Graphene Nano-Optics in the Terahertz Gap.

Graphene nano-optics at terahertz (THz) frequencies (ν) is theoretically anticipated to feature extraordinary effects. However, interrogating such phenomena is nontrivial, since the atomically thin graphene dimensionally mismatches the THz radiation wavelength reaching hundreds of micrometers. Greater challenges happen in the THz gap (0.1-10 THz) wherein light sources are scarce. To surpass these barriers, we use a nanoscope illuminated by a highly brilliant and tunable free-electron laser to image the graphene nano-optical response from 1.5 to 6.0 THz. For ν < 2 THz, we observe a metal-like behavior of graphene, which screens optical fields akin to noble metals, since this excitation range approaches its charge relaxation frequency. At 3.8 THz, plasmonic resonances cause a field-enhancement effect (FEE) that improves the graphene imaging power. Moreover, we show that the metallic behavior and the FEE are tunable upon electrical doping, thus providing further control of these graphene nano-optical properties in the THz gap.

Review on infrared nanospectroscopy of natural 2D phyllosilicates.

Phyllosilicates have emerged as a promising class of large bandgap lamellar insulators. Their applications have been explored from the fabrication of graphene-based devices to 2D heterostructures based on transition metal dichalcogenides with enhanced optical and polaritonics properties. In this review, we provide an overview of the use of infrared (IR) scattering-type scanning near-field optical microscopy (s-SNOM) for studying nano-optics and local chemistry of a variety of 2D natural phyllosilicates. Finally, we bring a brief update on applications that combine natural lamellar minerals into multifunctional nanophotonic devices driven by electrical control.

Impacts of dielectric screening on the luminescence of monolayer WSe2.

Single layers of transition metal dichalcogenides (TMDCs), such as WSe2have gathered increasing attention due to their intense electron-hole interactions, being considered promising candidates for developing novel optical applications. Within the few-layer regime, these systems become highly sensitive to the surrounding environment, enabling the possibility of using a proper substrate to tune desired aspects of these atomically-thin semiconductors. In this scenario, the dielectric environment provided by the substrates exerts significant influence on electronic and optical properties of these layered materials, affecting the electronic band-gap and the exciton binding energy. However, the corresponding effect on the luminescence of TMDCs is still under discussion. To elucidate these impacts, we used a broad set of materials as substrates for single-layers of WSe2, enabling the observation of these effects over a wide range of electrical permittivities. Our results demonstrate that an increasing permittivity induces a systematic red-shift of the optical band-gap of WSe2, intrinsically related to a considerable reduction of the luminescence intensity. Moreover, we annealed the samples to ensure a tight coupling between WSe2and its substrates, reducing the effect of undesired adsorbates trapped in the interface. Ultimately, our findings reveal how critical the annealing temperature can be, indicating that above a certain threshold, the heating treatment can induce adverse impacts on the luminescence. Furthermore, our conclusions highlight the influence the dielectric properties of the substrate have on the luminescence of WSe2, showing that a low electrical permittivity favours preserving the native properties of the adjacent monolayer.

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO3 or H3BO3.

In this work, we synthesized and studied the spectroscopic properties of (NH4)2(SO4)2Y(H2O)6 (Y = Ni, Mg) crystals doped with AgNO3 or H3BO3. These crystals constitute a series of hexahydrated salts known as Tutton salts. We investigated the influence of dopants on the vibrational modes of the tetrahedral ligands NH4 and SO4, octahedral complexes Mg(H2O)6 and Ni(H2O)6, and H2O molecules present in these crystals through Raman and infrared spectroscopies. We were able to identify bands that are attributed to the presence of Ag and B dopants, as well as band shifts caused by the presence of these dopants in the crystal lattice. A detailed study of the crystal degradation processes was performed by thermogravimetric measurements, where there was an increase in the initial temperature of crystal degradation due to the presence of dopants in the crystal lattice. Raman spectroscopy of the crystal residues after the thermogravimetric measurements helped us to elucidate the degradation processes occurring after the crystal pyrolysis process.

Distinctive g-Factor of Moiré-Confined Excitons in van der Waals Heterostructures.

We investigated the valley Zeeman splitting of excitonic peaks in the microphotoluminescence (µPL) spectra of high-quality hBN/WS2/MoSe2/hBN heterostructures under perpendicular magnetic fields up to 20 T. We identify two neutral exciton peaks in the µPL spectra; the lower-energy peak exhibits a reduced g-factor relative to that of the higher energy peak and much lower than the recently reported values for interlayer excitons in other van der Waals (vdW) heterostructures. We provide evidence that such a discernible g-factor stems from the spatial confinement of the exciton in the potential landscape created by the moiré pattern due to lattice mismatch or interlayer twist in heterobilayers. This renders magneto-µPL an important tool to reach a deeper understanding of the effect of moiré patterns on excitonic confinement in vdW heterostructures.

