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

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.

Tip-enhanced Raman spectroscopy with amplitude-controlled tapping-mode AFM.

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for analyzing chemical compositions at the nanoscale owing to near-field light localized at a metallic tip. In TERS, atomic force microscopy (AFM) is commonly used for tip position control. AFM is often controlled under the contact mode for TERS, whereas the tapping mode, which is another major operation mode, has not often been employed despite several advantages, such as low sample damage. One of the reasons is the low TERS signal intensity because the tip is mostly away from the sample during the tapping motion. In this study, we quantitatively investigated the effect of the tapping amplitude on the TERS signal. We numerically evaluated the dependence of the TERS signal on tapping amplitude. We found that the tapping amplitude had a significant effect on the TERS signal, and an acceptable level of TERS signal was obtained by reducing the amplitude to a few nanometers. We further demonstrated amplitude-controlled tapping-mode TERS measurement. We observed a strong dependence of the TERS intensity on the tapping amplitude, which is in agreement with our numerical calculations. This practical but essential study encourages the use of the tapping mode for further advancing TERS and related optical techniques.

Polarization Raman Imaging of Organic Monolayer Islands for Crystal Orientation Analysis.

An organic semiconductor film made of diphenyl derivative dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DPh-DNTT) has high carrier mobility. However, this mobility may be greatly affected by the crystal orientation of the DPh-DNTT's first layer. Polarization Raman microscopy is widely used to quantitatively analyze the molecular orientation, and thus holds great potential as a powerful tool to investigate the crystal orientation of monolayer DPh-DNTT with high spatial resolution. In this study, we demonstrate polarization Raman imaging of monolayer DPh-DNTT islands for crystal orientation analysis. We found that the DPh-DNTT sample indicated a strong dependence of the Raman intensity on the incident polarization direction. Based on the polarization dependence, we developed an analytical method of determining the crystal orientation of the monolayer DPh-DNTT islands and experimentally confirmed that our technique was highly effective at imaging the islands' crystal orientation with a spatial resolution of a few hundred nanometers.