Hai Hu

Far-field nanoscale infrared spectroscopy of vibrational fingerprints of molecules with graphene plasmons

Infrared spectroscopy, especially for molecular vibrations in the fingerprint region between 600 and 1,500 cm−1, is a powerful characterization method for bulk materials. However, molecular fingerprinting at the nanoscale level still remains a significant challenge, due to weak light–matter interaction between micron-wavelengthed infrared light and nano-sized molecules. Here we demonstrate molecular fingerprinting at the nanoscale level using our specially designed graphene plasmonic structure on CaF2 nanofilm. This structure not only avoids the plasmon–phonon hybridization, but also provides in situ electrically-tunable graphene plasmon covering the entire molecular fingerprint region, which was previously unattainable. In addition, undisturbed and highly confined graphene plasmon offers simultaneous detection of in-plane and out-of-plane vibrational modes with ultrahigh detection sensitivity down to the sub-monolayer level, significantly pushing the current detection limit of far-field mid-infrared spectroscopies. Our results provide a platform, fulfilling the long-awaited expectation of high sensitivity and selectivity far-field fingerprint detection of nano-scale molecules for numerous applications.

Far-Field Spectroscopy and Near-Field Optical Imaging of Coupled Plasmon-Phonon Polaritons in 2D van der Waals Heterostructures

A new hybridized plasmon-phonon polariton mode in graphene/h-BN van der Waals heterostructures is presented, featuring the ultrahigh field confinement characteristic of the graphene plasmon and the long lifetime property of the h-BN transverse optical phonon. This enables an ultralong hybrid plasmon lifetime of up to 1.6 ps (with ultrahigh mode confinement up to >l0(2)/7000 and ultrasmall group velocity down to 0.001c, where c is the speed of light in vacuum), superior to any localized plasmon ever demonstrated.

Tuning the Interfacial Mechanical Behaviors of Monolayer Graphene/PMMA Nanocomposites

The van der Waals (vdW) force dominated interface between graphene and polymer matrix creates weak points in the mechanical sense. Chemical functionalization was expected to be an effective approach in transfer of the outstanding performance of graphene across multiple length scales up to the macroscopic level, due to possible improvements in the interfacial adhesion. However, published works showed the contradiction that improvements, insensitivity, or even worsening of macro-mechanical performance have all been reported in graphene-based polymer nanocomposites. Particularly central cause of such discrepancy is the variations in graphene/polymer interfacial chemistry, which is critical in nanocomposites with vast interfacial area. Herein, O3/H2O gaseous mixture was utilized to oxidize monolayer graphene sheet with controlled functionalization degrees. Hydrogen bonds (H bonds) are expected to form between oxidized graphene sheet/poly(methyl methacrylate) (PMMA) at the interface. On the basis of in situ tensile-micro Raman spectroscopy, the impacts of bonding types (vdW and H-bonds) on both key interfacial parameters (such as interfacial shear strength and critical length) and failure modes of graphene/PMMA nanocomposite were clarified for the first time at the microscopic level. Our results show that owing to improved interfacial interaction via H bonds, the interface tends to be stiffening and strengthening. Moreover, the mechanical properties of the functionalized graphene/PMMA interface will be set by the competition between the enhanced interfacial adhesion and the degraded elastic modulus of graphene, which was caused by structural defects in the graphene sheet during the functionalization process and could lead to catastrophic failure of graphene sheets in our experimental observation. Our results will be helpful to design various nanofiller-based nanocomposites with high mechanical performance.

Substrate Phonon‐Mediated Plasmon Hybridization in Coplanar Graphene Nanostructures for Broadband Plasmonic Circuits

The mode hybridization between adjacent graphene nanoribbons determines the integration density of graphene-based plasmonic devices. Here, plasmon hybridization in graphene nanostructures is demonstrated through the characterization of the coupling strength of plasmons in graphene nanoribbons as a function of charge density and inter-ribbon spacing using Fourier transform infrared microscopy. In combination with numerical simulations, it is shown that the plasmon coupling is strongly mediated by the substrate phonons. For polar substrates, the plasmon coupling strength is limited by the plasmon-phonon interactions. In contrast, a nonpolar substrate affects neither the energy distribution of the original plasmon modes in graphene nanostructures nor their plasmon interactions, which increases exponentially as the inter-ribbon spacing decreases. To further explore the potential of graphene broadband plasmonics on nonpolar substrates, a scheme is proposed that uses a metal-dielectric heterostructure to prevent the overlap of plasmons between neighboring graphene nanoribbons. The device structures retain the plasmon resonance frequency of the graphene ribbons and maximally isolate the plasmonic components from the surrounding electromagnetic environment, allowing modular design in integrated plasmonic circuits.

