NanoRamanTM Platform AFM-Raman/PL, TERS/TEPL, SNOM, Chemical and Physical Imaging at the Nanoscale - HORIBA
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NanoRamanTM
Platform
AFM-Raman/PL, TERS/TEPL,
SNOM, Chemical and Physical
Imaging at the Nanoscale
Since its introduction in the early 80’s,
Scanning Probe Microscopy (SPM) has Nano The ultimate versatile platform for
made nanoscale imaging an affordable
physical and chemical characterization
reality. The technique provides a continuously
growing variety of surface analysis methods
for the physical characterization of materials,
yet label-free chemical sensitivity is still
RamanTM
challenging.... Powerful
Raman spectroscopy has long provided
a versatile way to determine the structure
Key Features imultaneous SPM and spectroscopic measurements.
S
and chemical composition of molecules and, High numerical aperture objectives from both top and side for best co-localized spatial resolution
ULTI-SAMPLE ANALYSIS PLATFORM
M
despite its diffraction-limited spatial resolution, and best TERS collection efficiency.
has become a standard method in fields Macro, micro and nano scale measurements can
High-throughput and high speed measurements.
ranging from materials science to the life be performed on the same platform.
sciences. Broad range of detection wavelengths, from deep UV to Infrared.
ASE OF USE
E High spectral resolution with the LabRAM HR Evolution spectrometer.
In combination, the two techniques Fully automated operation, start measuring
yield an attractive and unique tool within minutes, not hours!
for entering the nano-world.
With over a decade of experience in this
exciting new field, we have refined the
RUE CONFOCALITY
T 1 2 3
High spatial resolution, automated mapping
technique to its utmost with uncompromised
performance to bring you a tool that is not stages, full microscope visualization options.
only extremely powerful and versatile,
HIGH COLLECTION EFFICIENCY
but is also so easy to use, fast and reliable
that generating outstanding data is Top-down, oblique and bottom Raman detection
virtually effortless. for optimum resolution and throughput in both
co-localized and tip-enhanced measurements.
IGH SPECTRAL RESOLUTION
H
Ultimate spectral resolution performance,
multiple gratings with automated switching, Enabling feature: IR laser diode High collection: Wide optical access Ease of use: Tip replacement
for AFM feedback Avoiding Optical High numerical aperture objectives for Tip replacement without removing the
wide spectral range analysis for Raman and
Interferences for TERS application both top and side illuminations sample or disturbing the optics
Photoluminescence.
HIGH SPATIAL RESOLUTION 4 5 6
Nanoscale spectroscopic resolution (down
to 10 nm) through Tip-Enhanced Optical
Spectroscopies (TERS: Tip-Enhanced Raman
Spectroscopy and TEPL: Tip-Enhanced
Photoluminescence).
MULTI-TECHNIQUE / MULTI-ENVIRONMENT
Numerous SPM modes including AFM,
conductive and electrical modes (cAFM,
KPFM), STM, liquid cell and electrochemical Ease of use: Auto tip-alignment and Ease of use: XYZ Objective Scanner Stability: High resonance frequency
2
environment, together with chemical mapping tuning Operator independent, great Easy Raman laser to tip alignment for AFM scanners High performance without
5 reproducibility in tip exchange long-term stability active vibration isolation
3 1 through TERS/TEPL.
Full control of the two instruments through one
4 workstation and a powerful software control,
SPM and spectrometer can be operated
simultaneously or independently.
Simple and Fast
OBUSTNESS / STABILITY
R ne-click cantilever alignment, frequency tuning and optimization, requiring no manual adjustments.
O
6
High resonance frequency AFM scanners, Easy cantilever exchange without affecting the sample and breaking the alignment.
operation far away from noises! High Fast and intuitive Raman laser to AFM tip alignment with Objective Scanner.
performance is obtained without active vibration Full control through one workstation.
