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

bfoster@mme1.combfoster@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