New Microscopies New Microscopies for Polymer Analysesfor Polymer Analyses
…… WhatWhat’’s in YOUR toolkit?s in YOUR toolkit?
Barbara FosterBarbara FosterMicroscopy/Marketing & EducationMicroscopy/Marketing & Education
[email protected]@mme1.com
*IDKYCDT!*IDKYCDT!
Light/Confocal +(Chemical Fingerprints)Light/Confocal +(Chemical Fingerprints)FTFT--IRIRRamanRaman
AFM +++AFM +++In Liquids (including electrochemistry)In Liquids (including electrochemistry)Thermal AnalysisThermal AnalysisUltramicrotomyUltramicrotomyWith NSOM, Raman confocal and fluorescence With NSOM, Raman confocal and fluorescence spectroscopyspectroscopy
*I didn’t know you could do that!
FTFT--IR + MicroscopyIR + MicroscopyLight from the microscope impinges on the surface and undergoes Light from the microscope impinges on the surface and undergoes total internal reflectiontotal internal reflection
In the process of reflecting, the beam generates a small, In the process of reflecting, the beam generates a small, evanescent field at the interface, which penetrates the second evanescent field at the interface, which penetrates the second material. If the second material absorbs this e n e r g y, the material. If the second material absorbs this e n e r g y, the intensity for the reflected beam is reduced or attenuated. intensity for the reflected beam is reduced or attenuated.
This absorption is selective, This absorption is selective, dependent on the chemistry dependent on the chemistry of the second material. of the second material.
Scanning the attenuation over Scanning the attenuation over a specific wavelength region a specific wavelength region (2500(2500––16,250 nm or 4000 to 16,250 nm or 4000 to 650cm650cm--1) produces a spectrum 1) produces a spectrum that provides a specific molecular that provides a specific molecular fingerprint for the second material.fingerprint for the second material.
Smiths Detection
Target Target MeasureMeasureLocate glass particle in oil (No contact)
Spectrum of oil
Mixed spectrum – oil + glass Pure spectrum, glass
Raman Confocal Raman Confocal
Like FTLike FT--IR: another Vibrational SpectroscopyIR: another Vibrational SpectroscopyInelastic scatteringInelastic scattering
Compliments FTCompliments FT--IRIRFTFT--IR does not work well with IR does not work well with materials exhibiting strong materials exhibiting strong OO--H or NH or N--H effects; H effects; Raman doesRaman does
The Challenges: The Challenges: Very weak signal! (10Very weak signal! (10--44 of fluorescence; 10of fluorescence; 10--77 or 10or 10--8 8 of ambient)of ambient)Often in same spectral range as fluorescenceOften in same spectral range as fluorescence
Raman + Raman + ……Renishaw
Horiba/JY
Ion diffusion across a polymer membraneIon diffusion across a polymer membrane
Triflate in water (anion)Trifluoromethane sulfonateNote peaks at 766 nm and 1034 nm for un-coordinated anion
Li+ triflate complex at varying depths
Horiba/JY
> d
Li+ doped p(EtO) cast on vanadium oxide ceramicMobile cation: Li+Anion: Triflate
Scanning Probe Microscopy Scanning Probe Microscopy (SPM)(SPM)
Atomic Force Microscopy (AFM)Atomic Force Microscopy (AFM)Scanning Tunneling Microscopy (STM)Scanning Tunneling Microscopy (STM)
What do What do YOUYOU need to do?need to do?
STM
Shear Force
300°C
Raman
Magnetism
Adhesion
Lithography
Roughness
Conductivity
Resistance
Near Field
Vacuum
LiquidBiology
Elasticity
Nanotubes
Nanotechnology
Polymers
Education
How does AFM work?How does AFM work?
Sample
Piezo
Photodiode Feedback loop
Laser
Tip
Image
Multiple configurationsMultiple configurations
STM image of carbon nanotube deposited on HOPG substrate.Atomic structure of nanotube is clearly visible.
12x12 nm
Image courtesy of Prof. V.K. Nevolin, Moscow Institute of Electronic Engineering.
