Scattering-type Scanning Near-field Optical Microscopy Research Articles

Optically driven plasmons in graphene/hBN van der Waals heterostructures: simulating s-SNOM measurements

Abstract Converting transverse photons into longitudinal two-dimensional plasmon-–polaritons (2D-PP) and vice versa presents a significant challenge within the fields of photonics and plasmonics. Therefore, understanding the mechanism which increases the photon – 2D-PP conversion efficiency could significantly contribute to those efforts. In this study, we theoretically examine how efficiently incident radiation, when scattered by a silver spherical nanoparticle (Ag-NP), can be transformed into 2D-PP within van der Waals (vdW) heterostructures composed of hexagonal boron nitride and graphene (hBN/Gr composites). We show that the Dirac plasmon (DP) excitation efficiency depends on the Ag-NP radius as R 3, and decreases exponentially with Ag-NP height h, so that for a certain Ag-NP geometry up to 25 % of the incident electrical field is channeled into the DP. We demonstrate that the linear plasmons (LPs) excitation efficiency can be manipulated by changing the graphene–graphene distance Δ (or hBN thickness) or by changing the number of graphene layers N. By increasing Δ and/or N the LPs move towards smaller wave vectors Q and become accessible by the Ag-NP dipole field, so that for N ≥ 5 the excitation of more than one LP is possible. These results are supported by recent scattering-type scanning near-field optical microscopy (s-SNOM) measurements. Furthermore, we show that Ag-NPs with specific parameters preferentially hybridizes with DPs of a particular wavelength λ D , facilitating selective excitation of DPs. The obtained tuning possibilities could have a significant impact on applied plasmonics, photonics or optoelectronics.

Nano-infrared imaging of epitaxial graphene on SiC revealing doping and thickness inhomogeneities

We report on a nano-infrared (IR) imaging and spectroscopy study of epitaxial graphene on silicon carbide (SiC) by using scattering-type scanning near-field optical microscopy (s-SNOM). With nano-IR imaging, we reveal in real space microscopic domains with distinct IR contrasts. By analyzing the nano-IR, atomic force microscopy, and scanning tunneling microscopy imaging data, we conclude that the imaged domains correspond to single-layer graphene, bilayer graphene (BLG), and higher-doped BLG. With nano-IR spectroscopy, we find that graphene can screen the SiC phonon resonance, and the screening is stronger at more conductive sample regions. Our work offers insights into the rich surface properties of epitaxial graphene and demonstrates s-SNOM as an efficient and effective tool in characterizing graphene and possibly other two-dimensional materials.

Nano-compositional imaging of the lanthanum silicide system at THz wavelengths.

Terahertz scattering-type scanning near-field optical microscopy (THz-sSNOM) provides a noninvasive way to probe the low frequency conductivity of materials and to characterize material compositions at the nanoscale. However, the potential capability of atomic compositional analysis with THz nanoscopy remains largely unexplored. Here, we perform THz near-field imaging and spectroscopy on a model rare-earth alloy of lanthanum silicide (La-Si) which is known to exhibit diverse compositional and structural phases. We identify subwavelength spatial variations in conductivity that is manifested as alloy microstructures down to much less than 1 μm in size and is remarkably distinct from the surface topography of the material. Signal contrasts from the near-field scattering responses enable mapping the local silicon/lanthanum content differences. These observations demonstrate that THz-sSNOM offers a new avenue to investigate the compositional heterogeneity of material phases and their related nanoscale electrical as well as optical properties.

Research advances in polaritonics based on near-field optical imaging technique

Polaritons, as hybrid excitations of light and matter, are important for miniaturizing the integrated nano-optoelectronic devices due to their capability of manipulating nanolight. Recently, the state-of-the-art nano-imaging technique (e.g. scattering-type scanning near-field optical microscope) has visualized various types of polaritons and revealed the physical mechanism behind them. The nanometer-resolution imaging not only deepens our understanding of fundamentals of polaritons but also promotes the studies of polariton manipulation and applications. In this review paper, we systematically summarize the recent near-field study of polaritons. Rather than other previous reviews focusing on polaritons in two-diemnsional materials, our review extends the polaritonic systems to multiple dimensions (3D/2D/1D), at the same time we also collect the latest progress of polaritons in anisotropic systems. Moreover, we show the recent study of polariton manipulation and their corresponding applications, e.g. sub-diffractional imaging, focusing, optical modulator, nanostructure diagnosis and molecular sensing. Our review also look forward to future opportunities of polaritonics and its nanophotonic applications.

