Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells....
Transcript of Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells....
![Page 1: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/1.jpg)
Recent Advancements in Nanoscale IR Spectroscopy and Imaging
Anirban Roy, Qichi Hu, Honghua Yang, Miriam Unger and Curtis Marcott
![Page 2: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/2.jpg)
Outline
• Company Background
• Introduction to AFM-IR
• Latest AFM-IR Advancements
• Resonance Enhanced AFM-IR
• HyperSpectral Imaging/Spectroscopy
• Tapping AFM-IR Imaging/Spectroscopy
• Technical Overview
• Applications
• s-SNOM Technology and Applications
• Tunable IR Laser Options
• Summary
7/18/2019 2Bruker Confidential
![Page 3: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/3.jpg)
Bruker Nano Acquires Anasys Instruments
7/18/2019 3Bruker Confidential
• Bruker Nano Surfaces Division acquired Anasys Instruments Corp on April 10th 2018
• All nanoIR products are now integrated into the Bruker Nano Product Support
![Page 4: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/4.jpg)
Nanoscale IR spectroscopy
nanoIR™ 1st Generation
AFM-IR
nanoIR2™ 2nd Generation AFM-IR
Top Down Configuration & Resonance Enhanced
nanoIR2-s™ Combined
IR s-SNOM & AFM-IR
nanoIR2-FS™ 3RD GenerationFASTspectra
2010 2014 2015
2016 2017
Tapping AFM-IRHYPERspectra
NEWnanoIR3™
Latest Generation nanoIR platform with
Tapping AFM-IR
2018
7/18/2019 Bruker Confidential 4
![Page 5: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/5.jpg)
Infrared Spectroscopy Introduction
2 ≠ 0 01 = 0 0
IR Spectrum
Source: Wikipedia
IR light wave
![Page 6: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/6.jpg)
Power and Limitations of Infrared Microspectroscopy
Multilayer film, courtesy of Dr. Curtis Marcott
0
.5
1
1.5
2
1800 1600 1400 1200 1000
Wavenumber
Ab
so
rb
an
ce
PET
Tie Layer
EVOH
LDPE
FT-IR
IR microspectroscopy
annual publications
microscope
IR spectra Chemical Image IR microspectroscopy
applications
• Materials Science
• Consumer products
• Pharmaceuticals
• Life sciences
• Health & beauty
• Forensics
Abbe diffration limit:
Practical resolution many microns
![Page 7: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/7.jpg)
AFM-Based IR Spectroscopy (AFM-IR)
7/18/2019 7Bruker Confidential
Time (ms)
Dazzi, A.; Prazeres, R.; Glotin, F.; Ortega, J.M.; Opt. Lett. 2005, 30, 2388-2390.
Ernst AbbeAlexandre Dazzi
2014 Ernst Abbe Award
![Page 8: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/8.jpg)
Nanoscale IR Spectroscopy
7/18/2019 8Bruker Confidential
![Page 9: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/9.jpg)
nanoscale infrared imaging & spectroscopy capabilities
Chemical composition & nanoscale property mapping
Nanoscale IR chemical analysis
Rich, interpretable spectra
directly correlates to FTIR
Monolayer sensitivity & high spatial resolution
7/18/2019 Bruker Confidential 9
![Page 10: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/10.jpg)
Organic nanoContaminants
Polymer blends & Block
Copolymers
Multilayer films Nanofibers
Nano-Composites
Broad range of nanoIR applications
+++
Perovskites &
Solar CellsnanoIR spectra
2D Materials/Graphene
Life Science
7/18/2019 Bruker Confidential 10
![Page 11: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/11.jpg)
Resonance Enhanced Mode
7/18/2019 11Bruker Confidential
![Page 12: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/12.jpg)
Deflection signal
laser signal
Resonance Enhanced Mode
![Page 13: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/13.jpg)
Laser repetition rate
Forced resonance makes AFM-IR more sensitive
![Page 14: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/14.jpg)
