Manipulation of domain-wall solitons in bi- and trilayer graphene.

Topological dislocations and stacking faults greatly affect the performance of functional crystalline materials1-3. Layer-stacking domain walls (DWs) in graphene alter its electronic properties and give rise to fascinating new physics such as quantum valley Hall edge states4-10. Extensive efforts have been dedicated to the engineering of dislocations to obtain materials with advanced properties. However, the manipulation of individual dislocations to precisely control the local structure and local properties of bulk material remains an outstanding challenge. Here we report the manipulation of individual layer-stacking DWs in bi- and trilayer graphene by means of a local mechanical force exerted by an atomic force microscope tip. We demonstrate experimentally the capability to move, erase and split individual DWs as well as annihilate or create closed-loop DWs. We further show that the DW motion is highly anisotropic, offering a simple approach to create solitons with designed atomic structures. Most artificially created DW structures are found to be stable at room temperature.

Coupled One-Dimensional Plasmons and Two-Dimensional Phonon Polaritons in Hybrid Silver Nanowire/Silicon Carbide Structures.

Surface plasmons (SPs) and phonon polaritons (PhPs) are two distinctive quasiparticles resulting from the strong coupling of photons with electrons and optical phonons, respectively. In this Letter, we investigate the interactions between one-dimensional (1D) plasmons in silver nanowires with two-dimensional (2D) surface phonon polaritons of the silicon carbide (SiC) substrate. Using near-field infrared spectroscopy of the silver nanowire-SiC heterostructure at wavelengths close to the phonon resonance of SiC, we observe that the 1D plasmon dispersion is strongly modified by the 2D phonon polaritons in SiC. In particular, we observe for the first time well-defined 1D plasmon oscillations with the plasmon wavelengths longer than the free-space photon wavelengths due to the 1D plasmon-2D phonon polariton coupling. Our work demonstrates that unusual polariton behavior can emerge from interactions between polariton excitons of different dimensionality, which can enable new ways to engineer plasmons in hybrid structures.

Evolution of anatase surface active sites probed by in situ sum-frequency phonon spectroscopy.

Surface active sites of crystals often govern their relevant surface chemistry, yet to monitor them in situ in real atmosphere remains a challenge. Using surface-specific sum-frequency spectroscopy, we identified the surface phonon mode associated with the active sites of undercoordinated titanium ions and conjoint oxygen vacancies, and used it to monitor them on anatase (TiO2) (101) under ambient conditions. In conjunction with theory, we determined related surface structure around the active sites and tracked the evolution of oxygen vacancies under ultraviolet irradiation. We further found that unlike in vacuum, the surface oxygen vacancies, which dominate the surface reactivity, are strongly regulated by ambient gas molecules, including methanol and water, as well as weakly associated species, such as nitrogen and hydrogen. The result revealed a rich interplay between prevailing ambient species and surface reactivity, which can be omnipresent in environmental and catalytic applications of titanium dioxides.

Soliton-dependent plasmon reflection at bilayer graphene domain walls.

Layer-stacking domain walls in bilayer graphene are emerging as a fascinating one-dimensional system that features stacking solitons structurally and quantum valley Hall boundary states electronically. The interactions between electrons in the 2D graphene domains and the one-dimensional domain-wall solitons can lead to further new quantum phenomena. Domain-wall solitons of varied local structures exist along different crystallographic orientations, which can exhibit distinct electrical, mechanical and optical properties. Here we report soliton-dependent 2D graphene plasmon reflection at different 1D domain-wall solitons in bilayer graphene using near-field infrared nanoscopy. We observe various domain-wall structures in mechanically exfoliated graphene bilayers, including network-forming triangular lattices, individual straight or bent lines, and even closed circles. The near-field infrared contrast of domain-wall solitons arises from plasmon reflection at domain walls, and exhibits markedly different behaviours at the tensile- and shear-type domain-wall solitons. In addition, the plasmon reflection at domain walls exhibits a peculiar dependence on electrostatic gating. Our study demonstrates the unusual and tunable coupling between 2D graphene plasmons and domain-wall solitons.

Valley and band structure engineering of folded MoS(2) bilayers.

Artificial structures made of stacked two-dimensional crystals have recently been the focus of intense research activity. As in twisted or stacked graphene layers, these structures can show unusual behaviours and new phenomena. Among the various layered compounds that can be exfoliated, transition-metal dichalcogenides exhibit interesting properties governed by their structural symmetry and interlayer coupling, which are highly susceptible to stacking. Here, we obtain-by folding exfoliated MoS2 monolayers-MoS2 bilayers with different stacking orders, as monitored by second harmonic generation and photoluminescence. Appropriate folding can break the inversion symmetry and suppress interlayer hopping, evoking strong valley and spin polarizations that are not achieved in natural MoS2 bilayers of Bernal stacking. It can also enlarge the indirect bandgap by more than 100 meV through a decrease in the interlayer coupling. Our work provides an effective and versatile means to engineer transition-metal dichalcogenide materials with desirable electronic and optical properties.

Electrical control of optical plasmon resonance with graphene.