Infrared nanoimaging of neuronal ultrastructure and nanoparticle interaction with cells.

Here we introduce scattering-type scanning near-field optical microscopy (s-SNOM) as a novel tool for nanoscale chemical-imaging of sub-cellular organelles, nanomaterials and of the interactions between them. Our setup uses a tuneable mid-infrared laser and a sharp scanning probe to image at a resolution substantially surpassing the diffraction limit. The laser can be tuned to excite vibrational modes of functional groups in biomolecules, (e.g. amide moieties), in a way that enables direct chemical mapping without the need for labelling. We, for the first time, chemically image neuronal ultrastructure, identify neuronal organelles and sub-organelle structures as small as 10 nm and validate our findings using transmission electron microscopy (TEM). We produce chemical and morphological maps of neurons treated with gold nanospheres and characterize nanoparticle size and intracellular location, and their interaction with the plasma membrane. Our results show that the label-free nature of s-SNOM means it has a 'true' chemical resolution of up to 20 nm which can be further improved. We argue that it offers significant potential in nanomedicine for nanoscale chemical imaging of cell ultrastructure and the subcellular distribution of nanomaterials within tissues.

Generic arrays of surface-positioned and shallow-buried gold multi-shapes as reference samples to benchmark near-field microscopes. Part 1: Applications in s-SNOM depth imaging

A wide palette of nanoscale imaging techniques operating in the near-field regime has been reported to date, enabling an important number of scientific breakthroughs. While the tuning and benchmarking of near-field microscopes represent a very important step for optimizing the outputs of the imaging sessions, no generally acknowledged standards exist yet in terms of calibration of near-field microscopes, which would play an important role in fully exploiting the potential of these instruments. With this work, we aim to contribute to filling in this gap, by introducing a prototypical sample, that holds potential for becoming a benchmark with respect to comparing the performances of diverse near-field measurement techniques, including traditional, aperture based, scanning near field microscopy (SNOM), or apertureless variants, such as scattering-type scanning nearfield optical microscopy (s-SNOM). The proposed samples have been thoroughly simulated, and an easy fabrication procedure is presented and demonstrated. In this latter context, Au-SiO2 samples sharing different configurations, in terms of geometry, number and depth of contrast yielding layers, enabling both surface and sub-surface nanoscopy measurements, were designed and fabricated. We argue that the proposed prototypical samples can be highly useful for benchmarking the outputs of various near-field microscopy techniques, as they facilitate a broad range of tests, relevant for comparing the performances and accuracy of many diverse investigation methods. We also introduce a methodology for numerically simulating the samples and their near-field after illuminating them with light of different wavelengths, as well as their simple process flow. This methodology can considerably augment their future use as a prototypical sample for the evaluation and calibration of current and next generation near-field nanoscopy techniques. Experimental evidence on the usefulness of these samples as s-SNOM testing and benchmarking tools is provided in the context of differentiation of surface and sub-surface structures, and influence of tip-sample distance on attainable amplitude and phase signals. We consider these efforts to represent an important, required step, in advancing the near-field imaging field, with important potential to augment the outputs of current near-field imaging systems, and to facilitate the development and benchmarking of next generation of near-field instrumentation.