Critical Atomic Resolution
AFM Topography & Phase images AFM Topography & Phase images ––PolyethylenePolyethylene
Topography Phase
Scan size: 4x4μm
AFM Topography & Phase imagesAFM Topography & Phase imagesPolyethylene oxidePolyethylene oxide
Topography Phase
Scan size: 25x25 µm
Electromotive Electromotive ForceForce Microscopy (EFM)Microscopy (EFM)Polymer blend: aPPPolymer blend: aPP--MAMA
A.V. Krayev et al. Polymer 45 (2004) 8195 -82000
Polymer blend (aPP-MA) with two different dielectric constants
Scan size: 1.5 x 1.5 μm
Surface potential distribution Surface potential distribution ––Scanning Kelvin Mode (SKM)Scanning Kelvin Mode (SKM)
Potential (2-pass, semi-contact)Topography
AAzobenzenezobenzene derivative derivative -- selfself--assembled filmassembled film
Scan size: 45Scan size: 45x45 µm
Atomic Force Acoustical Microscopy Atomic Force Acoustical Microscopy Polyethylene strips (HD/LD)Polyethylene strips (HD/LD)
Topography AFAM
Scan size: 10x10 μm
AFAM senses local surface elasticity with high lateral resolution + Quantitation
AFAMAFAMSpherulite, branchedSpherulite, branched--chain polyethylenechain polyethylene
Topography AFAM(Highlights growth in radial direction)
Scan Size: 12x12 μm
Nanolithography & manipulationNanolithography & manipulation
Nanolithography (mechanical or oxidative)
NanomanipulationNanomanipulation
Manipulation of the Nanotubes by LithographyIllustrating movement in a specified direction
MIEE, Institute of Fullerene & Nanomaterials of RAS, Russia
External Magnetic Field External Magnetic Field -- setupsetup
Demagnetization Demagnetization of hard disk (MFM/external)of hard disk (MFM/external)
a) H=0Oe b) H=1050Oe c) H=1280Oe
d) H=1380Oe e) H=1460Oe f) H=1520Oe
High Throughput AFM (HTCM)High Throughput AFM (HTCM)
AFM +AFM +RL stageRL stageAutomation softwareAutomation software
ApplicationsApplicationsPolymer batch studies*Polymer batch studies*BiotechBiotech
SynthesisProperty
Characterization
Data ProcessingDatabase/Libraries
Optimization
Atomic Force Microscopy. Influence of Processing Conditions for
Polyethylene Compositions.Structural Dispersion Parameters and
Mechanical Properties.
NT-LAB, KAZAN GROUP.
AFM, TopographyScan size: 7x7 µm
0 100 200 300 400 500 600000
001
002
003
004
Carbon particles size, nm
Part
icle
vol
. fra
ctio
n
Carbon black particleCarbon black particle distribution distribution within LDPE, Banbury batch mixerwithin LDPE, Banbury batch mixer
*Dutch Polymer Institute, TUE, Eindhoven, The Netherlands
200 300 400 500 600 700 8000,000
0,001
0,002
0,003
Объ
емная доля
частиц
Carbon particles size, nmAFM/TopographyScan size: 4x4 µm
Part
icle
vol
. fra
ctio
n
Carbon black particles distribution within Carbon black particles distribution within LDPE, Tyson mixer (7LDPE, Tyson mixer (7--section screwsection screw ) )
*Dutch Polymer Institute, TUE, Eindhoven, The Netherlands
100 200 300 400 500 600
01
02
03
04
Carbon particles size, nmAFM/TopographyScan size: 7x7 µm
Part
icle
vol
. fra
ctio
n
Carbon black particles distribution within Carbon black particles distribution within HDPE, Tyson mixer (7HDPE, Tyson mixer (7--section screwsection screw ..
*Dutch Polymer Institute, TUE, Eindhoven, The Netherlands
High Throughput ApplicationsHigh Throughput Applications
MORPHOLOGYMORPHOLOGYStructure determines functionStructure determines functionMorphology is a clue to internal chemical structure and Morphology is a clue to internal chemical structure and determines material propertiesdetermines material properties
THERMAL PROPERTIES DISTRIBUTIONTHERMAL PROPERTIES DISTRIBUTIONLOCAL Tm and Tg, MELTING, CRYSTALLIZATIONLOCAL Tm and Tg, MELTING, CRYSTALLIZATION……
MECHANICAL PROPERTIESMECHANICAL PROPERTIESHARDNESS, STIFFNESS, FRICTION, ADHESION HARDNESS, STIFFNESS, FRICTION, ADHESION ……
OPTICAL PROPERTIESOPTICAL PROPERTIESCHEMICAL COMPOSITION, REFLECTION CHEMICAL COMPOSITION, REFLECTION ……
AFM: Thermal StudiesAFM: Thermal Studies
Experimental: Experimental: A polymer test grating was heated at the constant rate up to 105A polymer test grating was heated at the constant rate up to 105ooC, held at C, held at
this temperature for 5 minutes, then heated further to a maximumthis temperature for 5 minutes, then heated further to a maximumtemperature of 155temperature of 155ooC.C.
