What s s in YOUR toolkit?

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Bryan Baldwin
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1 New Microscopies for Polymer Analyses What s s in YOUR toolkit? Barbara Foster Microscopy/Marketing & Education bfoster@mme1.com

2 *IDKYCDT! Light/Confocal +(Chemical Fingerprints) FT-IR Raman AFM +++ In Liquids (including electrochemistry) Thermal Analysis Ultramicrotomy With NSOM, Raman confocal and fluorescence spectroscopy *I didn t know you could do that!

FT-IR + Microscopy Light from the microscope impinges on the surface and undergoes total internal reflection In the process of reflecting, the beam generates a small, evanescent field at the

3 FT-IR + Microscopy Light from the microscope impinges on the surface and undergoes total internal reflection In the process of reflecting, the beam generates a small, evanescent field at the interface, which penetrates the second material. If the second material absorbs this e n e r g y, the intensity for the reflected beam is reduced or attenuated. This absorption is selective, dependent on the chemistry of the second material. Scanning the attenuation over a specific wavelength region ( ,250 nm or 4000 to 650cm-1) produces a spectrum that provides a specific molecular fingerprint for the second material. Smiths Detection

4 Target Measure Locate glass particle in oil (No contact) Spectrum of oil Mixed spectrum oil + glass Pure spectrum, glass

Raman Confocal Like FT-IR: another Vibrational Spectroscopy Inelastic scattering Compliments FT-IR FT-IR does not work well with materials exhibiting strong

5 Raman Confocal Like FT-IR: another Vibrational Spectroscopy Inelastic scattering Compliments FT-IR FT-IR does not work well with materials exhibiting strong O-H H or N-H N H effects; Raman does The Challenges: Very weak signal! (10-4 of fluorescence; 10-7 or 10-8 of ambient) Often in same spectral range as fluorescence

6 Raman + Renishaw Horiba/JY

7 Ion diffusion across a polymer membrane Triflate in water (anion) Trifluoromethane sulfonate Note peaks at 766 nm and 1034 nm for un-coordinated anion Li+ triflate complex at varying depths > d Li+ doped p(eto) cast on vanadium oxide ceramic Mobile cation: Li+ Anion: Triflate Horiba/JY

8 Scanning Probe Microscopy (SPM) Atomic Force Microscopy (AFM) Scanning Tunneling Microscopy (STM)

9 What do YOU need to do? STM 300 C Lithography Resistance Near Field Vacuum Nanotechnology Education Adhesion Roughness Conductivity Shear Force Magnetism Elasticity Liquid Biology Nanotubes Polymers Raman

10 How does AFM work? Photodiode Feedback loop Laser Piezo Tip Image Sample

11 Multiple configurations

Atomic structure of nanotube is clearly visible.

12 Critical Atomic Resolution 12x12 nm STM image of carbon nanotube deposited on HOPG substrate. Atomic structure of nanotube is clearly visible. Image courtesy of Prof. V.K. Nevolin, Moscow Institute of Electronic Engineering.

13 AFM Topography & Phase images Polyethylene Topography Phase Scan size: 4x4μm

14 AFM Topography & Phase images Polyethylene oxide Topography Phase Scan size: 25x25 µm

15 Electromotive Force Microscopy (EFM) Polymer blend: app-ma Polymer blend (app-ma) with two different dielectric constants Scan size: 1.5 x 1.5 μm A.V. Krayev et al. Polymer 45 (2004)

16 Surface potential distribution Scanning Kelvin Mode (SKM) Topography Potential (2-pass, semi-contact) Azobenzene derivative - self-assembled film Scan size: 45x45 µm

17 Atomic Force Acoustical Microscopy Polyethylene strips (HD/LD) Topography AFAM AFAM senses local surface elasticity with high lateral resolution + Quantitation Scan size: 10x10 μm

18 AFAM Spherulite, branched-chain chain polyethylene Topography AFAM (Highlights growth in radial direction) Scan Size: 12x12 μm

19 Nanolithography & manipulation Nanolithography (mechanical or oxidative)

20 Nanomanipulation Manipulation of the Nanotubes by Lithography Illustrating movement in a specified direction MIEE, Institute of Fullerene & Nanomaterials of RAS, Russia

