Nanospectroscopy and nanospectrometry. Using heat to map materials at the nanoscale. Craig Prater CTO Anasys Instruments

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1 Nanospectroscopy and nanospectrometry Using heat to map materials at the nanoscale. Craig Prater CTO Anasys Instruments

2 Using heat to probe materials at the nanoscale Nano Thermal Analysis Nanoscale Mass Spectrometry Deflection Temperature T m = 152 C Nanoscale IR spectroscopy

3 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

4 Nano Thermal Analysis ThermaLever Probe Deflection Temperature Sample T m = 152 C Rapid T g and melt temperatures for thin films & heterogenous materials

5 Domain formation in immiscible polymer blends Nanothermal analysis on individual domains C 153 C 6 x 6 um composition map

6 T g measurements in multilayer films Tie Layer vs. EVOH

7 Mechanical Property Imaging Topography Amplitude Frequency Stiffer material Softer material Contact resonance/stiffness 1 µm ~5 khz shift in contact resonance Yamanaka, K. and S. Nakano, Applied Physics A: Materials Science & Processing 66(0): S313-S317, Rabe, U., et al., Applied Physics A: Materials Science & Processing 66(0): S277-S282, Yuya, P.A., et al., Journal of Applied Physics 104(7): , 2008.

8 Nanomechanical spectroscopy Lorentz Contact Resonance Hendrik Lorentz Magnet Pole piece B Self-heatable AFM probe I F Oscillating current Sample Oscillating Lorentz force Nanomechanical spectra

9 LCR nanomechanical imaging and spectroscopy coating paper

10 Contact resonance detecting thermal transitions in highly filled epoxies Conventional nanota: T g difficult to detect LCR easily detects T g Cantilever deflection (V) Contact resonance frequency (Hz) Temperature ( C) Temperature ( C)

11 Dynanamic nanomechanical analysis on PET Nanoscale DMA Amplitude Phase Tg melt Time-temperature superposition Activation energies

12 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

13 AFM-based mass spectrometry Data courtesy of Olga Ovchinnikova and Gary van Berkel (ORNL)

14 Nano mass spec of complex polymer blends Topography-before Elasticity inlet to MS sample window for camera viewing extraction capillary + + x-y-z ESI solvent flow position stage heating AFM probe HV Ovchinnikova, et al. ACS Nano 2011 Topography-after Mass spec intensity Ovchinnikova, et al. ACS Nano 2015

15 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

16 Infrared light, heat and molecular vibrations William Herschel

17 Infrared spectroscopy chemical analysis via molecular vibrations IR light wave IR Spectrum ν 1 = ν 0 ν 0 + HEAT ν 2 ν 0 ν 0 Source: Wikipedia

18 IR + microscopy, power and limits FTIR 2 IR spectra Chemical Images IR microspectroscopy applications PET microscope Absorbance Tie Layer EVOH LDPE Wavenumber Multilayer film, courtesy of Dr. Curtis Marcott Materials Science Consumer products Pharmaceuticals Life sciences Health & beauty Forensics IR microspectroscopy annual publications Abbe diffration limit: Practical resolution many microns

19 AFM-based IR spectroscopy (AFM-IR) Alexandre Dazzi 2014 Ernst Abbe Award Dazzi, A.; Prazeres, R.; Glotin, F.; Ortega, J.M.; Opt. Lett. 2005, 30,

20 AFM-IR: Nannoscale infrared spectroscopy Cantilever oscillation ~ IR absorption coefficient Correlation to FTIR w/o peak shifts

21 AFM-IR animation

22 Nanoscale infrared spectroscopy-overview Nanoscale chemical analysis Rich interpretable spectra Publications & Productivity Chemical composition/optical property imaging Sensitivity to single monolayers +

23 Diverse AFM-IR applications 1640 Polymer blends Multilayer films Plasmonics Normalized ringdown amplitude (at 1448 cm -1 ) AFM image Life sciences Printing Biofuels

24 Improved sensitivity-resonant Enhanced AFM-IR Pulse IR source at contact resonant frequency of cantilever Continuous oscillation Sample thickness down to single monolayers Conventional AFM-IR Resonance enhanced Quantum Cascade Laser Lu, F.; Belkin, M. Opt. Exp. 2011, 19, F. Lu, M. Jin, M.A. Belkin, Nat. Photon (2014)

25 Resonant enhanced AFM-IR of PEG monolayer Topography IR image at 1340 cm -1 CH 2 scissor CH 2 wag C-O-C Asym

26 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

27 Visualizing chemical changes with temperature Normalized ringdown amplitude* 46 C 60 C 70 C 80 C 90 C 100 C 1380* AFM image Wavenumber (cm -1 )

28 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

29 Electrospun Polymer Fibers 1728 (α crystalline phase) 1740 (β + oriented amorphous phase) AFM IMAGE PHBHx nanofibers 390nm IR 1740cm -1 β + oriented amorphous phase 390nm 9nm 1728cm -1 α crystalline phase 372nm Low α in shell Liang Gong et al Macromolecules, 2015, 48 (17), pp

