DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Infrared vibrational nano-crystallography and nano-imaging

Abstract

Molecular solids and polymers can form low-symmetry crystal structures that exhibit anisotropic electron and ion mobility in engineered devices or biological systems. The distribution of molecular orientation and disorder then controls the macroscopic material response, yet it is difficult to image with conventional techniques on the nanoscale. We demonstrated a new form of optical nanocrystallography that combines scattering-type scanning near-field optical microscopy with both optical antenna and tip-selective infrared vibrational spectroscopy. From the symmetry-selective probing of molecular bond orientation with nanometer spatial resolution, we determined crystalline phases and orientation in aggregates and films of the organic electronic material perylenetetracarboxylic dianhydride. Mapping disorder within and between individual nanoscale domains, the correlative hybrid imaging of nanoscale heterogeneity provides insight into defect formation and propagation during growth in functional molecular solids.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1];  [1]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1530255
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 2; Journal Issue: 10; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Muller, Eric A., Pollard, Benjamin, Bechtel, Hans A., van Blerkom, Peter, and Raschke, Markus B. Infrared vibrational nano-crystallography and nano-imaging. United States: N. p., 2016. Web. doi:10.1126/sciadv.1601006.
Muller, Eric A., Pollard, Benjamin, Bechtel, Hans A., van Blerkom, Peter, & Raschke, Markus B. Infrared vibrational nano-crystallography and nano-imaging. United States. https://doi.org/10.1126/sciadv.1601006
Muller, Eric A., Pollard, Benjamin, Bechtel, Hans A., van Blerkom, Peter, and Raschke, Markus B. Fri . "Infrared vibrational nano-crystallography and nano-imaging". United States. https://doi.org/10.1126/sciadv.1601006. https://www.osti.gov/servlets/purl/1530255.
@article{osti_1530255,
title = {Infrared vibrational nano-crystallography and nano-imaging},
author = {Muller, Eric A. and Pollard, Benjamin and Bechtel, Hans A. and van Blerkom, Peter and Raschke, Markus B.},
abstractNote = {Molecular solids and polymers can form low-symmetry crystal structures that exhibit anisotropic electron and ion mobility in engineered devices or biological systems. The distribution of molecular orientation and disorder then controls the macroscopic material response, yet it is difficult to image with conventional techniques on the nanoscale. We demonstrated a new form of optical nanocrystallography that combines scattering-type scanning near-field optical microscopy with both optical antenna and tip-selective infrared vibrational spectroscopy. From the symmetry-selective probing of molecular bond orientation with nanometer spatial resolution, we determined crystalline phases and orientation in aggregates and films of the organic electronic material perylenetetracarboxylic dianhydride. Mapping disorder within and between individual nanoscale domains, the correlative hybrid imaging of nanoscale heterogeneity provides insight into defect formation and propagation during growth in functional molecular solids.},
doi = {10.1126/sciadv.1601006},
journal = {Science Advances},
number = 10,
volume = 2,
place = {United States},
year = {Fri Oct 07 00:00:00 EDT 2016},
month = {Fri Oct 07 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 50 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Nanoscale structure measurements for polymer-fullerene photovoltaics
journal, January 2012

  • DeLongchamp, Dean M.; Kline, R. Joseph; Herzing, Andrew
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee02725a

Second-harmonic near-field imaging of ferroelectric domain structure of YMnO 3
journal, March 2009


Nanoscale polymer recognition by spectral signature in scattering infrared near-field microscopy
journal, November 2004

  • Taubner, T.; Hillenbrand, R.; Keilmann, F.
  • Applied Physics Letters, Vol. 85, Issue 21
  • DOI: 10.1063/1.1827334

Nanoscale-resolved chemical identification of thin organic films using infrared near-field spectroscopy and standard Fourier transform infrared references
journal, January 2015

  • Mastel, Stefan; Govyadinov, Alexander A.; de Oliveira, Thales V. A. G.
  • Applied Physics Letters, Vol. 106, Issue 2
  • DOI: 10.1063/1.4905507

Polarized X-ray scattering reveals non-crystalline orientational ordering in organic films
journal, April 2012

  • Collins, B. A.; Cochran, J. E.; Yan, H.
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3310

IR and SFM study of PTCDA thin films on different substrates
journal, September 2005


