Imaging Spectroscopic Ellipsometry Research Articles

Fast thickness mapping of large-area exfoliated two-dimensional transition metal dichalcogenides by imaging spectroscopic ellipsometry

Two-dimensional transition metal dichalcogenides (2D TMDCs) have gained significant attention from the scientific community due to their exceptional properties, making them extremely attractive for optoelectronic and photonic applications. However, many exfoliation or synthesis techniques yield 2D crystals with limited crystalline quality and/or small lateral size. Here, we report a facile Au-assisted exfoliation method, yielding high-quality, large-area monolayers with lateral sizes of hundreds of micrometers. A self-assembled monolayer of (3-aminopropyl)triethoxysilane (APTES) is employed to improve the adhesion between the 2D material and the target substrate, dramatically improving the yield and reliability of the exfoliation process. The monolayer nature of the final sample is then assessed by means of Imaging Spectroscopic Ellipsometry (iSE), which enables a quick and reliable thickness mapping over millimeter-sized areas.

Local dielectric function of hBN-encapsulated WS2 flakes grown by chemical vapor deposition

Hexagonal boron nitride (hBN), sometimes referred to as white graphene, receives growing interest in the scientific community, especially when combined into van der Waals (vdW) homo- and heterostacks, in which novel and interesting phenomena may arise. hBN is also commonly used in combination with two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs). The realization of hBN-encapsulated TMDC homo- and heterostacks can indeed offer opportunities to investigate and compare TMDC excitonic properties in various stacking configurations. In this work, we investigate the optical response at the micrometric scale of mono- and homo-bilayer WS2 grown by chemical vapor deposition and encapsulated between two single layers of hBN. Imaging spectroscopic ellipsometry is exploited to extract the local dielectric functions across one single WS2 flake and detect the evolution of excitonic spectral features from monolayer to bilayer regions. Exciton energies undergo a redshift by passing from hBN-encapsulated single layer to homo-bilayer WS2, as also confirmed by photoluminescence spectra. Our results can provide a reference for the study of the dielectric properties of more complex systems where hBN is combined with other 2D vdW materials into heterostructures and are stimulating towards the investigation of the optical response of other technologically-relevant heterostacks.

Systematic analysis of the Rayleigh–Wood anomalies and the symmetry relations of 2D‐periodic nanostructures by imaging spectroscopic ellipsometry

AbstractPeriodic arrays of metallic nanostructures were fabricated by electron beam lithography and studied by means of spectroscopic imaging ellipsometry in the near infrared to ultraviolet spectral ranges. The sample consists of gold nanodisc and nanorod gratings on a silicon substrate. Spectroscopic imaging ellipsometry, allowing for the simultaneous observation of all gratings with microscopic resolution, was used to systematically analyze the varying grating and nanostructure parameters. The ellipsometric spectra obtained for a full in‐plane sample rotation proved to be a highly sensitive measure of the gratings’ Rayleigh–Wood anomalies. Their dependence on the sample azimuth was in excellent agreement with the Rayleigh lines calculated from the grating parameters and could be tracked for both the ambient‐to‐grating and the grating–substrate interfaces. Contrary to other studies on similarly sized nanoparticle arrays, we found no indication of localized plasmon resonance in the visible range of the spectrum, but only a weak NIR response truncated by the Rayleigh lines. Finally, the symmetry of the structures was investigated by imaging Mueller‐matrix measurements.

Anomalous optical response of graphene on hexagonal boron nitride substrates

Graphene/hBN heterostructures can be considered as one of the basic building blocks for the next-generation optoelectronics mostly owing to the record-high electron mobilities. However, currently, the studies of the intrinsic optical properties of graphene are limited to the standard substrates (SiO2/Si, glass, quartz) despite the growing interest in graphene/hBN heterostructures. This can be attributed to a challenging task of the determination of hBN’s strongly anisotropic dielectric tensor in the total optical response. In this study, we overcome this issue through imaging spectroscopic ellipsometry utilizing simultaneous analysis of hBN’s optical response with and without graphene monolayers. Our technique allowed us to retrieve the optical constants of graphene from graphene/hBN heterostructures in a broad spectral range of 250–950 nm. Our results suggest that graphene’s absorption on hBN may exceed the one of graphene on SiO2/Si by about 60%.

Local Optical Properties in CVD-Grown Monolayer WS2 Flakes.

Excitons dominate the light absorption and re-emission spectra of monolayer transition-metal dichalcogenides (TMD). Microscopic investigations of the excitonic response in TMD almost invariably extract information from the radiative recombination step, which only constitutes one part of the picture. Here, by exploiting imaging spectroscopic ellipsometry (ISE), we investigate the spatial dependence of the dielectric function of chemical vapor deposition (CVD)-grown WS2 flakes with a microscopic lateral resolution, thus providing information about the spatially varying, exciton-induced light absorption in the monolayer WS2. Comparing the ISE results with imaging photoluminescence spectroscopy data, the presence of several correlated features was observed, along with the unexpected existence of a few uncorrelated characteristics. The latter demonstrates that the exciton-induced absorption and emission features are not always proportional at the microscopic scale. Microstructural modulations across the flakes, having a different influence on the absorption and re-emission of light, are deemed responsible for the effect.

Interaction Forces on Polyampholytic Hydrogel Gradient Surfaces.