Thermal near-field scattering characteristics for dielectric materials

In this study, we passively analyzed the near-field characteristics of thermally excited evanescent waves, which are radiation waves generated by the local dynamics of materials, including electron motions and lattice vibrations. The thermally excited evanescent waves on aluminium nitride (AlN) and gallium nitride (GaN) were measured using passive spectroscopic scattering-type scanning near-field optical microscopy (s-SNOM) in the wavelength ranges of 10.5–12.2 μm and 14.0–15.0 μm, which include the surface phonon-polariton (SPhP) wavelength of the studied dielectrics. We determined the unique decay characteristics of AlN and GaN, indicating a ten-fold increase in the probe area contributing to the scattering of waves near the SPhP wavelength compared to that in other wavelength ranges. The extended probe area correlated with the polariton decay lengths, indicating that the non-enhanced polaritons around K ~ ω/c were dominant in the scattered waves near the SPhP wavelength. In addition to the conventional passive detection mechanisms for metals, the proposed detection scheme will be a versatile passive detection model in the near future.

Hierarchical Self-Assembly of Carbon Dots into High-Aspect-Ratio Nanowires.

We report a spontaneous and hierarchical self-assembly mechanism of carbon dots prepared from citric acid and urea into nanowire structures with large aspect ratios (>50). Scattering-type scanning near-field optical microscopy (s-SNOM) with broadly tunable mid-IR excitation was used to interrogate details of the self-assembly process by generating nanoscopic chemical maps of local wire morphology and composition. s-SNOM images capture the evolution of wire formation and the complex interplay between different chemical constituents directing assembly over the nano- to microscopic length scales. We propose that residual citrate promotes tautomerization of melamine surface functionalities to produce supramolecular shape synthons comprised of melamine-cyanurate adducts capable of forming long-range and highly directional hydrogen-bonding networks. This intrinsic, heterogeneity-driven self-assembly mechanism reflects synergistic combinations of high chemical specificity and long-range cooperativity that may be harnessed to reproducibly fabricate functional structures on arbitrary surfaces.

Polarization Sensitivity in Scattering-Type Scanning Near-Field Optical Microscopy—Towards Nanoellipsometry

Electric field enhancement mediated through sharp tips in scattering-type scanning near-field optical microscopy (s-SNOM) enables optical material analysis down to the 10-nm length scale and even below. Nevertheless, the out-of-plane electric field component is primarily considered here due to the lightning rod effect of the elongated s-SNOM tip being orders of magnitude stronger than any in-plane field component. Nonetheless, the fundamental understanding of resonantly excited near-field coupled systems clearly allows us to take profit from all vectorial components, especially from the in-plane ones. In this paper, we theoretically and experimentally explore how the linear polarization control of both near-field illumination and detection can constructively be implemented to (non-)resonantly couple to selected sample permittivity tensor components, e.g., explicitly to the in-plane directions as well. When applying the point-dipole model, we show that resonantly excited samples respond with a strong near-field signal to all linear polarization angles. We then experimentally investigate the polarization-dependent responses for both non-resonant (Au) and phonon-resonant (3C-SiC) sample excitations at a 10.6 µm and 10.7 µm incident wavelength using a tabletop CO2 laser. Varying the illumination polarization angle thus allows one to quantitatively compare the scattered near-field signatures for the two wavelengths. Finally, we compare our experimental data to simulation results and thus gain a fundamental understanding of the polarization’s influence on the near-field interaction. As a result, the near-field components parallel and perpendicular to the sample surface can be easily disentangled and quantified through their polarization signatures, connecting them directly to the sample’s local permittivity.

Role of Local Conductivities in the Plasmon Reflections at the Edges and Stacking Domain Boundaries of Trilayer Graphene.

We employed infrared scattering-type scanning near-field optical microscopy (IR-sSNOM) to study surface plasmon polaritons (SPPs) in trilayer graphene (TLG). Our study reveals systematic differences in near-field IR spectra and SPP wavelengths between Bernal (ABA) and rhombohedral (ABC) TLG domains on SiO2, which can be explained by stacking-dependent intraband conductivities. We also observed that the SPP reflection profiles at ABA-ABC boundaries could be mostly accounted for by an idealized domain boundary defined by the conductivity discontinuity. However, we identified distinct shapes in the SPP profiles at the edges of the ABA and ABC TLG, which cannot be solely attributed to idealized edges with stacking-dependent conductivities. Instead, this can be explained by the presence of various edge structures with local conductivities differing from those of bulk TLGs. Our findings unveil a new structural element that can control SPP, and provide insights into the structures and electronic states of the edges of few-layer graphene.