Single Monolayer Sensitivity
F. Lu, M. Jin, and M.A. Belkin, Nat. Photonics 8, 307–312 (2013).
![Page 15: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/15.jpg)
Resonance enhanced AFM-IR of PEG monolayer
Topography IR image at 1340 cm-1
C-O-C AsymCH2 wag
CH2 scissor
![Page 16: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/16.jpg)
Halobacterium
Salinarum deposited
on a Au substrate
Amide
IAmide II
To
po
gra
ph
y
IR Im
ag
e
at 1
54
0 c
m-1
3 x 4 μm
Purple Membrane (Resonance Enhanced AFM-IR)
![Page 17: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/17.jpg)
QCLs are getting faster!
0
0.2
0.4
0.6
0.8
1
1.2
7809801180138015801780
Ab
sorp
tio
n (
au)
Wavenumber (cm-1)
Single spectrum, 400 msec sweep, 0.2 msec time constant, no averaging
Anasys AFM-IR 100 msec
FTIR
![Page 18: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/18.jpg)
Faster Scanning Enables Hyperspectral Imaging
X
Y
A
B
C
Figure 5. Illustration of the hyperspectral image cube. High speed AFM-based IR spectroscopy allow for the first time practical hyperspectral imaging, i.e., where spectra are mapped at matrix of XY points. One can extract segments of the hyperspectral cube to obtain (A) chemical maps that show spatial variation in absorption at a given wavelength, (B) spectral line maps showing the variation in spectra in one direction, or (C) individual spectra at any X,Y location.
Hyperspectral image cube
![Page 19: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/19.jpg)
Hyperspectral animation
5-mm x 5-mm, 50 x 50 spectrum array on PS/PMMA/epoxy blend
Move cursor onto above image and click on arrow to start animation
![Page 20: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/20.jpg)
Hyperspectral array PCA weight maps
AFM image PS PMMA Epoxy
5-mm x 5-mm, 50 x 50 spectrum array on PS/PMMA/epoxy blend
• New hyperspectral imaging provides point by point spectra over a large
number of data points to provide an array of spectra and chemical images
at specific wavenumbers
• Principle component analysis can be applied to identify specific chemical
components and their spatial distribution
![Page 21: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/21.jpg)
nanoIR3-s™ S-SNOM - High Performance s-SNOM Imaging
• IR s-SNOM platform for optical & chemical Imaging• Supports multiple laser types, visible, nearIR• Electrical nanoscale property mapping• Upgradeable to nanoIR-spectroscopy
NEW nanoIR3 platform configurations
nanoIR3-s™ High Performance IR nano-spectroscopy
• Complementary s-SNOM & Tapping AFM-IR• Highest Performance IR nano-spectroscopy• Broadband Spectroscopy & Chemical Imaging• Nanoscale property mapping• Versatility & Easy to Use
nanoIR3™ - Latest Generation nanoIR platform with Tapping AFM-IR
• Highest performance nanoIR spectra with AFM-IR• Sub-10nm resolution IR chemical imaging with Tapping AFM-
IR• Correlates to FTIR & industry databases• Easy to use for fast, productive measurements
s-SNOM imaging Phase and Amplitude on HbN
Plasmonic Imaging on Graphene with Tapping AFM-IR & s-SNOM
nanoIR Spectroscopy of Polyethersulphone (PES)
7/18/2019 Bruker Confidential 21
![Page 22: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/22.jpg)
Sample Environmental Control
Sample transfer port for nanoIR3-s
• Protects sample in controlled gas environment from glove box to nanoIR system to protect
• includes integrated humidity sensor with optional high sensitivity humidity and oxygen sensors
Humidity control & heater & cooler
• For control of humidity/gas & temperature for in-situ AFM-IR
• 4% to 95% non condensing
• 4°C to 80°C heating and cooling
7/18/2019 Bruker Confidential 22
![Page 23: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/23.jpg)
IR Polarization Control & extended IR range
Polarizer OptionOptional & upgradeable
7/18/2019 Bruker Confidential 23
![Page 24: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/24.jpg)
nanoIR nanoscale property mapping modes
7/18/2019 24
7/18/2019 Bruker Confidential 24
![Page 25: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/25.jpg)