XploRA Nano: OmegaScope AFM combined isolation.
with XploRA Raman microscope
AFM-Raman and TERS made easy
TERS Tip
Reliable AFM-TERS tips
Reflection
Configuration Excitation OmniTM Tip-Enhanced Raman Spectroscopy TERS
p
probes* are designed to acquire topography and Raman
Raman Field spectral information of a sample simultaneously.
scattering
Enhancement
s Tip in contact
Tip retracted
The combination of HORIBA's NanoRaman system
Sample with OmniTM TERS probes provides the ideal high-
enhancement TERS solution. The OmniTM TERS probes
are compatible with XploRA Nano, LabRAM HR
Nano, LabRAM Soleil Nano, OmegaScope and TRIOS
*Manufactured for HORIBA by APP NANO
Raman Excitation systems. They are nanofabricated using highly doped
scattering p
single crystal silicon with unparalleled reproducibility,
What is co-localized
s
Transmission robustness and sharpness for consistent high resolution
Configuration
AFM-Raman? imaging capabilities.
Raman and SPM (Scanning Probe Microscope) i-based AFM tips coated with gold or silver (with
S Multilayer structure: tip optimized to minimize
How TERS works? analysis can be combined on a single microscope protective layer) interference from silicon substrate in the spectra
system. Co-localized AFM-Raman measurement Allow all modes of TERS operation: top, side, Innovative packaging to extend tip shelf life
is the sequential or simultaneous acquisition and bottom optical accesses TERS active layer: silver with protective layer, or
In TERS, the Raman excitation laser is focused
of correlated SPM and Raman maps. Suitable for TERS and TEPL measurements with the gold
at the tip of an SPM probe coated with either gold
or silver . Matching the wavelength of the AFM and other SPM techniques like STM following lasers: 532, 594, 633, 638, 671, 785, and 830
Raman laser to the natural surface plasmonic or tuning-fork Shear-Force or Normal-Force nm
frequency of the noble metal generates an intense microscopy, provide topographic, mechanical,
localized evanescent electromagnetic fied or thermal, electrical, and magnetic properties down
«hot spot» at the probe tip . The field extends to molecular resolution (on the order of nm, over
only for a few nanometers from the tip surface. μm2 area). On the other hand, confocal Raman
Since the intensity of the Raman spectra from spectroscopy and imaging provides specific
the sample is proportional to the local electric chemical information about the material, with a
field, bringing the hot spot close to the sample
significantly enhances the Raman signal, often by
diffraction limited spatial resolution.
TERS proven samples
a power of 105 or 106 .
HORIBA offers a set of test samples: one
is single-wall carbon nanotubes (CNTs)
together with graphene oxide flakes (GO)
suitably dispersed to allow easy imaging.
This sample is used to demonstrate a
routine 20 nm resolution in TERS imaging.
Another sample is dedicated to
demonstration of AFM molecular resolution.
LabRAM Soleil Nano: OmegaScope AFM, equipped
with its environmental chamber, combined with
LabRAM Soleil Raman microscope
Large area - difficult samples
Forsterite 1 Forsterite 2 Enstatite
Whitlockite Anorthite Rhodonite Aspirin Paracetamol Caffeine Coating
Silicon Carbide
1 mm 1 mm 500 µm 20 µm 1 µm 6 µm 1µm 1µm
Raman image - Mineral - Macro map Raman image - Sectioned pharmaceutical tablet Automatic panoramic AFM AFM (topography) – 3D Top Mode AFM (topography) - MFM – AFM (topography) – Zinc oxide AFM (topography) – 150 nm
across a sectioned meteorite (contact mode) – imaging - Optical Fiber Ferrite garnet film nanorods - Z range is 3.6 µm gold nanoparticules