Electrical and optical properties of transition metal dichalcogenides on talc dielectrics.

Advanced van der Waals (vdW) heterostructure devices rely on the incorporation of high quality dielectric materials which need to possess a low defect density as well as being atomically smooth and uniform. In this work we explore the use of talc dielectrics as a potentially clean alternative substrate to hexagonal boron nitride (hBN) for few-layer transition metal dichalcogenide (TMDC) transistors and excitonic TMDC monolayers. We find that talc dielectric transistors show small hysteresis which does not depend strongly on sweep rate and show negligible leakage current for our studied dielectric thicknesses. We also show narrow photoluminescence linewidths down to 10 meV for different TMDC monolayers on talc which highlights that talc is a promising material for future van der Waals devices.

Sub-diffractional cavity modes of terahertz hyperbolic phonon polaritons in tin oxide.

Hyperbolic phonon polaritons have recently attracted considerable attention in nanophotonics mostly due to their intrinsic strong electromagnetic field confinement, ultraslow polariton group velocities, and long lifetimes. Here we introduce tin oxide (SnO2) nanobelts as a photonic platform for the transport of surface and volume phonon polaritons in the mid- to far-infrared frequency range. This report brings a comprehensive description of the polaritonic properties of SnO2 as a nanometer-sized dielectric and also as an engineered material in the form of a waveguide. By combining accelerator-based IR-THz sources (synchrotron and free-electron laser) with s-SNOM, we employed nanoscale far-infrared hyper-spectral-imaging to uncover a Fabry-Perot cavity mechanism in SnO2 nanobelts via direct detection of phonon-polariton standing waves. Our experimental findings are accurately supported by notable convergence between theory and numerical simulations. Thus, the SnO2 is confirmed as a natural hyperbolic material with unique photonic properties essential for future applications involving subdiffractional light traffic and detection in the far-infrared range.

Synchrotron infrared nanospectroscopy on a graphene chip.

A recurring goal in biology and biomedicine research is to access the biochemistry of biological processes in liquids that represent the environmental conditions of living organisms. These demands are becoming even more specific as microscopy techniques are fast evolving in the era of single cell analysis. In the modality of chemical probes, synchrotron infrared spectroscopy (µ-FTIR) is a technique that is extremely sensitive to vibrational responses of materials; however, the classical optical limits prevent the technique to access the biochemistry of specimens at the subcellular level. In addition, due to the intricate environmental requirements and strong infrared absorption of water, µ-FTIR of bioprocesses in liquids remains highly challenging. In phase with these challenges, on-chip liquid cells emerge as a versatile alternative to control the water thickness while providing a biocompatible chemical environment for analytical analyses. In this work we report the development of a liquid platform specially designed for nanoscale infrared analysis of biomaterials in wet environments. A key advantage of our designed platform is the use of graphene as an optical window that interfaces wet and dry environments in the liquid cell. By combining near-field optical microscopy and synchrotron infrared radiation, we measure the nanoscale fingerprint IR absorbance of a variety of liquids often used in biological studies. Further, we demonstrate the feasibility of the platform for the chemical analysis of protein clusters immersed in water with a clear view of the proteins' secondary structure signatures. The simplicity of the proposed platform combined with the high quality of our data makes our findings a template for future microfluidic devices targeting dynamic nanoscale-resolved chemical analysis.

Dipole modelling for a robust description of subdiffractional polariton waves.

The nanophotonics of van der Waals (vdW) materials relies critically on the electromagnetic properties of polaritons defined on sub-diffraction length scales. Here, we use a full electromagnetic Hertzian dipole antenna (HDA) model to describe the hyperbolic phonon polaritons (HP2s) in vdW crystals of hexagonal boron nitride (hBN) on a gold surface. The HP2 waves are investigated by broadband synchrotron infrared nanospectroscopy (SINS) which covers the type I and type II hyperbolic bands simultaneously. Basically, polariton waves, observed by SINS, are assigned to the resultant electric field from the summation over the irradiated electric fields of dipoles distributed along the crystal edge and at the tip location and a non-propagating field. The values of polariton momenta and damping extracted from the HDA model present excellent agreement with theoretical predictions. Our analysis shows that the confinement factor of type I HP2s exceeds that of the type II ones by up to a factor of 3. We extract anti-parallel group velocities (vg) for type I (vg,typeI = -0.005c, c is the light velocity in a vacuum) in relation to type II (vg,typeII = 0.05c) polaritonic pulses, with lifetimes of ∼0.6 ps and ∼0.3 ps, respectively. Furthermore, by incorporating consolidated optical-near field theory into the HDA model, we simulate real-space images of polaritonic standing waves for hBN crystals of different shapes. This approach reproduces the experiments with a minimal computational cost. Thus, it is demonstrated that the HDA modelling self-consistently explains the measured complex-valued polariton near-field, while being a general approach applicable to other polariton types, like plasmon- and exciton-polaritons, active in the wide range of vdW materials.