Requires extreme thermal stabilityRequires extreme thermal stability>5nm XY drift over 1 hr at 150>5nm XY drift over 1 hr at 150ooCC
Results:Results:The general softening of the sample features shown in these The general softening of the sample features shown in these images coincides well with the decreasing peakimages coincides well with the decreasing peak--toto--valley roughness valley roughness shown in the final graph. Also, note the melting point prior toshown in the final graph. Also, note the melting point prior to the the final dramatic relaxation.final dramatic relaxation.
Sample courtesy of Dr. Yen Peng Kong, University of California,Sample courtesy of Dr. Yen Peng Kong, University of California, IrvineIrvine
Polymer Relaxation StudyPolymer Relaxation Study
28C 95C
115C155C
Polymer relaxationPolymer relaxationPolymer relaxation
0
20
40
60
80
100
120
25 45 65 85 105 125 145
Temperature [C]
Pea
k-to
-val
ley
[nm
]
AFM + Liquid CellsAFM + Liquid Cells
Three approaches to liquid cellsThree approaches to liquid cells
Quasi-hermetic flow-through device
Hermetically sealedflow-through device
• Compatible with standard Petri dishes
• Provides simultaneous optical andAFM observation
•For experiments in a closed environment
The smaller device The smaller device ––the better resolutionthe better resolution
Miniature Liquid Cell for Molecular Resolution
Thermally controlled Liquid CellThermally controlled Liquid Cell
Petri Dish
Heater
PTFEScan Size: 2x2 mm
Images obtained in liquidImages obtained in liquid
Block-copolymerScan size: 0.5x0.5 mm
STM STM -- ElectrochemistryElectrochemistry
1
5
2
4
6
3
7
STM STM –– ElectrochemistryElectrochemistry
A and B: -50mVCu crystal growth
Work Electrode: CuSubstrate: PlatinumElectrolyte: H2SO4+CuSO4
Scan area: 1x1 μm
C: + 30mVCu crystals dissolved
(clear surface)
A B C
AFM for the Classroom AFM for the Classroom
ScannerScannerApproach mechanism* Approach mechanism* Base with manual Base with manual sample positioningsample positioningControllerControllerPCI/PCMCIA cardPCI/PCMCIA cardNova SoftwareNova Software
Compact, Robust, Road-worthy
New AFM Hybrids New AFM Hybrids
AFM/Ultramicrotome AFM/Ultramicrotome
Fully integrated AFM plus Fully integrated AFM plus UltramicrotomeUltramicrotome
Images directly from the Images directly from the block face, producing block face, producing prepre--aligned serial sectionsaligned serial sections
True 3D True 3D From the bulkFrom the bulkAt the nanoscaleAt the nanoscale
3D3D--tomographytomography
AFM module scans the surface to make force-
contrasted high resolution image
Ultramicrotome module removes
thin slice to prepare the
surface for next AFM scanning
File of 2D AFM images is then reconstructed into the 3D model
UltrastructureUltrastructure
TEM image of similar nematode part
Sample and TEM image courtesy of Dr. M. Mueller and Dr. N. Matsko, ETH Zurich
AFM phase imageNematode section, 10x10 µm.
AFM TopographyPS/HIPS blend with silica
Scan size: 12x12 µm
Filled PolymerFilled Polymer
Composite polymer Composite polymer Inner structureInner structure
PS/HIPS blend with silica 15 sequential AFM images• Each section is 40x20 µm • Space between sections: 200 nm (Sample courtesy of Dr. Aliza Tzur, Technion, Israel)
3-D reconstruction:
(Can be animated in actual software application)
3D model of cotton fibers3D model of cotton fibers
3D reconstruction Cotton fibers coated with polyelectrolytes.Scan area: 48×36×6.0 um24 sectionsSpaces between sections 250 nm). .
Sample courtesy of Dr. J. P. Hinestroza, Cornell University.
The full workstationThe full workstation
Light microscopyLight microscopyFluorescenceFluorescenceLaser Scanning Confocal microscopy (CM)Laser Scanning Confocal microscopy (CM)Nearfield Scanning microscopy (NSOM)Nearfield Scanning microscopy (NSOM)AFM (40 different techniques)AFM (40 different techniques)Raman Spectroscopy (Confocal Raman, Raman Spectroscopy (Confocal Raman, TERS)TERS)Fluorescence Spectroscopy Fluorescence Spectroscopy
NTEGRA-TERS equipment
PMT Ext2
AFM\SNOM Heads
X Y - Stage
Ntegra base
Z - Scanner Controller
PC
Objective
Fully Integrated LM/CM/AFM/NSOM/Fully Integrated LM/CM/AFM/NSOM/Raman/Fluorescence/TERS Work StationRaman/Fluorescence/TERS Work Station
Light Microscopy (XP) + AFMLight Microscopy (XP) + AFMIsotactic polypropyleneIsotactic polypropylene
Light Microscopy, X Pol AFM Phase ImageTaken from the red inset Scan area: 50 x 50μm
SNOM imagesSNOM imagesMitochondriaMitochondria
Shear-force Topography Fluorescence SNOM
Scan size: 15x15 μm
RAMAN
SPECTRA
Carbon nanotubesCarbon nanotubes
1351 cm-1
173 cm-1
1593 cm-1
AFMScan size: 5x5 μm
Tightly focused laser beam
Glass wafer
Sample
Au or Ag coated AFM tip
Zone of strong field enhancement
To the enhanced Raman signal detection system
TERS PrincipleTERS PrincipleAu or Ag coated tip placed 1-2 nm above the sample surface (in semi-contact mode) will provide strong Raman signal enhancement (by several orders of magnitude).
