Abstract

Tip-enhanced Raman scattering (TERS) microscopy attracts increasing attention for visualization and characterization of strain distribution on crystalline samples at a nanoscale due to nano-sized fields localized at a metal tip. However, as the metal tip approaches close to a sample surface, a force acts between the tip and sample, which can induce unwanted perturbation on the local strain of the sample. Analysis and evaluation of intrinsic strains on samples with a high reliability demands a technique to correlate TERS spectra with the tip-sample force. Here, we present a TERS microscope based on a frequency-modulation atomic force microscope (FM-AFM) using a quartz tuning fork (QTF) as a force sensor. By continuously monitoring a shift in the resonance frequency of the QTF during TERS, the tip-sample force can be directly measured in both attractive and repulsive force regions, which is not possible by other AFMs. TERS spectra of single-walled carbon nanotubes (CNTs) were measured simultaneously while changing the tip-sample distance and hence the tip-sample force acting on the CNTs. We found that TERS occurs at the tip-sample distance where the repulsive force dominantly works and mostly decays out in the attractive force region.

Highlights

  • In this paper, we aim to expand the previous work11 and to establish force-correlative spectroscopy in Tip-enhanced Raman scattering (TERS) microscopy, i.e., a technique to measure tip-sample force simultaneously with TERS spectra

  • Tip-enhanced spectra are discussed in conjunction with the tip-sample force in the repulsive force region and in the attractive force region that is not accessible with the conventional TERS microscopy based on contact- and tapping-mode atomic force microscope (AFM)

  • A high resolution TERS microscopy image of a single carbon nanotubes (CNTs) is shown to demonstrate the imaging capability of the developed TERS microscope based on frequency-modulation atomic force microscope (FM-AFM)

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Summary

Introduction

We aim to expand the previous work11 and to establish force-correlative spectroscopy in TERS microscopy, i.e., a technique to measure tip-sample force simultaneously with TERS spectra. From the amount of frequency shift ∆f, the tip-sample force can be determined, with positive and negative ∆f corresponding to the repulsive and attractive tip-sample force, respectively. We demonstrate simultaneous measurements of TERS spectra and tip-sample force using CNTs as a sample.

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