Characterizing and controlling infrared phonon anomaly of bilayer graphene in optical-electrical force nanoscopy.

We, for the first time, report the nanoscopic imaging study of anomalous infrared (IR) phonon enhancement of bilayer graphene, originated from the charge imbalance between the top and bottom layers, resulting in the enhancement of E1u mode of bilayer graphene near 0.2 eV. We modified the multifrequency atomic force microscope platform to combine photo-induced force microscope with electrostatic/Kelvin probe force microscope constituting a novel hybrid nanoscale optical-electrical force imaging system. This enables to observe a correlation between the IR response, doping level, and topographic information of the graphene layers. Through the nanoscale spectroscopic image measurements, we demonstrate that the charge imbalance at the graphene interface can be controlled by chemical (doping effect via Redox mechanism) and mechanical (triboelectric effect by the doped cantilever) approaches. Moreover, we can also diagnosis the subsurface cracks on the stacked few-layer graphene at nanoscale, by monitoring the strain-induced IR phonon shift. Our approach provides new insights into the development of graphene-based electronic and photonic devices and their potential applications.

Direct Electrochemical Functionalization of Graphene Grown on Cu Including the Reaction Rate Dependence on the Cu Facet Type.

We present an electrochemical method to functionalize single-crystal graphene grown on copper foils with a (111) surface orientation by chemical vapor deposition (CVD). Graphene on Cu(111) is functionalized with 4-iodoaniline by applying a constant negative potential, and the degree of functionalization depends on the applied potential and reaction time. Our approach stands out from previous methods due to its transfer-free method, which enables more precise and efficient functionalization of single-crystal graphene. We report the suggested effects of the Cu substrate facet by comparing the reactivity of graphene on Cu(111) and Cu(115). The electrochemical reaction rate changes dramatically at the potential threshold for each facet. Kelvin probe force microscopy was used to measure the work function, and the difference in onset potentials of the electrochemical reaction on these two different facets are explained in terms of the difference in work function values. Density functional theory and Monte Carlo calculations were used to calculate the work function of graphene and the thermodynamic stability of the aniline functionalized graphene on these two facets. This study provides a deeper understanding of the electrochemical behavior of graphene (including single-crystal graphene) on Cu(111) and Cu(115). It also serves as a basis for further study of a broad range of reagents and thus functional groups and of the role of metal substrate beneath graphene.

Near-field probing of image phonon-polaritons in hexagonal boron nitride on gold crystals.

Near-field mapping has been widely used to study hyperbolic phonon-polaritons in van der Waals crystals. However, an accurate measurement of the polaritonic loss remains challenging because of the inherent complexity of the near-field signal and the substrate-mediated loss. Here we demonstrate that large-area monocrystalline gold flakes, an atomically flat low-loss substrate for image polaritons, provide a platform for precise near-field measurement of the complex propagation constant of polaritons in van der Waals crystals. As a topical example, we measure propagation loss of the image phonon-polaritons in hexagonal boron nitride, revealing that their normalized propagation length exhibits a parabolic spectral dependency. Furthermore, we show that image phonon-polaritons exhibit up to a twice longer normalized propagation length, while being 2.4 times more compressed compared to the case of the dielectric substrate. We conclude that the monocrystalline gold flakes provide a unique nanophotonic platform for probing and exploitation of the image modes in low-dimensional materials.

Ultracompact electro-optic waveguide modulator based on a graphene-covered λ/1000 plasmonic nanogap.

The extreme field confinement and electro-optic tunability of plasmons in graphene make it an ideal platform for compact waveguide modulators, with device footprints aggressively scaling orders of magnitude below the diffraction limit. The miniaturization of modulators based on graphene plasmon resonances is however inherently constrained by the plasmon wavelength, while their performance is bounded by material loss in graphene. In this report, we propose to overcome these limitations using a graphene-covered λ/1000 plasmonic nanogap waveguide that concentrates light on length scales more than an order of magnitude smaller than the graphene plasmon wavelength. The modulation mechanism relies on interference between the non-resonant background transmission and the transmission mediated by the gate-tunable nanogap mode, enabling modulation depths over 20 dB. Since the operation of the device does not rely on graphene plasmons, the switching behavior is robust against low graphene carrier mobility even under 1000 cm2/Vs, which is desirable for practical applications.

Real-space imaging of acoustic plasmons in large-area graphene grown by chemical vapor deposition.

