Noncontact tip-enhanced Raman spectroscopy for nanomaterials and biomedical applications

Tip-enhanced Raman spectroscopy (TERS) has been established as one the most efficient analytical techniques for probing vibrational states with nanoscale resolution. While TERS may be a source of unique information about chemical structure and interactions, it has a limited use for materials with rough or sticky surfaces. Development of the TERS approach utilizing a non-contact scanning probe microscopy mode can significantly extend the number of applications. Here we demonstrate a proof of the concept and feasibility of a non-contact TERS approach and test it on various materials. Our experiments show that non-contact TERS can provide 10 nm spatial resolution and a Raman signal enhancement factor of 105, making it very promising for chemical imaging of materials with high aspect ratio surface patterns and biomaterials.

[1]  H. Uji‐i,et al.  Silver nanowires for highly reproducible cantilever based AFM-TERS microscopy: towards a universal TERS probe. , 2018, Nanoscale.

[2]  B. Weckhuysen,et al.  Nanoscale chemical imaging of solid-liquid interfaces using tip-enhanced Raman spectroscopy. , 2018, Nanoscale.

[3]  Fabiana A. Caetano,et al.  Tip-enhanced Raman spectroscopy of amyloid β at neuronal spines. , 2017, The Analyst.

[4]  Duane D. Miller,et al.  Novel Selective Agents for the Degradation of Androgen Receptor Variants to Treat Castration-Resistant Prostate Cancer. , 2017, Cancer research.

[5]  M. R. Wagner,et al.  Breakdown of Far-Field Raman Selection Rules by Light-Plasmon Coupling Demonstrated by Tip-Enhanced Raman Scattering. , 2017, The journal of physical chemistry letters.

[6]  Volker Deckert,et al.  Mastering high resolution tip-enhanced Raman spectroscopy: towards a shift of perception. , 2017, Chemical Society reviews.

[7]  Satoshi Kawata,et al.  Tip-enhanced Raman spectroscopy - from early developments to recent advances. , 2017, Chemical Society reviews.

[8]  M. Scully,et al.  Gap-mode enhancement on MoS2 probed by functionalized tip-enhanced Raman spectroscopy , 2016 .

[9]  V. Bocharova,et al.  Graphene Oxide as a Radical Initiator: Free Radical and Controlled Radical Polymerization of Sodium 4-Vinylbenzenesulfonate with Graphene Oxide. , 2016, ACS macro letters.

[10]  Y. Ozaki,et al.  Tip-enhanced Raman spectroscopic measurement of stress change in the local domain of epitaxial graphene on the carbon face of 4H-SiC(000-1). , 2014, Physical chemistry chemical physics : PCCP.

[11]  Naresh Kumar,et al.  Accurate measurement of enhancement factor in tip-enhanced Raman spectroscopy through elimination of far-field artefacts. , 2014 .

[12]  Satoshi Kawata,et al.  A 1.7 nm resolution chemical analysis of carbon nanotubes by tip-enhanced Raman imaging in the ambient , 2014, Nature Communications.

[13]  Satoshi Kawata,et al.  Tip-enhanced nano-Raman analytical imaging of locally induced strain distribution in carbon nanotubes , 2013, Nature Communications.

[14]  J. L. Yang,et al.  Chemical mapping of a single molecule by plasmon-enhanced Raman scattering , 2013, Nature.

[15]  T. Heinz,et al.  Intrinsic line shape of the Raman 2D-mode in freestanding graphene monolayers. , 2013, Nano letters.

[16]  Rebecca L. Agapov,et al.  Protecting TERS probes from degradation: extending mechanical and chemical stability , 2013 .

[17]  N. Lavrik,et al.  Large scale atmospheric pressure chemical vapor deposition of graphene , 2013 .

[18]  S. Kawata,et al.  Far-field free tapping-mode tip-enhanced Raman microscopy , 2013 .

[19]  S. Kawata,et al.  Highly reproducible tip‐enhanced Raman scattering using an oxidized and metallized silicon cantilever tip as a tool for everyone , 2012 .

[20]  Volker Deckert,et al.  Structure and composition of insulin fibril surfaces probed by TERS. , 2012, Journal of the American Chemical Society.

[21]  Renato Zenobi,et al.  Developments in and practical guidelines for tip-enhanced Raman spectroscopy. , 2012, Nanoscale.

[22]  C. Barrios,et al.  Highly Stable, Protected Plasmonic Nanostructures for Tip Enhanced Raman Spectroscopy , 2009 .

[23]  D. Roy,et al.  Novel methodology for estimating the enhancement factor for tip-enhanced Raman spectroscopy , 2009 .

[24]  V. Nampoori,et al.  Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser , 2008 .

[25]  S. Kawata,et al.  Confinement of enhanced field investigated by tip-sample gap regulation in tapping-mode tip-enhanced Raman microscopy , 2007 .

[26]  T. Frauenheim,et al.  DFTB+, a sparse matrix-based implementation of the DFTB method. , 2007, The journal of physical chemistry. A.

[27]  Henryk A. Witek,et al.  Modeling vibrational spectra using the self-consistent charge density-functional tight-binding method. I. Raman spectra , 2004 .

[28]  Thomas Frauenheim,et al.  Atomistic simulations of complex materials: ground-state and excited-state properties , 2002 .

[29]  Klaus D. Jandt,et al.  Atomic force microscopy of biomaterials surfaces and interfaces , 2001 .

[30]  Sándor Suhai,et al.  Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties , 1998 .

[31]  D. Braunstein Imaging an F‐actin structure with noncontact scanning force microscopy , 1995 .

[32]  I. Sokolov On the limits of the spectroscopic ability of AFM and the interaction between an AFM tip and a sample , 1994 .

[33]  E. Altman,et al.  Noncontact Atomic Force Microscopy: An Emerging Tool for Fundamental Catalysis Research. , 2015, Accounts of chemical research.

[34]  P. Hendra,et al.  The laser-Raman and infra-red spectra of poly(methyl methacrylate) , 1969 .