120 scans – CoCr features
on Si surface Sample
courtesy of Dr A.N. Shokin,
NIIFP; Image courtesy of Dr
A. Temiryazev, IRE RAS.
True confocality - 3D maps High spectral resolution - High selectivity
Quartz CO2 (gas)
Bead Matrix Water + CO2 (aqueous) Emulsion matrix TiO2 particles 5L 4L 3L 2L 1L MoS2 cSi polySi ncSi Compressive strain Tensile strain
10 µm 10 µm 10 µm 40 µm 10 µm 2 µm 1 µm
Raman image - XYZ volume map Raman image - Fluid inclusion- Raman image - Emulsion - Titanium dioxide Combined Photoluminescence Raman image - Layered MoS2 Raman image - Silicon chip Raman image - Nano-indented
of expanded polymer bead in XYZ volume map through fluid particles in emulsion and Raman image - 2D crystal structure - Map image was - crystalline, poly and nano- silicon – mapping of mechanical
matrix inclusion in a quartz matrix of WS2 created from low frequency crystalline silicon regions stress
(
Multi SPM techniques
9 µm 3 µm 2 µm 1 µm 1 µm 1 µm 350 nm 250 nm
AFM – Bacillus Cereus MFM - Yttrium Iron Garnet (YIG) Lateral Force Modulation – KPFM – DTP (pentacene Nano Lithography – Vector force AFM in liquid – Virus like particles AFM in liquid – plasmid DNA AFM (height) – DNA origami on
vegetative cells film Sample courtesy of Dr A.V. Polymer-fullerene blend derivative) on gold scratching on polycarbonate (VLP) Sample courtesy of Prof. O. V. on mica mica –Sample courtesy of Prof.
Maryakhin (P3HT:PCBM) Karpova (Lomonosov Moscow State Michael Norton, Marshall University
University)
Tip-Enhanced Raman Spectroscopy
CH stretching (Polymer)
CH stretching (Polymer)
G band (Graphene)
G band (Graphene Oxide)
2D band (Graphene)
5 µm 400 nm 500 nm 500 nm 400 nm 200 nm
TEPL image – WSe2 flake AFM and TERS images - Patterned AFM and TERS images - Circular TERS image – Graphene oxide on TERS/TEPL image – MoS2 flake on TERS/TEPL image – CVD
on Si substrate graphene oxide flake by “pulsed- pattern imprinted in CVD grown gold Si substrate Sample courtesy of Dr grown WS2 on Si substrate
force lithography” graphene transferred to gold Filippo Fabbri (IMEM) Sample courtesy of Dr Adam
Schwartzberg (Berkeley Lab)
D band (defects)
2D band (Graphitic structure)
600 nm 800 nm 200 nm
600 nm 500 nm 600 nm 10 nm 25 nm
KPFM and TERS images TERS and AFM images – SAMs of TERS images - Array of gold TERS and AFM images – Carbon TERS image – Gold nanodisks TERS images – Engineered TERS image – Single wall carbon
– Graphene Oxide (COOH azobenzene thiols on gold disks on Si functionalized with nanotubes on glass (SERS substrate) Sample courtesy of DNA – (left) A/T and (right) G/C nanotube on gold – spatial
functionalized) flakes on gold 1,4 Aminothiophenol. Sample Dr Jean-François Bryche (Sherbrooke homopolymeric blocks Data resolution 8 nm
courtesy of Dr Evgeniya Sheremet, University) courtesy of Dr Noah Kolodjieski,
Technische Universität Chemnitz RMD
Atomic
True molecular resolution resolution
80 nm 16 nm 22 nm 2 nm 1 nm
AFM (topography) - Molecular AFM (topography)- Cholesteryl AFM (topography) - Palmityl AFM (topography) - SAMs of STM (constant current mode) -
Resolution in Air - Melissic Acid Stearate on HOPG Palmitate on HOPG Palmityl Palmitate - the pitch HOPG
between adjacent alkane chains
is about 4 Å
10-6m 10-7m 10-8m 10-9m
...Micro... ... To Nanoscopy!
A stable and versatile solution
Integrated Software CUSTOMER "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/
STORIES 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
NanoRaman data acquisition A pioneer in TERS
versatile scanning probe microscope for the combination with Raman
spectroscopy. With the clever, fully motorized and automated instrument
with ONE software “The NanoRaman team of LPICM lab, Ecole
Polytechnique/CNRS, developed jointly with
alignment, every advanced measurement at the nanoscale become an
easy to configure experiment."
HORIBA Scientific the first HORIBA TERS Prof. Masamichi Yoshimura
system prototype a dozen or so years ago.