Tapping AFM-IR: Technical OverviewConcept
7/18/2019 25Bruker Confidential
Zt : Distance of the Tip
Zs : Sample expansion (photothermal)
k/g : Linear/non-linear force constant
as: Absorption coefficient
at: Tip oscillation amplitude
wp: Laser pulse rate
wn: cantilever eigen mode frequency (n=1,2,3…)
Resonance Condition: w1 + wp = w2
Fundamental
mode Pulse
rate
2nd Eigen
mode
zt
zs
n
n
n n
![Page 26: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/26.jpg)
Tapping AFM-IR: Technical OverviewSchematic
7/18/2019 26Bruker Confidential
Heterodyne Force Microscopy
M.T. Cuberes, J. Nanomater., 2009
Resonance Condition:
w1 + wp = w2
Signal
/w2
![Page 27: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/27.jpg)
Tapping AFM-IR: Key features
7/18/2019 27Bruker Confidential
• Broad Application range:
- Hard/soft sample, Adhesives, Membranes, Particulates
- Minimal sample/tip degradation due to absence of lateral forces
• Improved Sensitivity:
- Sensitivity enhanced by cantilever Q-factor – new probes
- AFM detector with higher sensitivity
- Efficient optical beam delivery optics with minimal loss
• High Spatial Resolution:
- Spatial resolution extends to ~10 nm or better
• Multimodal Imaging:
- Simultaneous chemical and viscoelastic property (Tapping Phase) imaging
![Page 28: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/28.jpg)
7/18/2019 28Bruker Confidential
Tapping AFM-IR: ApplicationsPolymer 01: PEMA/PMMA Blend
Tapping IR Image at 1026 cm-1
PEMA
PMMA
Tapping AFM-IR Spectra Height
Sample courtesy: University of Minnesota
![Page 29: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/29.jpg)
7/18/2019 29Bruker Confidential
Tapping AFM-IR: ApplicationsPolymer 02: PS/PMMA block copolymer
Sample courtesy: CEA-Leti
2 x 2 um2
Height
HeightTapping IR Image
at 1730 cm-1
5 nm
Tapping AFM-IR image at1730 cm-1 highlights PMMAspheres embedded in PSmatrix
Observed spatial resolution ~5 nm
![Page 30: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/30.jpg)
7/18/2019 30Bruker Confidential
Tapping AFM-IR: ApplicationsBio-pharmaceuticals 01: Skin/Dexamethasone
- Tapping AFM-IR image ratio at 1456/1740 cm-1
highlights the relative abundance of the drug in the lipophilic regions
(bright yellow)
Optical
1456
15321660
-CH2 bending
Present in both drug and
long chain lipids1740
Ester C=O
in the
lipids
Amide I & II bands
from Proteins
Height IR Image Ratio
1456/1740
Sample courtesy: FU Berlin
![Page 31: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/31.jpg)
7/18/2019 31Bruker Confidential
Tapping AFM-IR: ApplicationsBio-pharmaceuticals 02: Anti-cancer drug delivery
Centrone et al., Analyst, 2018, 143, 3808-3813
• Paclitaxel, a power anti-cancerdrug, suffers from low efficacyand side effects due to low watersolubility/recrystallization
• Recent study by Centrone andcoworkers highlights the use ofTapping AFM-IR technology toexplore the effect of differentencapsulations in drug delivery
• High resolution compositionalsensitivity of this techniqueunfolds new developments oflipid-polymer hybrid films in drugdelivery applications
![Page 32: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/32.jpg)
7/18/2019 32Bruker Confidential
Tapping AFM-IR: ApplicationsOrganic Photovoltaics: TQ1/PC70BM Blend
Height
IR Image Ratio
1598/1738
Donor (TQ1 polymer)
Acceptor (PC70BM)
- Tapping AFM-IR spectra and imageshighlights the polymer rich matrix and PC70BMrich domains
Sample courtesy: Karlstad University
![Page 33: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/33.jpg)
7/18/2019 33Bruker Confidential
Tapping AFM-IR: Applications2D Materials: Graphene/Graphene Oxide
Manuscript in prepLiu et al., Carbon, 2018, 127, 141-148
- Tapping AFM-IR spectra and imagesshow sensitivity to monolayer Grapheneand Graphene Oxide
Surface
Plasmon
Polariton
(SPP)
![Page 34: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/34.jpg)
7/18/2019 34Bruker Confidential
Tapping AFM-IR: ApplicationsFailure Analysis: Organic Nanocontaminations
Tapping AFM-IR
Spectra
FTIR Library Search
“…Knowing why devices fail is a must
when designing next-generation
products..”