21 External Magnetic Field - setup

22 Demagnetization of hard disk (MFM/external) a) H=0Oe b) H=1050Oe c) H=1280Oe d) H=1380Oe e) H=1460Oe f) H=1520Oe

23 High Throughput AFM (HTCM) AFM + RL stage Automation software Applications Polymer batch studies* Biotech

24 Optimization Synthesis Property Characterization Database/Libraries Data Processing

26 Atomic Force Microscopy. Influence of Processing Conditions for Polyethylene Compositions. Structural Dispersion Parameters and Mechanical Properties. NT-LAB, KAZAN GROUP.

$fraction 003 002 001 000 0 100 200 300 400 500 600 AFM, Topography Scan size: 7x7 µm Carbon particles size, nm *Dutch Polymer$

27 Carbon black particle distribution within LDPE, Banbury batch mixer 004 Particle vol. fraction AFM, Topography Scan size: 7x7 µm Carbon particles size, nm *Dutch Polymer Institute, TUE, Eindhoven, The Netherlands

28 Carbon black particles distribution within LDPE, Tyson mixer (7-section screw ) 0,003 Объемная Particle vol. доля fraction частиц 0,002 0,001 0, AFM/Topography Scan size: 4x4 µm Carbon particles size, nm *Dutch Polymer Institute, TUE, Eindhoven, The Netherlands

29 Carbon black particles distribution within HDPE, Tyson mixer (7-section screw. 04 Particle vol. fraction AFM/Topography Scan size: 7x7 µm Carbon particles size, nm *Dutch Polymer Institute, TUE, Eindhoven, The Netherlands

30 High Throughput Applications MORPHOLOGY Structure determines function Morphology is a clue to internal chemical structure and determines material properties THERMAL PROPERTIES DISTRIBUTION LOCAL Tm and Tg, MELTING, CRYSTALLIZATION MECHANICAL PROPERTIES HARDNESS, STIFFNESS, FRICTION, ADHESION OPTICAL PROPERTIES CHEMICAL COMPOSITION, REFLECTION

31 AFM: Thermal Studies

32 Polymer Relaxation Study Experimental: A polymer test grating was heated at the constant rate up to 105 o C, held at this temperature for 5 minutes, then heated further to a maximum temperature of 155 o C. Requires extreme thermal stability >5nm XY drift over 1 hr at 150 o C Results: The general softening of the sample features shown in these images coincides well with the decreasing peak-to to-valley roughness shown in the final graph. Also, note the melting point prior to the final dramatic relaxation. Sample courtesy of Dr. Yen Peng Kong, University of California, Irvine

33 28C 95C 115C 155C

34 Polymer relaxation Polymer relaxation 120 Peak-to-valley [nm] Temperature [C]

35 AFM + Liquid Cells

36 Three approaches to liquid cells Quasi-hermetic flow-through device Hermetically sealed flow-through device Compatible with standard Petri dishes Provides simultaneous optical and AFM observation For experiments in a closed environment

37 The smaller device the better resolution Miniature Liquid Cell for Molecular Resolution

38 Thermally controlled Liquid Cell Heater Petri Dish

39 Images obtained in liquid Block-copolymer Scan size: 0.5x0.5 mm PTFE Scan Size: 2x2 mm

40 STM - Electrochemistry

41 STM Electrochemistry A B C A and B: -50mV Cu crystal growth C: + 30mV Cu crystals dissolved (clear surface) Work Electrode: Cu Substrate: Platinum Electrolyte: H 2 SO 4 +CuSO 4 Scan area: 1x1 μm

42 AFM for the Classroom Scanner Approach mechanism* Base with manual sample positioning Controller PCI/PCMCIA card Nova Software Compact, Robust, Road-worthy

43 New AFM Hybrids

44 AFM/Ultramicrotome Fully integrated AFM plus Ultramicrotome Images directly from the block face, producing pre-aligned serial sections True 3D From the bulk At the nanoscale

45 3D-tomography AFM module scans the surface to make forcecontrasted 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

46 Ultrastructure TEM image of similar nematode part AFM phase image Nematode section, 10x10 µm. Sample and TEM image courtesy of Dr. M. Mueller and Dr. N. Matsko, ETH Zurich

47 Filled Polymer AFM Topography PS/HIPS blend with silica Scan size: 12x12 µm

Composite polymer Inner structure PS/HIPS

48 Composite polymer Inner 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 fibers 3D reconstruction Cotton fibers coated with polyelectrolytes. Scan area: 48 36 6.