Patterning organic single-crystal transistor arrays
journal, December 2006

  • Briseno, Alejandro L.; Mannsfeld, Stefan C. B.; Ling, Mang M.
  • Nature, Vol. 444, Issue 7121, p. 913-917
  • DOI: 10.1038/nature05427

Super-Resolution Optical Fluctuation Bio-Imaging with Dual-Color Carbon Nanodots
journal, December 2015


Membrane Helix Orientation from Linear Dichroism of Infrared Attenuated Total Reflection Spectra
journal, January 1999


Infrared spectroscopic study of the morphology of 3,4,9,10-perylene tetracarboxylic dianhydride films grown on H-passivated Si(111)
journal, September 2003

  • Scholz, Reinhard; Friedrich, Marion; Salvan, Georgeta
  • Journal of Physics: Condensed Matter, Vol. 15, Issue 38
  • DOI: 10.1088/0953-8984/15/38/005

Tapping Mode Atomic Force Microscopy on Polymers:  Where Is the True Sample Surface?
journal, June 2001

  • Knoll, A.; Magerle, R.; Krausch, G.
  • Macromolecules, Vol. 34, Issue 12
  • DOI: 10.1021/ma001311x

Optical nanocrystallography with tip-enhanced phonon Raman spectroscopy
journal, July 2009

  • Berweger, Samuel; Neacsu, Catalin C.; Mao, Yuanbing
  • Nature Nanotechnology, Vol. 4, Issue 8
  • DOI: 10.1038/nnano.2009.190

Introduction to Optical Methods for Characterizing Liquid Crystals at Interfaces
journal, February 2013

  • Miller, Daniel S.; Carlton, Rebecca J.; Mushenheim, Peter C.
  • Langmuir, Vol. 29, Issue 10
  • DOI: 10.1021/la304679f

Capillary forces in tapping mode atomic force microscopy
journal, October 2002


High-Mobility Field-Effect Transistors Fabricated with Macroscopic Aligned Semiconducting Polymers
journal, February 2014


Energy shift and wave function overlap of metal-organic interface states
journal, August 2011


Vibrational nano-spectroscopic imaging correlating structure with intermolecular coupling and dynamics
journal, April 2014

  • Pollard, Benjamin; Muller, Eric A.; Hinrichs, Karsten
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4587

High Mobility, Air Stable, Organic Single Crystal Transistors of an n-Type Diperylene Bisimide
journal, April 2012

  • Lv, Aifeng; Puniredd, Sreenivasa R.; Zhang, Jiahui
  • Advanced Materials, Vol. 24, Issue 19
  • DOI: 10.1002/adma.201104987

Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films
journal, November 2009

  • Rivnay, Jonathan; Jimison, Leslie H.; Northrup, John E.
  • Nature Materials, Vol. 8, Issue 12, p. 952-958
  • DOI: 10.1038/nmat2570

Molecular Stacking Induced by Intermolecular C-H···N Hydrogen Bonds Leading to High Carrier Mobility in Vacuum-Deposited Organic Films
journal, March 2011

  • Yokoyama, Daisuke; Sasabe, Hisahiro; Furukawa, Yukio
  • Advanced Functional Materials, Vol. 21, Issue 8
  • DOI: 10.1002/adfm.201001919

Relationship between Tribology and Optics in Thin Films of Mechanically Oriented Nanocrystals
journal, July 2012

  • Wong, Liana; Hu, Chunhua; Paradise, Ruthanne
  • Journal of the American Chemical Society, Vol. 134, Issue 29
  • DOI: 10.1021/ja304799a

Chemisorption, Morphology, and Structure of a n-Type Perylene Diimide Derivative at the Interface with Gold: Influence on Devices from Thin Films to Single Molecules
journal, January 2015

  • Ciccullo, Francesca; Savu, Sabine-Antonia; Gerbi, Andrea
  • Chemistry - A European Journal, Vol. 21, Issue 9
  • DOI: 10.1002/chem.201404901

High-Resolution Scanning X-ray Diffraction Microscopy
journal, July 2008


Ultrabroadband infrared nanospectroscopic imaging
journal, May 2014

  • Bechtel, H. A.; Muller, E. A.; Olmon, R. L.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 20
  • DOI: 10.1073/pnas.1400502111

Polarization Properties in Apertureless-Type Scanning Near-Field Optical Microscopy
journal, September 2015


Epitaxial Growth of Pentacene Films on Metal Surfaces
journal, February 2004


Nanoscale Probing of Dynamics in Local Molecular Environments
journal, October 2015