Key Features
Head of the Surface Science Laboratory
Later commercialized, the prototype featured Toyota Technological Institute, Japan
STM and AFM SPM modes combined with
side illumination in Raman backscattering
NE SOFTWARE for the acquistion of AFM,
O configuration. Owing to its excellent
Raman and Photoluminescence signals in
TERS/TEPL and AFM-Raman/PL co-localized
performance and relative ease of use, it was
applied with success to the study of various
Great technical support
materials and nanostructures such as self- “We have been working for two years on a versatile configuration of
measurements.
assembled organic monolayers, carbon the NanoRaman platform from HORIBA that allows both reflection and
LabSpec 6 SPECTROSCOPY SUITE nanotubes, patterned semiconductors, transmission measurements. As researchers in an electrochemistry Lab,
for Integrated Multivariate and high level analysis etc. Among the outstanding scientific we were searching for analytical tools which enable the characterization
at a touch of a button. PCA, MCR, HCA, DCA. successes achieved with the system, the of materials at the nanoscale and under the condition of their operation.
world premiere demonstration of stimulated The stability of the SPM system (true atomic/molecular resolution) and
NIQUE IMAGING MODES and
U (pump - probe) TERS is to be mentioned. the robustness of the optical coupling, which enables fast and effective
Being quite user-open and versatile, the TERS mappings, totally met our expectations. The versatility of the Horiba
processing, including: Spec-TopTM mode -
prototype measurement configuration could system already made possible new characterization pathways such as
Patented TERS imaging mode: TERS be successfully adapted to accommodate TERS in liquid and electrochemical TERS. We have also greatly enjoyed
ULTI-AREA ANALYSIS: Because
M
measurement is performed when the tip a polarization control of both excitation and the technical assistance from Horiba which has definitively boosted our
full rectangular area scans can be too scattered radiations, an external laser pump,
is in direct contact with the surface, transition instrumental developments”.
time-consuming, several trapezoidal as well as an additional detector for Tip-
between the pixels of the map is performed Enhanced Photoluminescence.
areas can be selected on the AFM image Dr. Ivan T. Lucas and Prof. Emmanuel Maisonhaute
in semicontact mode, which preserves the Since the pioneering years of the TERS Laboratory “Interfaces and Electrochemical Systems”,
for Raman mapping.
sharpness and enhancing properties of the tip. prototype, HORIBA Scientific have Sorbonne University, France
URVES MAP: Spectroscopic and Force
C developed a novel, module-based TERS
UAL-SPEC MODE: Acquisition of 2 different
D system featuring a large number of SPM
curves can be performed through images modes (STM, AFM, tuning-fork, etc.)
Raman maps. The far-field-map can be
characterizing the local stiffness or the implementable under various illumination
subtracted from the near-field-map, giving – collection conditions (off-axis, top and
adhesion distribution. Force constant
thus a pure TERS image. bottom backscattering). Thanks to the
calibration (Sader method).
customer-oriented culture of HORIBA, the
NanoRaman team of LPICM is currently
A fully automated system
updating its “historical” prototype with the With our NanoRaman instrument from HORIBA, we have the full power
novel TERS system. It will allow us not of Raman, AFM, TERS, TEPL, and many other related modes bundled
only to pursue our actual research topics into one system operating in reflection. Every member of my group from
by adding new measurements, but also to bachelor student level to postdoc researcher enjoys the easy usage of
initiate new research areas, impossible to this fully motorized/automated system that can deliver correlated surface
address with the present system.“ characterization data from microscale down to nanoscale resolution. We
are using this AFM/Raman platform for research on optical and electrical
Prof. Razvigor Ossikovski properties of nanomaterials every day and we are appreciating the enormous
Nano-Raman team leader potential of the TERS technique for studying nanomaterials such as CNTs
LPICM, Ecole Polytechnique, France and 2D TMDCs with unprecedented spatial resolution down to 2 nm.
Prof. Dietrich R.T. Zahn
Head of the Semiconductor Physics Research Group
Multi-area Raman Force curves; 3D topographic image Spectroscopic curve; Technische Universität Chemnitz, Germany
mapping (color); Adhesion map distribution tip-to-sample distance
background image is versus Raman shift
the AFM topography
Find out more at www.horiba.com/nanoraman
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info.sci@horiba.com
for sample analysis and hands-on training for
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This document is not contractually binding under any circumstances - Printed in France - ©HORIBA Jobin Yvon 03/2021
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LabRAM HR Nano: OmegaScope AFM, equipped with its enclosure,
combined with LabRAM HR Evolution Raman microscope
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