Probing the micro- and nanoscopic properties of dental materials using infrared spectroscopy: A proof-of-principle study.

The preservation of oral health over a person's lifespan is a key factor for a high quality of life. Sustaining oral health requires high-end dental materials with a plethora of attributes such as durability, non-toxicity and ease of application. The combination of different requirements leads to increasing miniaturization and complexity of the material components such as the composite and adhesives, which makes the precise characterization of the material blend challenging. Here, we demonstrate how modern IR spectroscopy and imaging from the micro- to the nanoscale can provide insights on the chemical composition of the different material sections of a dental filling. We show how the recorded IR-images can be used for a fast and non-destructive porosity determination of the studied adhesive. Furthermore, the nanoscale study allows precise assessment of glass cluster structures and distribution within their characteristic organically modified ceramic (ORMOCER) matrix and an assessment of the interface between the composite and adhesive material. For the study we used a Fourier-Transform-IR (FTIR) microscope and a quantum cascade laser-based IR-microscope (QCL-IR) for the microscale analysis and a scattering-type scanning near-field optical microscopy (s-SNOM) for the nanoscale analysis. The paper ends with an in-depth discussion of the strengths and weaknesses of the different imaging methods to give the reader a clear picture for which scientific question the microscopes are best suited for. STATEMENT OF SIGNIFICANCE: Modern resin-based composites for dental restoration are complex multi-compound materials. In order to improve these high-end materials, it is important to investigate the molecular composition and morphology of the different parts. An emergent method to characterize these materials is infrared spectroscopic imaging, which combines the strength of infrared spectroscopy and an imaging approach known from optical microscopy. In this work, three state of the art methods are compared for investigating a dental filling including FTIR- and quantum cascade laser IR-imaging microscopy for the microscale and scattering-type scanning near-field optical microscopy for the nanoscale.

Near-field observation of mid-infrared edge modes in topological photonic crystals

Topological photonic crystals inherit the unique properties of topological insulators, including topologically protected energy transfer and unidirectional propagation, which offer an excellent platform for exploring exotic physics and developing photonic devices. However, topological photonic crystals possessing mid-infrared edge modes that have potential applications in infrared imaging, biosensing, thermal radiation energy transfer, etc., are seldom brought into focus. In this work, we study the topological properties of a photonic crystal slab (PCS) consisting of silicon square veins in the mid-infrared, which is intended to mimic the two-dimensional Su–Schrieffer–Heeger model. By interfacing topologically trivial and nontrivial PCSs, mid-infrared edge modes can appear at domain wall, according to the principle of bulk-edge correspondence. It is also demonstrated high-efficiency mid-infrared light transport can be achieved by these edge modes. In addition, adjusting the vertical offset near the interface can manipulate the bandwidth for various applications and turns the connected PCS structure to a photonic realization of Rice–Mele model. We further fabricate the PCS and provide an experimental observation of transverse-electric-like edge modes in mid-infrared by using the scattering-type scanning near-field optical microscope. Additionally, we integrate it with phase change material of nanoscale thickness, Ge2Sb2Te5, to realize an ultrafast and switchable topological waveguide with zero static power. This work not only enriches the fundamental understanding of topological physics in mid-infrared optical settings, but also shows promising prospects in compact devices for energy transfer and information processing for light sources in these wavelengths, for instance, thermal radiation.

Rough surface effect in terahertz near-field microscopy: 3D simulation analysis.

Terahertz scattering-type scanning near-field optical microscopy (THz-s-SNOM) has emerged as a powerful technique for high-resolution imaging. However, most previous studies have focused on simplified smooth surface models, overlooking the realistic surface roughness induced by contamination during sample preparation. In this work, we present a novel 3D model, to the best of our knowledge, that combines the point dipole model with the finite element method to investigate the influence of sample morphology on scattered signals. We explore surfaces with a protrusion, a depression, and random roughness, characterizing the variations in scattered signals and highlighting the role of higher-order scattering in mitigating surface roughness effects. Our findings provide valuable insights into the impact of sample morphology on THz-s-SNOM imaging.

