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

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

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

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

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

Domain formation in immiscible polymer blends Nanothermal analysis on individual domains + + + + + + 129 C 153 C 6 x 6 um composition map

T g measurements in multilayer films Tie Layer vs. EVOH

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, 1998. Rabe, U., et al., Applied Physics A: Materials Science & Processing 66(0): S277-S282, 1998. Yuya, P.A., et al., Journal of Applied Physics 104(7): 074916-7, 2008.

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

LCR nanomechanical imaging and spectroscopy coating paper

Contact resonance detecting thermal transitions in highly filled epoxies Conventional nanota: T g difficult to detect LCR easily detects T g 10 460000 Cantilever deflection (V) 9 8 7 6 5 4 3 2 1 Contact resonance frequency (Hz) 455000 450000 445000 440000 435000 0 40 90 140 190 430000 0 50 100 150 200 250 Temperature ( C) Temperature ( C)

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

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

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

Infrared light, heat and molecular vibrations William Herschel

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

IR + microscopy, power and limits FTIR 2 IR spectra Chemical Images IR microspectroscopy applications PET microscope Absorbance 1.5 1.5 0 Tie Layer EVOH LDPE 1800 1600 1400 1200 1000 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

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, 2388-2390.

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

AFM-IR animation

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

Diverse AFM-IR applications 1640 Polymer blends Multilayer films Plasmonics Normalized ringdown amplitude (at 1448 cm -1 ) 1536 1448 1368 1276 AFM image Life sciences Printing Biofuels 5 4 3 2 1 0 1800 1600 1400 1200

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, 19946. F. Lu, M. Jin, M.A. Belkin, Nat. Photon. 8 307 (2014)

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

Visualizing chemical changes with temperature Normalized ringdown amplitude* 46 C 60 C 70 C 80 C 90 C 100 C 1380* AFM image 1500 1400 1300 1200 Wavenumber (cm -1 )

Electrospun Polymer Fibers 1728 (α crystalline phase) 1740 (β + oriented amorphous phase) AFM IMAGE PHBHx nanofibers 390nm IR MAPPING @ 1740cm -1 β + oriented amorphous phase 390nm 9nm shell @ 1728cm -1 α crystalline phase 372nm Low α in shell Liang Gong et al Macromolecules, 2015, 48 (17), pp 6197 6205

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) 2817-2826 2014

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

Looking inside single cells Topography 1740 cm -1 (triglyceride) Deniset-Besseau, et al, Chem. Lett., 5 (4) 654 658 (2014)

Protein secondary structure-collagen fibrils Collagen fibrils IR Amplitude [a.u.] Amide I Structural assignment Wavenumber (cm - 1 ) b-turn and Antiparallel b-sheets 1695-1665 a-helix 1660-1650 Random coil 1645-1630 Low density Native/High density Amyloid b-sheets 1635-1610 A. Kulik, F. S. Ruggeri et al., Nanoscale Infrared Spectroscopy of LHCII proteins and amyloids, Microscopy and analysis, 2014.

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.

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, 12 24. Diameter ~10 nm Length ~ µm M. Gross, Current Biology, 2012, 22, 381.

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.

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

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

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 -1 1372 cm -1 972 cm -1

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

Nanoscale IR spectroscopy of interface layers Normalized ringdown amplitude (AU) 3300 2916* 200 nm AFM image PE B C polyamide CH 2 peak width (cm -1 ) CH 2 peak position (cm -1 ) 60 50 40 30 20 10 0 2926 2924 2922 2920 2918 2916 0 500 1000 Position (nm) 2914 2912

Degraded poly(urethane) tubing AFM-IR spectra AFM image 1700 Crack formed toward the bulk PU Amplitude (AU) 1600 1652 1176 1108 1080 1228 1412 1312 *1532 Wavenumber (cm-1 ) Bulk PU OD *All spectra were normalized to 1532 cm -1

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

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

Defect identification Problem addressed: Characterization and identification of gel particles

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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 0750512. Collaborator acknowledgements do not imply endorsements from respective institutions.

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