, but imaging atomic lattices using this technique is difficult. Here, we examined a number of the common challenges encountered in LFM experiments and presented a universal protocol for obtaining reliable atomic-scale images of 2D materials under ambient environment. By studying a series of LFM images of graphene and transition metal dichalcogenides (TMDs), we have found that the accuracy and the contrast of atomic-scale images critically depended on several scanning parameters including the scan size and the scan rate. We applied this protocol to investigate the atomic structure of the ripped and self-folded edges of graphene and have found that these edges were mostly in the armchair direction. This finding is consistent with the results of several simulations results. Our study will guide the extensive effort on assembly and characterization of new 2D materials and heterostructures.

Nonperturbative chemical modification of graphene for protein micropatterning.

Graphene's extraordinary physical properties and its planar geometry make it an ideal candidate for a wide array of applications, many of which require controlled chemical modification and the spatial organization of molecules on its surface. In particular, the ability to functionalize and micropattern graphene with proteins is relevant to bioscience applications such as biomolecular sensors, single-cell sensors, and tissue engineering. We report a general strategy for the noncovalent chemical modification of epitaxial graphene for protein immobilization and micropatterning. We show that bifunctional molecule pyrenebutanoic acid-succinimidyl ester (PYR-NHS), composed of the hydrophobic pyrene and the reactive succinimide ester group, binds to graphene noncovalently but irreversibly. We investigate whether the chemical treatment perturbs the electronic band structure of graphene using X-ray photoemission (XPS) and Raman spectroscopy. Our results show that the sp(2) hybridization remains intact and that the π band maintains its characteristic Lorentzian shape in the Raman spectra. The modified graphene surfaces, which bind specifically to amines in proteins, are micropatterned with arrays of fluorescently labeled proteins that are relevant to glucose sensors (glucose oxidase) and cell sensor and tissue engineering applications (laminin).

Controlled AFM manipulation of small nanoparticles and assembly of hybrid nanostructures.

We demonstrate controlled manipulation of semiconductor and metallic nanoparticles (NPs) with 5-15 nm diameters and assemble these NPs into hybrid structures. The manipulation is accomplished under ambient environment using a commercial atomic force microscope (AFM). There are particular difficulties associated with manipulating NPs this small. In addition to spatial drift, the shape of an asymmetric AFM tip has to be taken into account in order to understand the intended and actual manipulation results. Furthermore, small NPs often attach to the tip via electrostatic interaction and modify the effective tip shape. We suggest a method for detaching the NPs by performing a pseudo-manipulation step. Finally, we show by example the ability to assemble these small NPs into prototypical hybrid nanostructures with well-defined composition and geometry.

Moiré potential impedes interlayer exciton diffusion in van der Waals heterostructures.

The properties of van der Waals heterostructures are drastically altered by a tunable moiré superlattice arising from periodically varying atomic alignment between the layers. Exciton diffusion represents an important channel of energy transport in transition metal dichalcogenides (TMDs). While early studies performed on TMD heterobilayers suggested that carriers and excitons exhibit long diffusion, a rich variety of scenarios can exist. In a moiré crystal with a large supercell and deep potential, interlayer excitons may be completely localized. As the moiré period reduces at a larger twist angle, excitons can tunnel between supercells and diffuse over a longer lifetime. The diffusion should be the longest in commensurate heterostructures where the moiré superlattice is completely absent. Here, we experimentally demonstrate the rich phenomena of interlayer exciton diffusion in WSe2/MoSe2 heterostructures by comparing several samples prepared with chemical vapor deposition and mechanical stacking with accurately controlled twist angles.

Parallelization of thermochemical nanolithography.

One of the most pressing technological challenges in the development of next generation nanoscale devices is the rapid, parallel, precise and robust fabrication of nanostructures. Here, we demonstrate the possibility to parallelize thermochemical nanolithography (TCNL) by employing five nano-tips for the fabrication of conjugated polymer nanostructures and graphene-based nanoribbons.

The interplay between apparent viscosity and wettability in nanoconfined water.