Rational design and informed development of nontoxic antifouling coatings requires a thorough understanding of the interactions between surfaces and fouling species. With more complex antifouling materials, such as composites or zwitterionic polymers, there follows also a need for better characterization of the materials as such. To further the understanding of the antifouling properties of charge-balanced polymers, we explore the properties of layered polyelectrolytes and their interactions with charged surfaces. These polymers were prepared via self-initiated photografting and photopolymerization (SIPGP); on top of a uniform bottom layer of anionic poly(methacrylic acid) (PMAA), a cationic poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) thickness gradient was formed. Infrared microscopy and imaging spectroscopic ellipsometry were used to characterize chemical composition and swelling of the combined layer. Direct force measurements by colloidal probe atomic force microscopy were performed to investigate the forces between the polymer gradients and charged probes. The swelling of PMAA and PDMAEMA are very different, with steric and electrostatic forces varying in a nontrivial manner along the gradient. The gradients can be tuned to form a protein-resistant charge-neutral region, and we demonstrate that this region, where both electrostatic and steric forces are small, is highly compressed and the origin of the protein resistance of this region is most likely an effect of strong hydration of charged residues at the surface, rather than swelling or bulk hydration of the polymer. In the highly swollen regions far from charge-neutrality, steric forces dominate the interactions between the probe and the polymer. In these regions, the SIPGP polymer has qualitative similarities with brushes, but we were unable to quantitatively describe the polymer as a brush, supporting previous data suggesting that these polymers are cross-linked.

Large-Size Single-Crystal Oligothiophene-Based Monolayers for Field-Effect Transistors.

High structural quality of crystalline organic semiconductors is the basis of their superior electrical performance. Recent progress in quasi two-dimensional (2D) organic semiconductor films challenges bulk single crystals because both demonstrate competing charge-carrier mobilities. As the thinnest molecular semiconductors, monolayers offer numerous advantages such as unmatched flexibility and light transparency as well they are an excellent platform for sensing. Oligothiophene-based materials are among the most promising ones for light-emitting applications because of the combination of efficient luminescence and decent charge-carrier mobility. Here, we demonstrate single-crystal monolayers of unprecedented structural order grown from four alkyl-substituted thiophene and thiophene-phenylene oligomers. The monolayer crystals with lateral dimensions up to 3 mm were grown from the solution on substrates with various surface energies and roughness by drop or spin-casting with subsequent slow solvent evaporation. Our data indicate that 2D crystallization resulting in single-crystal monolayers occurs at the receding gas-solution-substrate contact line. The structural properties of the monolayers were studied by grazing-incidence X-ray diffraction/reflectivity, atomic force and differential interference contrast microscopies, and imaging spectroscopic ellipsometry. These highly ordered monolayers demonstrated an excellent performance in organic field-effect transistors approaching the best values reported for the thiophene or thiophene-phenylene oligomers. Our findings pave the way for efficient monolayer organic electronics highlighting the high potential of simple solution-processing techniques for the growth of large-size single-crystal monolayers with excellent structural order and electrical performance competing against bulk single crystals.

Imaging spectroscopic ellipsometry of MoS2

Micromechanically exfoliated mono- and multilayers of molybdenum disulfide (MoS2) are investigated by spectroscopic imaging ellipsometry. In combination with knife edge illumination, MoS2 flakes can be detected and classified on arbitrary flat and also transparent substrates with a lateral resolution down to 1–2 µm. The complex dielectric functions from mono- and trilayer MoS2 are presented. They are extracted from a multilayer model to fit the measured ellipsometric angles employing an anisotropic and an isotropic fit approach. We find that the energies of the critical points of the optical constants can be treated to be independent of the utilized model, whereas the magnitude of the optical constants varies with the used model. The anisotropic model suggests a maximum absorbance for a MoS2 sheet supported by sapphire of about 14% for monolayer and of 10% for trilayer MoS2. Furthermore, the lateral homogeneity of the complex dielectric function for monolayer MoS2 is investigated with a spatial resolution of 2 µm. Only minor fluctuations are observed. No evidence for strain, for a significant amount of disorder or lattice defects can be found in the wrinkle-free regions of the MoS2 monolayer from complementary µ-Raman spectroscopy measurements. We assume that the minor lateral variation in the optical constants are caused by lateral modification in the van der Waals interaction presumably caused by the preparation using micromechanical exfoliation and viscoelastic stamping.

Characterization of Thermally Reduced Graphene Oxide by Imaging Ellipsometry

The dispersion functions for the refractive index and the extinction coefficient of single- and multiple-layer graphene oxide samples were measured by imaging spectroscopic ellipsometry in the wavelength range of 350−1000 nm and were compared to previously reported results measured by confocal microscopy. The dispersion functions for thin platelets were also compared to those obtained by standard spectroscopic ellipsometry on a deposit consisting of many overlapping graphene oxide layers. Changes were observed in both the thickness of the deposits and the values of the dispersion parameters following heating. A model is proposed to explain these observations, based on the removal of water between the graphene-oxide layers upon thermal treatment.

N and k testing of magnetic heads with imaging spectroscopic ellipsometry

AbstractThe method of imaging spectroscopic ellipsometry is applied on magnetic read/write heads of hard disks. By means of spectroscopic ellipsometry, an optical model of the TiC/Al2O3 substrate including surface roughness and concentration gradient of TiC in the alumina substrate is generated. Surface roughness is measured with both ellipsometry and atomic force microscopy (AFM). The granular structure of TiC/Al2O3 is investigated in micrographs of n and k. It is discussed how Delta mapping of the magnetic pole area of the head can be used to measure DLC coating thickness and the variation of chemical constitution of the metal substrate. Repeatability of measurements of Delta is optimized in a one µm2 region of interest (ROI) on a metal stripe of the magnetic pole. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)