An acoustic plasmon mode in a graphene-dielectric-metal structure has recently been spotlighted as a superior platform for strong light-matter interaction. It originates from the coupling of graphene plasmon with its mirror image and exhibits the largest field confinement in the limit of a sub-nm-thick dielectric. Although recently detected in the far-field regime, optical near-fields of this mode are yet to be observed and characterized. Here, we demonstrate a direct optical probing of the plasmonic fields reflected by the edges of graphene via near-field scattering microscope, revealing a relatively small propagation loss of the mid-infrared acoustic plasmons in our devices that allows for their real-space mapping at ambient conditions even with unprotected, large-area graphene grown by chemical vapor deposition. We show an acoustic plasmon mode that is twice as confined and has 1.4 times higher figure of merit in terms of the normalized propagation length compared to the graphene surface plasmon under similar conditions. We also investigate the behavior of the acoustic graphene plasmons in a periodic array of gold nanoribbons. Our results highlight the promise of acoustic plasmons for graphene-based optoelectronics and sensing applications.

Modal evolution in asymmetric three- and four-layer plasmonic waveguides.

Through the employment of a novel approach in solving the dispersion for the three-layer plasmonic waveguides, considering lossy metals, we demonstrate that, besides well-known modes, the complete dispersion always contains high-lossy periodic solutions. Consideration of these solutions is shown to be crucial for the understanding of every aspect of dispersion evolution at broad spectral range when the thickness of the middle layer is varied. In particular, we show that generally considered modes of the three-layer waveguide transform into the single interface modes via interaction with high-lossy periodic solutions. Furthermore, the negative index mode is shown to experience a transition between low- and high-lossy regimes depending on the waveguide's thickness. Our results, avoiding complicated analytical analysis, perfectly integrate and importantly complement past theoretical works.

Direct Optical Probing of Transverse Electric Mode in Graphene.

Unique electrodynamic response of graphene implies a manifestation of an unusual propagating and localised transverse-electric (TE) mode near the spectral onset of interband transitions. However, excitation and further detection of the TE mode supported by graphene is considered to be a challenge for it is extremely sensitive to excitation environment and phase matching condition adherence. Here for the first time, we experimentally prove an existence of the TE mode by its direct optical probing, demonstrating significant coupling to an incident wave in electrically doped multilayer graphene sheet at room temperature. We believe that proposed technique of careful phase matching and obtained access to graphene's TE excitation would stimulate further studies of this unique phenomenon, and enable its potential employing in various fields of photonics as well as for characterization of graphene.

Plasmonic excitations of 1D metal-dielectric interfaces in 2D systems: 1D surface plasmon polaritons.

Surface plasmon-polariton (SPP) excitations of metal-dielectric interfaces are a fundamental light-matter interaction which has attracted interest as a route to spatial confinement of light far beyond that offered by conventional dielectric optical devices. Conventionally, SPPs have been studied in noble-metal structures, where the SPPs are intrinsically bound to a 2D metal-dielectric interface. Meanwhile, recent advances in the growth of hybrid 2D crystals, which comprise laterally connected domains of distinct atomically thin materials, provide the first realistic platform on which a 2D metal-dielectric system with a truly 1D metal-dielectric interface can be achieved. Here we show for the first time that 1D metal-dielectric interfaces support a fundamental 1D plasmonic mode (1DSPP) which exhibits cutoff behavior that provides dramatically improved light confinement in 2D systems. The 1DSPP constitutes a new basic category of plasmon as the missing 1D member of the plasmon family: 3D bulk plasmon, 2DSPP, 1DSPP, and 0D localized SP.

Unusual Otto excitation dynamics and enhanced coupling of light to TE plasmons in graphene.

Transverse-electric (TE) plasmons are a unique and unusual aspect of graphene's plasmonic response that are predicted to manifest when the sign of imaginary part of conductivity changes to negative near the spectral onset of interband transitions. Although thus far, a feasible platform for the direct experimental detection of TE plasmons at finite temperature is yet to be suggested. Here we analyze the dynamics of Otto-Kretschmann excitation of TE plasmons in graphene. We show that TE plasmons supported by graphene in an Otto configuration unusually exhibit a cutoff thickness between the coupling prism and the graphene layer that forbids their efficient coupling to an incident wave in the case of a single-layer graphene at typical finite temperatures. In contrast, significantly increased coupling in the case of an N-layer graphene insulator stack, owing to an N-fold increase of the effective graphene conductivity as the insulator thickness approaches zero, is predicted to provide a TE plasmon resonance that is easily detectable at room temperature.