Surface plasmon has the unique capability to concentrate light into subwavelength volume. Active plasmon devices using electrostatic gating can enable flexible control of the plasmon excitations, which has been demonstrated recently in terahertz plasmonic structures. Controlling plasmon resonance at optical frequencies, however, remains a significant challenge because gate-induced free electrons have very weak responses at optical frequencies. Here we achieve efficient control of near-infrared plasmon resonance in a hybrid graphene-gold nanorod system. Exploiting the uniquely strong and gate-tunable optical transitions of graphene, we are able to significantly modulate both the resonance frequency and quality factor of gold nanorod plasmon. Our analysis shows that the plasmon-graphene coupling is remarkably strong: even a single electron in graphene at the plasmonic hotspot could have an observable effect on plasmon scattering intensity. Such hybrid graphene-nanometallic structure provides a powerful way for electrical control of plasmon resonances at optical frequencies and could enable novel plasmonic sensing down to single charge transfer events.

Toward chiral sum-frequency spectroscopy.

Chiral sum-frequency (SF) spectroscopy that measures both the real and the imaginary components of the SF spectral response was demonstrated for the first time. It was based on interference of the SF signal with a dispersionless SF reference. Solutions of 1,1'-bi-2-naphthol (BN) were used as model systems, and their chiral SF spectra over the first exciton-split transitions were obtained. Chiral spectra are useful for determination of absolute configuration and conformation of chiral molecules.

Three-dimensional chiral imaging by sum-frequency generation.

A sum-frequency generation (SFG) microscope that is sensitive toward molecular chirality was demonstrated for the first time. Optically active images of chiral 1,1'-bi-2-naphthol solutions were obtained with submicron spatial resolution. Three-dimensional sectioning capability of our microscope was also demonstrated. This optically active SFG microscopy can potentially become a powerful imaging technique for biological samples.

A novel spectroscopic probe for molecular chirality.

Recent advances in developing sum frequency generation (SFG) as a novel spectroscopic probe for molecular chirality are reviewed. The basic principle underlying the technique is briefly described, in comparison with circular dichroism (CD). The significantly better sensitivity of the technique than CD is pointed out, and the reason is discussed. Bi-naphthol (BN) and amino acids are used as representatives for two different types of chiral molecules; the measured chirality in their electronic transitions can be understood by two different molecular models, respectively, that are extensions of models developed earlier for CD. Optically active or chiral SFG from vibrational transitions are weaker, but with the help of electronic-vibrational double resonance, the vibrational spectrum of a monolayer of BN has been obtained. Generally, optically active SFG is sufficiently sensitive to be employed to probe in-situ chirality of chiral monolayers and thin films.

A dynamic coupling model for sum frequency chiral response from liquids composed of molecules with a chiral side chain and an achiral chromophore.

A theoretical formulation for optically active sum frequency generation (OA-SFG) from isotropic chiral solutions was proposed for molecules with a chiral side chain and an intrinsically achiral chromophore. Adapting an electron correlation model first proposed by Höhn and Weigang for linear optical activity, we presented a dynamic coupling model for OA-SFG near the electronic resonance of the achiral chromophore. As a demonstration, we used this model to explain the observed OA-SFG spectra of a series of amino acids near the electronic resonance of the intrinsically achiral carboxyl group. Our model shows that the nonlinear chiroptical response comes about by the through-space correlative electronic interactions between the chiral side chain and the achiral chromophore, and its magnitude is determined by the position and orientation of the bonds that make up the chiral side chain. Using the bond polarizability values in the literature and the conformations of amino acids obtained from calculation, we were able to reproduce the relative OA-SFG strength from a series of amino acids.

Photo-induced chirality switching in a cobaloxime complex crystal.

Switching of molecular chirality under photo-irradiation was studied in a cobaloxime complex crystal. Excitation of the d-d transition of the Co(III) ion appeared to be much more effective in inducing the chirality change than excitation of the ligand-metal charge transfer band although the latter is more effective in breaking the Co-C bond that initiates the chirality switching. The chirality change versus irradiation time showed a steplike behavior suggesting that chirality switching of molecules occurred in correlation with their nearest neighbors.

Optically active sum frequency generation from molecules with a chiral center: amino acids as model systems.

With amino acids as model systems, optically active sum frequency generation (OA-SFG) was used to probe the chirality of molecules with a chiral center and an intrinsically achiral chromophore in isotropic solution for the first time. Like that of circular dichroism (CD), the OA-SFG's near electronic resonance originates from the extrachromophoric chiral perturbation on the carboxyl chromophore. The difference in the relative strengths of OA-SFG and CD among different amino acids can be explained by the difference in the details of perturbations.

Sum frequency vibrational spectroscopy of leucine molecules adsorbed at air-water interface.

Sum frequency vibrational spectroscopy was used to study adsorption of leucine molecules at air-water interface from solutions with different concentrations and pH values. The surface density and the orientation of the isopropyl head group of the adsorbed leucine molecules could be deduced from the measurements. It was found that the orientation depends on the surface density, but only weakly on bulk pH value at the saturated surface density. The vibrational spectra of the interfacial water molecules appeared to be strongly affected by the charge state of the adsorbed leucine molecules. Enhancement and inversion of polar orientation of interfacial water molecules by surface charges or field controllable by the bulk pH value were observed.

Surface vibrational spectroscopy on shear-aligned poly(tetrafluoroethylene) films.

Sum-frequency vibrational spectroscopy was used to obtain the first surface vibrational spectra of shear-deposited highly oriented poly(tetrafluoroethylene) (PTFE, Teflon) thin films. The surface PTFE chains appeared to lie along the shearing direction. Vibrational modes observed at 1142 and 1204 cm-1 were found to have the E1 symmetry, in support of some earlier analysis in the long-lasting controversy over the assignment of these modes.