Phase-separated polymer blend films are an important class of functional materials with numerous technological applications in solar cells, catalysis, and biotechnology. These technologies are underpinned by the precise control of phase separation at the nanometer length-scales, which is highly challenging to visualize using conventional analytical tools. Herein, we introduce tip-enhanced Raman spectroscopy (TERS), in combination with atomic force microscopy (AFM), confocal Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS), as a sensitive nanoanalytical method to determine lateral and vertical phase-separation in polystyrene (PS)-poly(methyl methacrylate) (PMMA) polymer blend films. Correlative topographical, molecular, and elemental information reveals a vertical phase separation of the polymers within the top ca. 20 nm of the blend surface in addition to the lateral phase separation in the bulk. Furthermore, complementary TERS and XPS measurements reveal the presence of PMMA within 9.2 nm of the surface and PS at the subsurface of the polymer blend. This fundamental work establishes TERS as a powerful analytical tool for surface characterization of this important class of polymers at nanometer length scales.

Visualizing Surface Phase Separation in PS-PMMA Polymer Blends at the Nanoscale.

Graphene nanoribbons (GNRs) exhibit a series of essential electronic properties, especially in establishing tunable bandgaps. The bandgaps are determined by structural features of GNRs, including orientation, width, backbone/edge structure, heteroatom doping, and overall quality. These parameters affect the electronic properties of the GNRs to a large extent. To better incorporate GNRs into nanoscale electronic devices, obtaining high-quality GNRs with precisely defined bandgaps is a significant necessity. To date, different preparation techniques have offered a vast range of available materials for fabricating GNRs, where hydrocarbon gases and halogen-containing aromatic molecular precursors are the most important candidates. Therefore, it is fundamental to categorize the existing techniques in preparation, bandgap modulation, application of GNRs, and obtaining systematic knowledge on how to take advantage of this frontier material. Herein, overall understandings on the synthesis strategies and bandgap engineering tactics related to GNRs are presented in detail. Various techniques of top-down approaches and bottom-up syntheses, the origin of GNRs’ bandgap from quantum confinement effect, a diversity of bandgap engineering tools, and the applications of GNR-based devices are comprehensively reviewed with critical comparisons. In addition, the remaining challenges and promising opportunities are listed to catalyze upcoming findings pushing forward the ultimate applications of GNRs. 

Preparation, Bandgap Engineering, and Performance Control of Graphene Nanoribbons

Optical nanoimaging techniques, such as tip-enhanced Raman spectroscopy (TERS), are nowadays indispensable for chemical and optical characterization in the entire field of nanotechnology and have been extensively used for various applications, such as visualization of nanoscale defects in two-dimensional (2D) materials. However, it is still challenging to investigate micrometer-sized sample with nanoscale spatial resolution because of severe limitation of measurement time due to drift of the experimental system. Here, we achieved long-duration TERS imaging of a micrometer-sized WS2 sample for 6 hours in a reproducible manner. Our ultrastable TERS system enabled to reveal the defect density on the surface of tungsten disulfide layers in large area equivalent to the device scale. It also helped us to detect rare defect-related optical signals from the sample. The present study paves ways to evaluate nanoscale defects of 2D materials in large area and to unveil remarkable optical and chemical properties of large-sized nanostructured materials.

Ultrastable tip-enhanced hyperspectral optical nanoimaging for defect analysis of large-sized WS2 layers

Nanoscale chemical and structural characterization of single biomolecules and assemblies is of paramount importance for applications in biology and medicine. It aims to describe the molecular structure of biomolecules and their interaction with unprecedented spatial resolution to better comprehend underlying molecular mechanisms of biological processes involved in cell activity and diseases. Tip-enhanced Raman scattering (TERS) spectroscopy appears particularly appealing to reach these objectives. This state-of-the-art TERS technique is as versatile as it is ultrasensitive. To perform a successful TERS experiment, special care and a thorough methodology for the preparation of the TERS system, the TERS probe tip, and sample are needed. Intense efforts have been deployed to characterize nucleic acids, proteins and peptides, lipid membranes, and more complex systems such as cells and viruses using TERS. Although the vast majority of studies have first been performed in dry conditions, they have allowed for several scientific breakthroughs. These include DNA and RNA sequencing, and the determination of relationships between protein structure and biological function by the use of increasingly exploitative chemometric tools for spectral data analysis. The nanoscale determination of the secondary structure of amyloid fibrils, protofibrils and oligomers implicated in neurodegenerative diseases could, for instance, be connected with the toxicity of these species, amyloid formation pathways, and their interaction with phospholipids. Single particles of different viral strains could be distinguished from one another by comparison of their protein and lipid contents. In addition, TERS has allowed for the evermore accurate description of the molecular organization of lipid membranes. Very recent advances also demonstrated the possibility to carry out TERS in aqueous medium, which opens thrilling perspectives for the TERS technique in biological, biomedical, and potential clinical applications.