Au or Ag glass coating creates for additional plasmon resonance enhancement.
Because the Raman signal immediately below the tip is much larger than neighboring far-field signals, the whole system resolution is limited only by the zone of field enhancement which in turn depends on the tip size.
Multiple modes: Localized, single point spectroscopy Line scanFull image map
TERSTERS--activeactive probesprobes
SEM image of the cantilever tip with electrochemically deposited Ag nanoparticles (originated from Ag hydrosol) protected with polymer matrix
SEM image of etched silver tip
500 nm
500 nm
Raman spectra, single-wall SiC nanotubes
Inte
nsity
, a.u
.
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
0 400 800 1200 1600 2000 2400 2800
Raman shift, cm-1
Raman spectrum of SWNT (bulk)
Tip-on mode
1595
TERS spectra of a single nanotube
2697
Tip-off mode
Top: Spectrum from highly concentrated specimen of the SWCNTs(scale: 1/15).
Bottom: Spectrum, single SWCNT, without TERS
Middle:Spectrum, single SWCNT, with TERS
λex= 488nm, Pex~200μW
tint=5sec.
Simultaneous TERS/AFM imagingSimultaneous TERS/AFM imaging
AFM image
Raman signal map1
2
TERS images of single SWNT were acquired simultaneously in 1595 cm-1 (pictured) and 2697 cm-1 Raman bands, with simultaneous AFAM acquisition using TERS-active cantilever.
1
40 nm
TERS image:W, narrow point = 40 nm.
2
4.5 nm
AFM line profile: Ht = 4.5 nm. Confirms: single nanotube.
Transmitted light or Epi versionsTransmitted light or Epi versions
Conventional Transmitted Light VersionConventional Transmitted Light Version
New High Aperture HeadNew High Aperture Head““SeesSees”” around cornersaround cornersIntegrates wellIntegrates well
Getting startedGetting started……..
www.SpectroscopyNow.comwww.SpectroscopyNow.comCoates, J., Ency of Analyt Chem Coates, J., Ency of Analyt Chem –– Interpretation of IR spectraInterpretation of IR spectraJY JY –– Raman TutorialRaman Tutorial
www.Microscopy.infowww.Microscopy.info (lists of AFM,FT(lists of AFM,FT--IR, and Raman providers)IR, and Raman providers)
www.iscpubs.comwww.iscpubs.com (go to Articles(go to Articles archive)archive)FTFT--IRIR
Foster, B. AL, Nov 2001 Foster, B. AL, Nov 2001 ––RamanRaman
Foster, B., AL, Apr 2003Foster, B., AL, Apr 2003Foster, B., AL, May 2003Foster, B., AL, May 2003
AFMAFMFoster, B., AL, May 2004 (AFAM)Foster, B., AL, May 2004 (AFAM)Foster, B., AL, May 2005 (AFM + ultramicrotomy)Foster, B., AL, May 2005 (AFM + ultramicrotomy)Foster, B., AL, Nov 2005 (Raman/AFM/LM/CM/SNOM)Foster, B., AL, Nov 2005 (Raman/AFM/LM/CM/SNOM)
Thanks toThanks to……
Smiths Detection (FTSmiths Detection (FT--IR)IR)www.smithsdetection.comwww.smithsdetection.com
Horiba JY and Renishaw (Raman confocal)Horiba JY and Renishaw (Raman confocal)http://www.jobinyvon.com/http://www.jobinyvon.com/ (Go to PRODUCTS, (Go to PRODUCTS, then microscopy)then microscopy)www.renishaw.comwww.renishaw.com
NTNT--MDT and NTA (AFM)MDT and NTA (AFM)www.ntmdt.comwww.ntmdt.comwww.nanotechwww.nanotech--america.comamerica.com
Later this week, this presentation will be Later this week, this presentation will be available for download from: available for download from:
www.microscopyeducation.comwww.microscopyeducation.com