HORIBA's leading Raman technology is now integrated with AIST-NT’s scanning probe microscopy (SPM). The NanoRamanTM platform integrates Atomic Force Microscopy (AFM) that can provide physical sample information on the nanometer scale, including topography, hardness, adhesion, friction, surface potential, electrical and thermal conductivity, temperature and piezo response (among many others), near-field optical techniques (SNOM or NSOM), Scanning Tunneling Microscopy (STM), tuning fork techniques (Shear-force and Normal-force imaging modes), electrochemistry, all together with the chemical information obtained from Raman spectroscopy and Photoluminescence. The end result is a more comprehensive sample characterization in one versatile instrument, for fast simultaneous co-localized measurements, Tip-Enhanced Raman Spectroscopy (TERS) and Tip-Enhanced PhotoLuminescence (TEPL).
This protocol details procedures that will enable researchers to reliably perform TERS imaging using a transmission-mode AFM-TERS configuration on both biological and non-biological samples.
The proof of subnanometer resolution using TERS is demonstrated. The authors show direct nucleic acid sequencing using TERS of a single-stranded DNA. TERS signals with a step of 0.5 nm are collected, an optical resolution comparable to the bond length between two adjacent DNA bases.
Nanoscale chemical imaging in aqueous solution via TERS, with sub-15 nm spatial resolution, is demonstrated. Optical fields of a plasmonic substrate in aqueous solution are directly imaged, showing the potential of TERS to follow chemical transformations at solid-liquid interfaces.
TEPL is used to locally map the distribution of excitonic emission across monolayer MoSe2-WSe2 lateral heterostructures. Aging effects and their extent on the exciton-suppression process are quantitatively evaluated.
New zirconia-protected TERS probes are introduced and used for nanoscale spatially resolved characterization of a photocatalytic reaction within an aqueous environment.
The study demonstrates the remote-excitation of TERS with fine spatial resolution (10 nm). This solution avoid the laser interaction with the sample substrate and thus is free of Raman background noise.
The potential of TERS in identifying characteristic chemostructural elements of protein oligomeric forms associated with protein deposition diseases is here demonstrated. By exploiting the capability of nanometric resolution, spatial organization and surface character of individual oligomers were carefully inspected.
TERS imaging of individual lead titanate (PbTiO3) nanoislands is reported with a spatial resolution of ~3 nm. TER spectrum of the grain core reflects PbTiO3 close to the ferroelectric‐to‐paraelectric phase transition which is primarily related to the finite size of the grains.
The multi-parameter measurement methodology proposed in this paper greatly extends the capability of TERS allowing a direct correlation of local topography, chemical composition and electronic properties at the nanoscale here applied on carboxyl-modified graphene oxide.
AFM, TERS and TEPL are performed simultaneously and showed that the variation of the light emission properties is due to different effects depending on the shape of the MoS2 single layer, the concentration of point defect and the presence of nanoscale terrace in triangular monolayer.
1D and 2D patterns were successfully imprinted in flakes of single-layer graphene and graphene oxide by means of pulsed-force nanolithography using a single-crystal diamond AFM probe. The resulting patterns demonstrated dramatically-increased TERS activity compared to flat non-patterned areas.
TERS is used for the first time on synthetic MoSe2 monolayers, combined with other SPM techniques, all with sub-20 nm spatial resolution. Nanoscale heterogeneities in the Raman spectra of MoSe2 are uncovered and the presence of nanoscale domains of MoO3 in the 2D flakes is revealed.
”With our NanoRaman instrument from HORIBA, we have the full power of Raman, AFM, TERS, TEPL, and many other related modes bundled into one system operating in reflection. Every member of my group from bachelor student level to postdoc researcher enjoys the easy usage of this fully motorized/automated system that can deliver correlated surface characterization data from microscale down to nanoscale resolution. We are using this AFM/Raman platform for research on optical and electrical properties of nanomaterials every day and we are appreciating the enormous potential of the TERS techniquefor studying nanomaterials such as CNTs and 2D TMDCs with unprecedent spatial resolution down to 2 nm.”
"We are using the NanoRaman platform from HORIBA Scientific for research on carbon-based nanomaterials and especially the characterization of graphene oxide for energy applications. This AFM/Raman system is easy-to-use with help of the state-of-art hot spot search function and has number of unique build-in SPM techniques, including a unique imaging mode that makes TERS possible. HORIBA (and former AIST-NT) has developed one of the most stable and versatile scanning probe microscope for the combination with Raman spectroscopy. With the clever, fully motorized and automated instrument alignment, every advanced measurement at the nanoscale become an easy to configure experiment."
“We have been working for two years on a versatile configuration of the NanoRaman platform from HORIBA that allows both reflection and transmission measurements. As researchers in an electrochemistry Lab, we were searching for analytical tools which enable the characterization of materials at the nanoscale and under the condition of their operation. The stability of the SPM system (true atomic/molecular resolution) and the robustness of the optical coupling, which enables fast and effective TERS mappings, totally met our expectations. The versatility of the Horiba system already made possible new characterization pathways such as TERS in liquid and electrochemical TERS. We have also greatly enjoyed the technical assistance from Horiba which has definitively boosted our instrumental developments”.
“The nano-Raman team of LPICM lab, Ecole Polytechnique, developed jointly with HORIBA Scientific the first HORIBA TERS system prototype a dozen or so years ago. Later commercialized, the prototype featured STM and AFM SPM modes combined with side illumination in Raman backscattering configuration. Owing to its excellent performance and relative ease of use, it was applied with success to the study of various materials and nanostructures such as self-assembled organic monolayers, carbon nanotubes, patterned semiconductors, etc. Among the outstanding scientific successes achieved with the system, the world premiere demonstration of stimulated (pump - probe) TERS is to be mentioned. Being quite user-open and versatile, the prototype measurement configuration could be successfully adapted to accommodate a polarization control of both excitation and scattered radiations, an external laser pump, as well as an additional detector for Tip-Enhanced Photoluminescence.
Since the pioneering years of the TERS prototype, HORIBA Scientific have developed a novel, module-based TERS system featuring a large number of SPM modes (STM, AFM, tuning-fork, etc.) implementable under various illumination – collection conditions (off-axis, top and bottom backscattering). Thanks to the customer-oriented culture of HORIBA, the nano-Raman team of LPICM is currently updating its “historical” prototype with the novel TERS system. It will allow us not only to pursue our actual research topics by adding new measurements, but also to initiate new research areas, impossible to address with the present system.”
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