Understanding and manipulating fluids at the nanoscale is a matter of growing scientific and technological interest. Here we show that the viscous shear forces in nanoconfined water can be orders of magnitudes larger than in bulk water if the confining surfaces are hydrophilic, whereas they greatly decrease when the surfaces are increasingly hydrophobic. This decrease of viscous forces is quantitatively explained with a simple model that includes the slip velocity at the water surface interface. The same effect is observed in the energy dissipated by a tip vibrating in water perpendicularly to a surface. Comparison of the experimental data with the model shows that interfacial viscous forces and compressive dissipation in nanoconfined water can decrease up to two orders of magnitude due to slippage. These results offer a new understanding of interfacial fluids, which can be used to control flow at the nanoscale.

Sliding on a nanotube: interplay of friction, deformations and structure.

The frictional properties of individual carbon nanotubes (CNTs) are studied by sliding an atomic force microscopy tip across and along its principle axis. This direction-dependent frictional behavior is found to correlate strongly with the presence of structural defects, surface chemistry, and CNT chirality. This study shows that it is experimentally possible to tune the frictional/adhesion properties of a CNT by controlling the CNT structure and surface chemistry, as well as use friction force to predict its structural and chemical properties.

Direct fabrication of arbitrary-shaped ferroelectric nanostructures on plastic, glass, and silicon substrates.

A complementary metal-oxide-semico-nductor (CMOS)-compatible method for the direct fabrication of arbitrary-shaped Pb(Zr0.52 Ti0.48)O3 and PbTiO3 ferroelectric/piezoelectric nanostructures on plastic, silicon, and soda-lime glass substrates is reported. Thermochemical nanolithography is used to induce nanoscale crystallization of sol-gel precursor films. Ferroelectric lines with width ≥30 nm, spheres with diameter ≥10 nm, and densities up to 213 Gb in(-2) are produced.

Nanoscale tunable reduction of graphene oxide for graphene electronics.

The reduced form of graphene oxide (GO) is an attractive alternative to graphene for producing large-scale flexible conductors and for creating devices that require an electronic gap. We report on a means to tune the topographical and electrical properties of reduced GO (rGO) with nanoscopic resolution by local thermal reduction of GO with a heated atomic force microscope tip. The rGO regions are up to four orders of magnitude more conductive than pristine GO. No sign of tip wear or sample tearing was observed. Variably conductive nanoribbons with dimensions down to 12 nanometers could be produced in oxidized epitaxial graphene films in a single step that is clean, rapid, and reliable.

Atomic force microscope nanomanipulation with simultaneous visual guidance.

Atomic force microscopy (AFM) has been used to assemble prototype nanostructures consisting of colloidal nanoparticles. In the standard manipulation protocol, the AFM is used either as a manipulation tool or an imaging tool, but not both at the same time. We developed a new nanomanipulation protocol in which simultaneous visual guidance is obtained during manipulation. As an example, Au nanoparticles were manipulated on a substrate in two steps. First, a nanoparticle is kicked with the z feedback off. This kicking event reduces the static friction. Second, the nanoparticle is dribbled to a target position in tapping mode, and visual guidance is provided by a ghost trace of the nanoparticle. The new manipulation protocol greatly improves efficiency of manipulating small nanoparticles (15 nm in diameter or smaller). Our work highlights the importance and challenges of understanding friction at the nanoscale.

Robust Ohmic contact junctions between metallic tips and multiwalled carbon nanotubes for scanned probe microscopy.

We demonstrate a simple method that uses a scanning electron microscope for making a reliable low resistance contact between a single multiwalled carbon nanotube and a metallic tungsten probe tip or a Si cantilever. This method consists of using electron beam induced decomposition of background gases and voltage pulses to remove contaminants. The electrical quality of the contact is monitored in situ by measuring the current flow at constant bias or by observing the decay of current fluctuations. The quality of the contacts is confirmed via current-voltage spectroscopy. This method produces very stable, low resistance, mechanically robust contacts with high success rates approaching 100%.