Fabrication of pyramid-shaped gold tip for adiabatic nanofocusing of surface plasmon polaritons

Scattering-type scanning near-field optical microscopy based on adiabatic nanofocusing of surface plasmon polaritons (SPPs) is a powerful technique that can achieve free-background nanoscale optical resolution of material. However, the performance of the propagated confined modes strongly depends on the characteristic structure of the probe. Although the metallic pyramid structure provides excellent tightly confined modes, however, it is challenging to realize the required pyramid geometry. Here, we propose a simple method for fabricating a reproducible and controllable gold pyramid-shaped tip. The produced pyramid-shaped tips were made by electrochemical etching and by applying a pulse wave to the system. From a systematic study, we found that the key factor of fabrication of desired tip geometry is based on the platinum (Pt) wire shapes. Traditional circular-shaped platinum ring electrodes are used for gold tip fabrication in an electrochemical etching. In our method, we bent the Pt wire into a triangular shape as the electrode for the etching process. The influence of the geometrical ring shapes on the fabrication of the Au tip structure is investigated. The gold tip structure was optimized by controlling the Pt ring shape, and the desired pyramid-shaped gold tip was achieved with a yield of 70%. The obtained etched pyramid-shaped tips were then mounted along the side of one of the arms of a quartz tuning fork force sensor to test their performance for shear-force topographical image and for guiding SPPs along the pyramid wedge based on adiabatic nanofocusing microscopy. The result shows topographical images of indium tin oxide with a spatial resolution smaller than 20 nm. Furthermore, we experimentally demonstrate the generation of the SPPs that propagated adiabatically along the wedge of an appropriate fabricated pyramid-shaped tip toward a nanometer-size spot at the tip apex. The demonstration of this method strongly suggests that the obtained pyramid-shaped tip will enable new experiments probing the dynamics of optical excitations of individual metallic, semiconducting, and magnetic nanostructures.

13C- and 15N-labeling of amyloid-β and inhibitory peptides to study their interaction via nanoscale infrared spectroscopy

Interactions between molecules are fundamental in biology. They occur also between amyloidogenic peptides or proteins that are associated with different amyloid diseases, which makes it important to study the mutual influence of two polypeptides on each other’s properties in mixed samples. However, addressing this research question with imaging techniques faces the challenge to distinguish different polypeptides without adding artificial probes for detection. Here, we show that nanoscale infrared spectroscopy in combination with 13C, 15N-labeling solves this problem. We studied aggregated amyloid-β peptide (Aβ) and its interaction with an inhibitory peptide (NCAM1-PrP) using scattering-type scanning near-field optical microscopy. Although having similar secondary structure, labeled and unlabeled peptides could be distinguished by comparing optical phase images taken at wavenumbers characteristic for either the labeled or the unlabeled peptide. NCAM1-PrP seems to be able to associate with or to dissolve existing Aβ fibrils because pure Aβ fibrils were not detected after mixing.

Polaritonic Probe of an Emergent 2D Dipole Interface.

The use of work-function-mediated charge transfer has recently emerged as a reliable route toward nanoscale electrostatic control of individual atomic layers. Using α-RuCl3 as a 2D electron acceptor, we are able to induce emergent nano-optical behavior in hexagonal boron nitride (hBN) that arises due to interlayer charge polarization. Using scattering-type scanning near-field optical microscopy (s-SNOM), we find that a thin layer of α-RuCl3 adjacent to an hBN slab reduces the propagation length of hBN phonon polaritons (PhPs) in significant excess of what can be attributed to intrinsic optical losses. Concomitant nano-optical spectroscopy experiments reveal a novel resonance that aligns energetically with the region of excess PhP losses. These experimental observations are elucidated by first-principles density-functional theory and near-field model calculations, which show that the formation of a large interfacial dipole suppresses out-of-plane PhP propagation. Our results demonstrate the potential utility of charge-transfer heterostructures for tailoring optoelectronic properties of 2D insulators.