30 Vapor infiltration into PET fibers 60 TMA SVI cycles at 150 C 90 TMA SVI cycles at 90 C 90 TMA SVI cycles at 90 C Akyildiz H.I. et al, Journal of Materials Research 29 (23)

31 AFM-IR on plasmonic resonators A. M. Katzenmeyer, et al Adv. Optical Mater. 2014,

32 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

33 Looking inside single cells Topography 1740 cm -1 (triglyceride) Deniset-Besseau, et al, Chem. Lett., 5 (4) (2014)

34 Protein secondary structure-collagen fibrils Collagen fibrils IR Amplitude [a.u.] Amide I Structural assignment Wavenumber (cm - 1 ) b-turn and Antiparallel b-sheets a-helix Random coil Low density Native/High density Amyloid b-sheets A. Kulik, F. S. Ruggeri et al., Nanoscale Infrared Spectroscopy of LHCII proteins and amyloids, Microscopy and analysis, 2014.

35 Protein structure Proteins are large biological molecules, or macromolecules, consisting of one or more long chains of amino acid residues. Amino acids can form two different basilar structures: α-helix and β-sheet.

36 Amyloids and misfolding diseases Related to neurodegenerative disorders. Protein Native Structure Disease Amyloid β unfolded Alzheimer α-synuclein unfolded Parkinson Huntingtin (ex1) unfolded Huntington Josephin domain of Ataxin-3 Lysozyme globular globular Ataxia Systemic Amyloidosis lysozyme Adapted from Brain research Bulletin, Volume 81, 1, 2010, Diameter ~10 nm Length ~ µm M. Gross, Current Biology, 2012, 22, 381.

37 Secondary structure of individual oligomers and fibrils Conformational Change at Individual Aggregates Scale After 7 days, oligomeric and fibrillar species are present. Fibrillar structures possess higher antiparallel β-sheet content than misfolded oligomeric structures. Ruggeri et al., Nature Communications, 2015.

38 Resonance enhanced AFM-IR: 5 nm biological membrane Halobacterium Salinarum deposited on a Au substrate Topography 1.5 x 3 μm Amide I Amide II IR Image at 1660 cm -1

39 Outline Nanothermal + nanomechanical analysis AFM-MS: Nanoscale mass spectrometry AFM-IR: Nanoscale infrared spectroscopy Mixing it up: Heated tip IR spectroscopy Applications: Materials science Life sciences Industry Your questions

40 Characterization needs in industry Accelerate materials development Troubleshoot/ optimize processing Business value Defects and failure analysis Reverse engineering/ competitive analysis

41 Polymer nanocomposite 10 x 10 micron scan Height Image IR Image at 1100 cm -1 Si-O 1106 cm -1 SiO 2 nanoparticles dispersed in polypropylene 1456 cm cm cm -1

42 Nanothermal analysis of interface layers in multilayer films Problem addressed: nanota showed a very small Thermal but observable analysis of transition on the previously unseen very thin layer layers

43 Nanoscale IR spectroscopy of interface layers Normalized ringdown amplitude (AU) * 200 nm AFM image PE B C polyamide CH 2 peak width (cm -1 ) CH 2 peak position (cm -1 ) Position (nm)

44 Degraded poly(urethane) tubing AFM-IR spectra AFM image 1700 Crack formed toward the bulk PU Amplitude (AU) *1532 Wavenumber (cm-1 ) Bulk PU OD *All spectra were normalized to 1532 cm -1

45 Heat assisted magnetic recording (HAMR) Seagate Stipe et al Nature Photonics 2010

46 Fiber reinforced composites Problem addressed: Interfacial bonding/ processing defects Temperature Fiber Epoxy

47 Defect identification Problem addressed: Characterization and identification of gel particles

48 New Publications & previous webinars: Go There

49 Collaborator Acknowledgement Alexandre Dazzi Ariane Deniset-Bessseau Curt Marcott William King Jonathan Felts Bruce Chase John Rabolt Liang Gong Adele Boskey Mikhail Belkin Feng Lu Mingzhou Jin Olga Ochinikova Gary Van Berkel Greg Meyers Isao Noda Gloria Story Bernard Van Eerdenbrugh Lynne Taylor Andrea Centrone Donna Hurley Jason Kilgore Andrzej Kulik Francesco Simone Ruggeri Konstantin Vodopyanov Markus Raschke group Tom Eby Usha Gundusharma Jiping Ye Sean King This work was supported in part by NIST-ATP Award #70NANB7H7025 and the National Science Foundation Award NSF-SBIR Collaborator acknowledgements do not imply endorsements from respective institutions.

50 Summary Heat is a powerful tool for probing material properties at the nanoscale Nanoscale heated probes used for nanothermal and nanomechanical analysis and nano-mass spec Nanoscale absorbed heat used for nanoscale IR spectroscopy Lots of applications in materials science, life sciences and industry