V. Lakshminarayanan
www.rfdesign.com, 2011
• AFM-IR technology complementstraditional analytical tools used for failureanalysis in nanoscale semiconductordevices/architectures
• Enhanced sensitivity extends to sampleswith thickness <20 nm
• Tapping AFM-IR technology demonstratespositive identification of nanoscale organiccontaminants on Silicon wafer
![Page 35: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/35.jpg)
Tapping AFM-IR Measurementson nanocontaminant sample
• Tapping AFM-IR spectra show absorption bands consistent with earlier measurements performed onsite – contamination is most likely synthetic polyester (PET/PBT)
• IR signal sensitivity goes down to 3 nm thick residue (bright green)
• Each spectrum is an average of 5 measurements, NOT smoothed
25 nm
35 nm27 nm
18 nm12 nm
5 nm 3 nm
Sample Thickness1730
1264
1242
11001020
35 nm
Heig
ht
![Page 36: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/36.jpg)
Tapping AFM-IR of a Biological Membrane
Wavenumber (cm-1)
mm
![Page 37: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/37.jpg)
Polymeric Nanoparticles for drug delivery
PLA
PLGAantibiotic
PVA
Antibiotic = pipemidic acid
FTIR spectra of products
![Page 38: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/38.jpg)
AFM-IR contact modeTapping AFM-IR
Mapping at 1760 cm-1 center on ester carbonyl band of PLA
PLA/PVA nanoparticle
Polymeric Nanoparticles for drug delivery
![Page 39: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/39.jpg)
PLA/PVA nanoparticle
Mapping at 1425 cm-1 center on absorption band of PVA
Polymeric Nanoparticles for drug delivery
![Page 40: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/40.jpg)
PLGA/PVA nanoparticles with antibiotic
topography
@1640 cm-1
@1425 cm-1
@1415 cm-1
![Page 41: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/41.jpg)
Benefits of Tapping AFM-IR approach
• Better spatial resolution/softer samples via tapping AFM
• Improved chemical imaging via heterodyne detection
• Insensitive to non-local background forces
• Material selectivity via resonance tuning
7/18/2019 SpSJ 2019 Kyoto
![Page 42: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/42.jpg)
Complementary: AFM-IR and s-SNOMscattering scanning nearfield optical microscopy
7/18/2019 42Bruker Confidential
s-SNOMAFM-IR
Thermal expansion proportional
to absorption and thermal
expansion coefficients
Scattered light depends on
complex optical constants
![Page 43: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/43.jpg)
Sensitivity of AFM-IR and s-SNOM
0.00
0.20
0.40
0.60
0.80
1.00
1.20
AFM-IR signalstrength
Organics Inorganics
![Page 44: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/44.jpg)
s-SNOM: complex optical property
Metal coated tip acts like an antenna to enhance and localize the light.