Nanoscale chemical characterization of biomolecules using tip-enhanced Raman spectroscopy.

Abstract Lack of appropriate tools for visualizing cell membrane molecules at the nanoscale in a non‐invasive and label‐free fashion limits our understanding of many vital cellular processes. Here, we use tip‐enhanced Raman spectroscopy (TERS) to visualize the molecular distribution in pancreatic cancer cell (BxPC‐3) membranes in ambient conditions without labelling, with a spatial resolution down to ca. 2.5 nm. TERS imaging reveals segregation of phenylalanine‐, histidine‐, phosphatidylcholine‐, protein‐, and cholesterol‐rich BxPC‐3 cell membrane domains at the nm length‐scale. TERS imaging also showed a cell membrane region where cholesterol is mixed with protein. Interestingly, the higher resolution TERS imaging revealed that the molecular domains observed on the BxPC‐3 cell membrane are not chemically “pure” but also contain other biomolecules. These results demonstrate the potential of TERS for non‐destructive and label‐free imaging of cell membranes with nanoscale resolution.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/anie.202210288

Nanoscale Chemical Imaging of Human Cell Membranes Using Tip‐Enhanced Raman Spectroscopy

Visualizing the molecular organization of lipid membranes is essential to comprehend their biological functions. However, current analytical techniques fail to provide a non-destructive and label-free characterization of lipid films under ambient conditions at nanometer length scales. In this work, we demonstrate the capability of tip-enhanced Raman spectroscopy (TERS) to probe the molecular organization of supported DPPC monolayers on Au (111), prepared using the Langmuir-Blodgett (LB) technique. High-quality TERS spectra were obtained, that permitted a direct correlation of the topography of the lipid monolayer with its TERS image for the first time. Furthermore, hyperspectral TERS imaging revealed the presence of nanometer-sized holes within a continuous DPPC monolayer structure. This shows that a homogeneously transferred LB monolayer is heterogeneous at the nanoscale. Finally, the high sensitivity and spatial resolution down to 20 nm of TERS imaging enabled reproducible, hyperspectral visualization of molecular disorder in the DPPC monolayers, demonstrating that TERS is a promising nanoanalytical tool to investigate the molecular organization of lipid membranes.

Nanoscale chemical imaging of supported lipid monolayers using Tip-enhanced Raman Spectroscopy

Visualising structural modification of patterned graphene nanoribbons using tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for nondestructive and label-free surface chemical characterization at nanometer length scales. However, despite being considered nondestructive, the interaction of the TERS probe used in the analysis can alter the molecular organization of the sample. In this study, we investigate the role of the atomic force microscopy (AFM) feedback (contact mode and tapping mode) on molecular perturbation in TERS analysis of soft samples using a self-assembled monolayer (SAM) of 2-chloro-4-nitrobenzene-1-thiol (Cl-NBT) as a test sample. Surprisingly, the tapping mode shows a consistently higher TERS signal resulting from a minimal perturbation of the Cl-NBT SAM compared to the contact mode. This study provides novel insights into the choice of the correct AFM-TERS operation mode for nanoscale chemical analysis of soft and delicate samples and is expected to expedite the growing application of TERS in this area.

Molecular Perturbation Effects in AFM-Based Tip-Enhanced Raman Spectroscopy: Contact versus Tapping Mode.

In Situ Visualization of Optoelectronic Behavior of Grain Boundaries in Monolayer WSe2 at the Nanoscale

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Nanoscale chemical imaging of supported lipid monolayers using Tip-enhanced Raman Spectroscopy

Visualising structural modification of patterned graphene nanoribbons using tip-enhanced Raman spectroscopy.

Molecular Perturbation Effects in AFM-Based Tip-Enhanced Raman Spectroscopy: Contact versus Tapping Mode.

In Situ Visualization of Optoelectronic Behavior of Grain Boundaries in Monolayer WSe2 at the Nanoscale