Exfoliation and characterization of a two-dimensional serpentine-based material.

We report on an experimental investigation of serpentine, an abundant phyllosilicate, as an alternative source of two-dimensional (2D) nanomaterials. We show, through scanning probe microscopy (SPM) measurements, that natural serpentine mineral can be mechanically exfoliated down to few-layer flakes, where monolayers can be easily resolved. The parent serpentine bulk material was initially characterized via conventional techniques like XRD, XPS, FTIR and Raman spectroscopies and the results show that it is predominantly constituted by the antigorite mineral. From ab initio calculations using density functional theory, we also determine the geometry and electronic structure of antigorite, the observed structural form of serpentine. Additionally, we further characterized electrical and mechanical properties of the obtained 2D material flakes using SPM and broadband synchrotron infrared nanospectroscopy. Wavelength tuning of the serpentine vibrational resonances, assigned to in- and out-of-plane molecular vibrations, are observed and compared with the FTIR characterization of the parent bulk material. They show that there is no degradation of serpentine's structural properties during its mechanical exfoliation down to nanometer-thin sheets. Therefore, our results introduce the serpentine mineral as an attractive low-cost candidate in 2D materials applications.

Anisotropic Flow Control and Gate Modulation of Hybrid Phonon-Polaritons.

Light-matter interaction in two-dimensional photonic or phononic materials allows for the confinement and manipulation of free-space radiation at sub-wavelength scales. Most notably, the van der Waals heterostructure composed of graphene (G) and hexagonal boron nitride (hBN) provides for gate-tunable hybrid hyperbolic plasmon phonon-polaritons (HP3). Here, we present the anisotropic flow control and gate-voltage modulation of HP3 modes in G-hBN on an air-Au microstructured substrate. Using broadband infrared synchrotron radiation coupled to a scattering-type near-field optical microscope, we launch HP3 waves in both hBN Reststrahlen bands and observe directional propagation across in-plane heterointerfaces created at the air-Au junction. The HP3 hybridization is modulated by varying the gate voltage between graphene and Au. This modifies the coupling of continuum graphene plasmons with the discrete hBN hyperbolic phonon polaritons, which is described by an extended Fano model. This work represents the first demonstration of the control of polariton propagation, introducing a theoretical approach to describe the breaking of the reflection and transmission symmetry for HP3 modes. Our findings augment the degree of control of polaritons in G-hBN and related hyperbolic metamaterial nanostructures, bringing new opportunities for on-chip nano-optics communication and computing.

Graphene/h-BN plasmon-phonon coupling and plasmon delocalization observed by infrared nano-spectroscopy.

We observed the coupling of graphene Dirac plasmons with different surfaces using scattering-type scanning near-field optical microscopy integrated into a mid-infrared synchrotron-based beamline. A systematic investigation of a graphene/hexagonal boron nitride (h-BN) heterostructure is carried out and compared with the well-known graphene/SiO2 heterostructure. Broadband infrared scanning near-field optical microscopy imaging is able to distinguish between the graphene/h-BN and the graphene/SiO2 heterostructure as well as differentiate between graphene stacks with different numbers of layers. Based on synchrotron infrared nanospectroscopy experiments, we observe a coupling of surface plasmons of graphene and phonon polaritons of h-BN (SPPP). An enhancement of the optical band at 817 cm(-1) is observed at graphene/h-BN heterostructures as a result of hybridization between graphene plasmons and longitudinal optical phonons of h-BN. Furthermore, longitudinal optical h-BN modes are preserved on suspended graphene regions (bubbles) where the graphene sheet is tens of nanometers away from the surface while the amplitude of transverse optical h-BN modes decrease.

Observation of strain-free rolled-up CVD graphene single layers: toward unstrained heterostructures.

Single layer graphene foils produced by chemical vapor deposition (CVD) are rolled with self-positioned layers of InGaAs/Cr forming compact multi-turn tubular structures that consist on successive graphene/metal/semiconductor heterojunctions on a radial superlattice. Using elasticity theory and Raman spectroscopy, we show that it is possible to produce homogeneously curved graphene with a curvature radius on the 600-1200 nm range. Additionally, the study of tubular structures also allows the extraction of values for the elastic constants of graphene that are in excellent agreement with elastic constants found in the literature. However, our process has the advantage of leading to a well-defined and nonlocal curvature. Since our curvature radius lies in a range between the large radius studied using mechanical bending and the reduced radius induced by atomic force microscopy experiments, we can figure out whether bending effects can be a majoritary driving force for modifications in graphene electronic status. From the results described in this work, one can assume that curvature effects solely do not modify the Raman signature of graphene and that strain phenomena observed previously may be ascribed to possible stretching due to the formation of local atomic bonds. This implies that the interactions of graphene with additional materials on heterostructures must be investigated in detail prior to the development of applications and devices.