Spatial resolution: tip radius 10~20 nm
Eb
![Page 45: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/45.jpg)
Previous: Spatio-spectral Imaging & Broadband Spectroscopy
J. Am. Chem. Soc., 2013, 135, 18292
Proc. Natl. Acad. Sci. 111, 7191 (2014)
Disadvantages: slow, limited
spectral resolution
Disadvantages: can’t do
narrowband imaging (e.g. for
compositional mapping)
Spatio-spectral Imaging Broadband Spectroscopy
![Page 46: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/46.jpg)
sSNOM 1580cm-1 sSNOM 1600cm-1AFM height
2um
2µm
Application: Fano-resonance Bilayer Graphene
Graphene 2, 38727 (2013)
![Page 47: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/47.jpg)
s-SNOM with a broadband laser source
![Page 48: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/48.jpg)
700
757
s-SNOM spectrum of polystyrene below 800 cm-1
SNOM
phase spectrum
FTIR
spectrum
15
μm
![Page 49: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/49.jpg)
nanoIR Laser Options
• AFM-IR lasers (Pulsed tunable OPO & QCL) can provide both spectroscopy & wavelength specific imaging
• Only CW/P QCL (tunable) lasers provide spectroscopy & wavelength specific imaging for s-SNOM
• nanoFTIR lasers only provide spectroscopy & imaging capabilities (AFM-IR&s-SNOM)
4000800 1800 2700 3600
C-H, OH, N-H
Stretch region
FASTspectra QCL
(w/Hyperspectral)
Fast OPO
Hyperspectral QCL
1950
1900
2800 3600
800 1800
4000
Nano FTIR - Advanced
OPO/DFG
POINTSpectra
CW/Pulse QCL laser
600
950
CO2 – 10.6um 943
650 20004000
Mid-IR range
Wavenumber(cm-1)
Fingerprint
Region
Triple Bonds &
conjugated bonds
2000 2300
1900950
![Page 50: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/50.jpg)
Additional Applications – from 2017-2018 publications
• Life Science
• Recent paper in Cell – Simone Ruggeri, Tuomas Knowles (Cambridge)
• AFM-IR in Fluid – Andrea Centrone (NIST)
• Malaria Infected Red Blood Cells – Bayden Wood (Monash)
• In vivo AFM-IR of Bacteria – Bayden Wood (Monash)
• Materials Science
• Deuterium-labeled polyolefin copolymer blend - Dow
• Core/Shell effect in electrospun PHB copolymer fibers – Delaware
• Functionalized graphene - Manchester
• h-BN – Photothermal AFM-IR of 2D Materials - Harvard
• Geoscience - Schlumberger & USGS
7/18/2019 50Bruker Confidential
![Page 51: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/51.jpg)
Additional Applications (continued)
• Atmospheric Aerosols – Mark Banaszak Holl (Michigan/Monash)
• Polarized AFM-IR – Karsten Hinrichs (ISAS)
7/18/2019 51Bruker Confidential
![Page 52: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/52.jpg)
Summary
7/18/2019 52Bruker Confidential
• Unmatched sensitivity for nanoIR spectroscopy & chemical imaging
• <10nm resolution chemical imaging
• Point spectroscopy in 1-2 secs
• HYPERspectral imaging/Spectroscopy for robust statistical analysis
• Easy to use, high performance AFM imaging with improved noise and sensitivity
Recent Technological Advancements in nanoscale IR Technology offers
![Page 53: Recent Advancements in Nanoscale IR Spectroscopy and …Perovskites & nanoIR spectra. Solar Cells. 2D Materials/Graphene. Life Science. ... • IR s-SNOM platform for optical & chemical](https://reader035.fdocuments.in/reader035/viewer/2022070703/5e7f011a1876016f327667e1/html5/thumbnails/53.jpg)
© Copyright Bruker Corporation. All rights reserved.
www.bruker.com
© Copyright Bruker Corporation. All rights reserved.