Pseudoheterodyne interferometry for multicolor near-field imaging.

We report the development and characterization of a detection technique for scattering-type scanning near-field optical microscopy (s-SNOM) that enables near-field amplitude and phase imaging at two or more wavelengths simultaneously. To this end, we introduce multispectral pseudoheterodyne (PSH) interferometry, where infrared lasers are combined to form a beam with a discrete spectrum of laser lines and a time-multiplexing scheme is employed to allow for the use of a single infrared detector. We first describe and validate the implementation of multispectral PSH into a commercial s-SNOM instrument. We then demonstrate its application for the real-time correction of the negative phase contrast (NPC), which provides reliable imaging of weak IR absorption at the nanoscale. We anticipate that multispectral PSH could improve data throughput, reduce effects of sample and interferometer drift, and help to establish multicolor s-SNOM imaging as a regular imaging modality, which could be particularly interesting as new infrared light sources become available.

Reference-free self-calibrating tip-based scattering-type THz near-field microscopy

In this work, we present a quantitative analysis model based on reference-free self-calibration to analyze scattered fields and approach curves on a dielectric substrate for terahertz scattering-type scanning near-field optical microscopy. The results of our model are compared with experimentally measured data and a fully numerical analysis based on a line dipole image method and a quasi-electrostatic approximation. The model is used to extract the effective radius of the tip and the relative permittivity of the silicon substrate to the near-field scattering signal. The measured approach curves on Au and silicon substrates show good agreement with the calculated approach curves, and the refractive index for silicon is precisely determined to be 3.42. For a tip-based THz scattering-type scanning near-field optical microscope, the proposed analysis model allows for the extraction of the effective probe radius and dielectric functions, thereby enabling conclusive measurements of geometric parameters and optical constants.

Near-Field Localization of the Boson Peak on Tantalum Films for Superconducting Quantum Devices.

Superconducting circuits are among the most advanced quantum computing technologies; however, their performance is limited by losses found in surface oxides and disordered materials. In this work, we demonstrate the identification and spatial localization of a near-field signature of loss centers on tantalum films using terahertz scattering-type scanning near-field optical microscopy. By utilizing terahertz nanospectroscopy, we observe a localized excess vibrational mode around 0.5 THz and identify this resonance as the boson peak, a signature of amorphous materials. Grazing-incidence wide-angle X-ray scattering reveals that oxides on freshly solvent-cleaned samples are amorphous, whereas crystalline phases emerge after aging in air. Through nanoscale localization of defect centers, our findings provide valuable insights for the optimization of fabrication procedures for new low-loss superconducting circuits.

Scanning Near-Field Optical Microscopy of Ultrathin Gold Films.

Ultrathin metal films are an essential platform for two-dimensional (2D) material compatible and flexible optoelectronics. Characterization of thin and ultrathin film-based devices requires a thorough consideration of the crystalline structure and local optical and electrical properties of the metal-2D material interface since they could be dramatically different from the bulk material. Recently, it was demonstrated that the growth of gold on the chemical vapor deposited monolayer MoS2 leads to a continuous metal film that preserves plasmonic optical response and conductivity even at thicknesses below 10 nm. Here, we examined the optical response and morphology of ultrathin gold films deposited on exfoliated MoS2 crystal flakes on the SiO2/Si substrate via scattering-type scanning near-field optical microscopy (s-SNOM). We demonstrate a direct relationship between the ability of thin film to support guided surface plasmon polaritons (SPP) and the s-SNOM signal intensity with a very high spatial resolution. Using this relationship, we observed the evolution of the structure of gold films grown on SiO2 and MoS2 with an increase in thickness. The continuous morphology and superior ability with respect to supporting SPPs of the ultrathin (≤10 nm) gold on MoS2 is further confirmed with scanning electron microscopy and direct observation of SPP fringes via s-SNOM. Our results establish s-SNOM as a tool for testing plasmonic films and motivate further theoretical research on the impact of the interplay between the guided modes and the local optical properties on the s-SNOM signal.