Probing optical anisotropy of nanometer-thin van der waals microcrystals by near-field imaging

Most van der Waals crystals present highly anisotropic optical responses due to their strong in-plane covalent bonding and weak out-of-plane interactions. However, the determination of the polarization-dependent dielectric constants of van der Waals crystals remains a nontrivial task, since the size and dimension of the samples are often below or close to the diffraction limit of the probe light. In this work, we apply an optical nano-imaging technique to determine the anisotropic dielectric constants in representative van der Waals crystals. Through the study of both ordinary and extraordinary waveguide modes in real space, we are able to quantitatively determine the full dielectric tensors of nanometer-thin molybdenum disulfide and hexagonal boron nitride microcrystals, the most-promising van der Waals semiconductor and dielectric. Unlike traditional reflection-based methods, our measurements are reliable below the length scale of the free-space wavelength and reveal a universal route for characterizing low-dimensional crystals with high anisotropies.The optical response of van der Waals layered crystals is strongly anisotropic. Here, the authors develop a nano-imaging technique to determine the in-plane and out-of-plane components of the anisotropic dielectric tensors in MoS2 and hBN, two representative van der Waals crystals.

Tunable Electronic Transport Properties of 2D Layered Double Hydroxide Crystalline Microsheets with Varied Chemical Compositions.

Transistors based on layered double hydroxides (LDH) single microcrystal are fabricated, whose conductivity of LDH can be tuned by varying metal cations or interlayer anions, but weakly affected by external electric field. The carrier mobility can reach about 1 × 10(-5) cm(2) V(-1) s(-1) , a value comparable to that of organic C60-based transistors. This work paves a way for future electrical applications of LDH.

Nanomaterial‐Based Plasmon‐Enhanced Infrared Spectroscopy

Surface-enhanced infrared absorption (SEIRA) has attracted increasing attention due to the potential of infrared spectroscopy in applications such as molecular trace sensing of solids, polymers, and proteins, specifically fueled by recent substantial developments in infrared plasmonic materials and engineered nanostructures. Here, the significant progress achieved in the past decades is reviewed, along with the current state of the art of SEIRA. In particular, the plasmonic properties of a variety of nanomaterials are discussed (e.g., metals, semiconductors, and graphene) along with their use in the design of efficient SEIRA configurations. To conclude, perspectives on potential applications, including single-molecule detection and in vivo bioassays, are presented.

Rigorous numerical modeling of scattering-type scanning near-field optical microscopy and spectroscopy

Over the last decade, scattering-type scanning near-field optical microscopy and spectroscopy have been widely used in nano-photonics and material research due to their fine spatial resolution and broad spectral range. A number of simplified analytical models have been proposed to quantitatively understand the tip-scattered near-field signal. However, a rigorous interpretation of the experimental results is still lacking at this stage. Numerical modelings, on the other hand, are mostly done by simulating the local electric field slightly above the sample surface, which only qualitatively represents the near-field signal rendered by the tip-sample interaction. In this work, we performed a more comprehensive numerical simulation which is based on realistic experimental parameters and signal extraction procedures. By directly comparing to the experiments as well as other simulation efforts, our methods offer a more accurate quantitative description of the near-field signal, paving the way for future studies ...

Perfect-absorption graphene metamaterials for surface-enhanced molecular fingerprint spectroscopy

Graphene plasmon with extremely strong light confinement and tunable resonance frequency represents a promising surface-enhanced infrared absorption (SEIRA) sensing platform. However, plasmonic absorption is relatively weak (approximately 1%-9%) in monolayer graphene nanostructures, which would limit its sensitivity. Here, we theoretically propose a hybrid plasmon-metamaterial structure that can realize perfect absorption in graphene with a low carrier mobility of 1000 cm2 V-1 s-1. This structure combines a gold reflector and a gold grating to the graphene plasmon structures, which introduce interference effect and the lightning-rod effect, respectively, and largely enhance the coupling of light to graphene. The vibration signal of trace molecules can be enhanced up to 2000-fold at the hotspot of the perfect-absorption structure, enabling the SEIRA sensing to reach the molecular level. This hybrid metal-graphene structure provides a novel path to generate high sensitivity in nanoscale molecular recognition for numerous applications.

Ultra-compact graphene plasmonic filter integrated in a waveguide*

Graphene plasmons have become promising candidates for deep-subwavelength nanoscale optical devices due to their strong field confinement and low damping. Among these nanoscale optical devices, band-pass filter for wavelength selection and noise filtering are key devices in an integrated optical circuit. However, plasmonic filters are still oversized because large resonant cavities are needed to perform frequency selection. Here, an ultra-compact filter integrated in a graphene plasmonic waveguide was designed, where a rectangular resonant cavity is inside a graphene nanoribbon waveguide. The properties of the filter were studied using the finite-difference time-domain method and demonstrated using the analytical model. The results demonstrate the band-pass filter has a high quality factor (20.36) and electrically tunable frequency response. The working frequency of the filter could also be tuned by modifying the cavity size. Our work provides a feasible structure for a graphene plasmonic nano-filter for future use in integrated optical circuits.