  • Atkin, Joanna M.; Sass, Paul M.; Teichen, Paul E.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 22
  • DOI: 10.1021/acs.jpclett.5b02093

Molecular organization in perylenetetracarboxylic dianhydride films
journal, May 1987

  • Akers, Kelly.; Aroca, Ricardo.; Hor, Ah Mee.
  • The Journal of Physical Chemistry, Vol. 91, Issue 11
  • DOI: 10.1021/j100295a061

Insight into carbon nanotube effect on polymer molecular orientation: an infrared dichroism study
journal, January 2011

  • Yuan, Cuiping; Zhang, Jinhao; Chen, Guangming
  • Chem. Commun., Vol. 47, Issue 3
  • DOI: 10.1039/C0CC03198D

High performance phototransistors based on single crystalline perylene-tetracarboxylic-dianhydride nanoparticle
journal, October 2013

  • Nguyen, Linh-Nam; Kumar Pradhan, Sunil; Yen, Chia-Nan
  • Applied Physics Letters, Vol. 103, Issue 18
  • DOI: 10.1063/1.4827975

Anisotropy Contrast in Phonon-Enhanced Apertureless Near-Field Microscopy Using a Free-Electron Laser
journal, June 2008


Switching orientation of adsorbed molecules: Reverse domino on a metal surface
journal, January 2016


Infrared Chemical Nano-Imaging: Accessing Structure, Coupling, and Dynamics on Molecular Length Scales
journal, March 2015

  • Muller, Eric A.; Pollard, Benjamin; Raschke, Markus B.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 7
  • DOI: 10.1021/acs.jpclett.5b00108

Model for quantitative tip-enhanced spectroscopy and the extraction of nanoscale-resolved optical constants
journal, August 2014


Super-resolution biomolecular crystallography with low-resolution data
journal, April 2010

  • Schröder, Gunnar F.; Levitt, Michael; Brunger, Axel T.
  • Nature, Vol. 464, Issue 7292
  • DOI: 10.1038/nature08892

Quantitative Measurement of Local Infrared Absorption and Dielectric Function with Tip-Enhanced Near-Field Microscopy
journal, April 2013

  • Govyadinov, Alexander A.; Amenabar, Iban; Huth, Florian
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1021/jz400453r

Discerning Variable Extents of Interdomain Orientational and Structural Heterogeneity in Solution-Cast Polycrystalline Organic Semiconducting Thin Films
journal, July 2015

  • Wong, Cathy Y.; Folie, Brendan D.; Cotts, Benjamin L.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
  • DOI: 10.1021/acs.jpclett.5b01416

Watching conformational- and photodynamics of single fluorescent proteins in solution
journal, January 2010

  • Goldsmith, Randall H.; Moerner, W. E.
  • Nature Chemistry, Vol. 2, Issue 3
  • DOI: 10.1038/nchem.545

General Strategy for Self-Assembly of Highly Oriented Nanocrystalline Semiconducting Polymers with High Mobility
journal, April 2014

  • Luo, Chan; Kyaw, Aung Ko Ko; Perez, Louis A.
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500758w

Membrane helix orientation from linear dichroism of infrared attenuated total reflection spectra
book, January 1999

  • Bechinger, Burkhard; Ruysschaert, Jean-Marie; Goormaghtigh, Erik
  • Spectroscopy of Biological Molecules: New Directions
  • DOI: 10.1007/978-94-011-4479-7_167

Watching Conformational and Photo-Dynamics of Single Fluorescent Proteins in Solution
journal, January 2010


High Mobility, Air Stable, Organic Single Crystal Transistors of an n-Type Diperylene Bisimide
journal, April 2012

  • Lv, Aifeng; Puniredd, Sreenivasa R.; Zhang, Jiahui
  • Advanced Materials, Vol. 24, Issue 19
  • DOI: 10.1002/adma.201104987

High-Mobility Field-Effect Transistors Fabricated with Macroscopic Aligned Semiconducting Polymers
journal, February 2014


Chemisorption, Morphology, and Structure of a n-Type Perylene Diimide Derivative at the Interface with Gold: Influence on Devices from Thin Films to Single Molecules
journal, January 2015

  • Ciccullo, Francesca; Savu, Sabine-Antonia; Gerbi, Andrea
  • Chemistry - A European Journal, Vol. 21, Issue 9
  • DOI: 10.1002/chem.201404901