49 3D model of cotton fibers 3D reconstruction Cotton fibers coated with polyelectrolytes. Scan area: um 24 sections Spaces between sections 250 nm).. Sample courtesy of Dr. J. P. Hinestroza, Cornell University.

50 The full workstation Light microscopy Fluorescence Laser Scanning Confocal microscopy (CM) Nearfield Scanning microscopy (NSOM) AFM (40 different techniques) Raman Spectroscopy (Confocal Raman, TERS) Fluorescence Spectroscopy

$Ext2 AFM\SNOM Heads PC X Y - Stage Ntegra$

51 Fully Integrated NTEGRA-TERS LM/CM/AFM/NSOM/ equipment Raman/Fluorescence/TERS Work Station PMT Ext2 AFM\SNOM Heads PC X Y - Stage Ntegra base Objective Z - Scanner Controller

52 Light Microscopy (XP) + AFM Isotactic polypropylene Light Microscopy, X Pol AFM Phase Image Taken from the red inset Scan area: 50 x 50μm

53 SNOM images Mitochondria Shear-force Topography Fluorescence SNOM Scan size: 15x15 μm

54 Carbon nanotubes 1593 cm cm cm -1 AFM Scan size: 5x5 μm R A M A N S P E C T R A

55 TERS Principle Au or Ag coated AFM tip Zone of strong field enhancement Sample Glass wafer To the enhanced Raman signal detection system Tightly focused laser beam Au or Ag coated tip placed 1-2 nm above the sample surface (in semicontact 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 scan Full image map

56 TERS-active probes 500 nm SEM image of etched silver tip 500 nm SEM image of the cantilever tip with electrochemically deposited Ag nanoparticles (originated from Ag hydrosol) protected with polymer matrix

57 Raman spectra, single-wall SiC nanotubes Intensity, a.u Raman spectrum of SWNT (bulk) TERS spectra of a single nanotube 1595 Tip-on mode 2697 Top: Spectrum from highly concentrated specimen of the SWCNTs (scale: 1/15). Bottom: Spectrum, single SWCNT, without TERS Middle: Spectrum, single SWCNT, with TERS Raman shift, cm -1 Tip-off mode λ ex = 488nm, P ex ~200μW t int =5sec.

58 Simultaneous TERS/AFM imaging AFM image nm 2 1 Raman signal map AFM line profile: Ht = 4.5 nm. Confirms: single nanotube nm TERS image: W, narrow point = 40 nm. 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.

59 Transmitted light or Epi versions Conventional Transmitted Light Version New High Aperture Head Sees around corners Integrates well

60 Getting started. Coates, J., Ency of Analyt Chem Interpretation of IR spectra JY Raman Tutorial (lists of AFM,FT-IR, and Raman providers) (go to Articles archive) FT-IR Foster, B. AL, Nov 2001 Raman AFM Foster, B., AL, Apr 2003 Foster, B., AL, May 2003 Foster, B., AL, May 2004 (AFAM) Foster, B., AL, May 2005 (AFM + ultramicrotomy) Foster, B., AL, Nov 2005 (Raman/AFM/LM/CM/SNOM)

61 Thanks to Smiths Detection (FT-IR) Horiba JY and Renishaw (Raman confocal) (Go to PRODUCTS, then microscopy) NT-MDT and NTA (AFM) america.com

62 Later this week, this presentation will be available for download from:

Other SPM Techniques. Scanning Probe Microscopy HT10

Other SPM Techniques. Scanning Probe Microscopy HT10 Other SPM Techniques Scanning Near-Field Optical Microscopy (SNOM) Scanning Capacitance Microscopy (SCM) Scanning Spreading Resistance Microscopy (SSRM) Multiprobe techniques Electrostatic Force Microscopy,