Epitaxial Growth of Pentacene Films on Metal Surfaces
journal, February 2004


Watching Conformational and Photo-Dynamics of Single Fluorescent Proteins in Solution
journal, January 2010


From Poor Resolution to Rich Insight
journal, June 2010


Infrared Chemical Nano-Imaging: Accessing Structure, Coupling, and Dynamics on Molecular Length Scales
journal, March 2015

  • Muller, Eric A.; Pollard, Benjamin; Raschke, Markus B.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 7
  • DOI: 10.1021/acs.jpclett.5b00108

Super-Resolution Optical Fluctuation Bio-Imaging with Dual-Color Carbon Nanodots
journal, December 2015


Relationship between Tribology and Optics in Thin Films of Mechanically Oriented Nanocrystals
journal, July 2012

  • Wong, Liana; Hu, Chunhua; Paradise, Ruthanne
  • Journal of the American Chemical Society, Vol. 134, Issue 29
  • DOI: 10.1021/ja304799a

Quantitative Measurement of Local Infrared Absorption and Dielectric Function with Tip-Enhanced Near-Field Microscopy
journal, April 2013

  • Govyadinov, Alexander A.; Amenabar, Iban; Huth, Florian
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1021/jz400453r

General Strategy for Self-Assembly of Highly Oriented Nanocrystalline Semiconducting Polymers with High Mobility
journal, April 2014

  • Luo, Chan; Kyaw, Aung Ko Ko; Perez, Louis A.
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500758w

Patterning organic single-crystal transistor arrays
journal, December 2006

  • Briseno, Alejandro L.; Mannsfeld, Stefan C. B.; Ling, Mang M.
  • Nature, Vol. 444, Issue 7121, p. 913-917
  • DOI: 10.1038/nature05427

Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films
journal, November 2009

  • Rivnay, Jonathan; Jimison, Leslie H.; Northrup, John E.
  • Nature Materials, Vol. 8, Issue 12, p. 952-958
  • DOI: 10.1038/nmat2570

The interplay between interface structure, energy level alignment and chemical bonding strength at organic–metal interfaces
journal, January 2015

  • Willenbockel, M.; Lüftner, D.; Stadtmüller, B.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 3
  • DOI: 10.1039/c4cp04595e

Probing the dynamics of geometrically confined ferroelectric mesogens at the air interface
journal, January 2015

  • Chandran, Achu; Choudhary, Amit; Singh, Pankaj
  • Soft Matter, Vol. 11, Issue 4
  • DOI: 10.1039/c4sm01824a

Nanoscale polymer recognition by spectral signature in scattering infrared near-field microscopy
journal, November 2004

  • Taubner, T.; Hillenbrand, R.; Keilmann, F.
  • Applied Physics Letters, Vol. 85, Issue 21
  • DOI: 10.1063/1.1827334

Nanoscale-resolved chemical identification of thin organic films using infrared near-field spectroscopy and standard Fourier transform infrared references
journal, January 2015

  • Mastel, Stefan; Govyadinov, Alexander A.; de Oliveira, Thales V. A. G.
  • Applied Physics Letters, Vol. 106, Issue 2
  • DOI: 10.1063/1.4905507

Ultrabroadband infrared nanospectroscopic imaging
journal, May 2014

  • Bechtel, H. A.; Muller, E. A.; Olmon, R. L.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 20
  • DOI: 10.1073/pnas.1400502111

Works referencing / citing this record:

Exploiting Phonon‐Resonant Near‐Field Interaction for the Nanoscale Investigation of Extended Defects
journal, January 2020

  • Hauer, Benedikt; Marvinney, Claire E.; Lewin, Martin
  • Advanced Functional Materials, Vol. 30, Issue 10
  • DOI: 10.1002/adfm.201907357

Scanning Probe Microscopy in Materials Science
book, January 2019


Ultrafast structural molecular dynamics investigated with 2D infrared spectroscopy methods
journal, October 2017


Hyperspectral infrared nanoimaging of organic samples based on Fourier transform infrared nanospectroscopy
journal, February 2017

  • Amenabar, Iban; Poly, Simon; Goikoetxea, Monika
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14402

Infrared nano-spectroscopy of ferroelastic domain walls in hybrid improper ferroelectric Ca3Ti2O7
journal, November 2019


Toward understanding the adsorption mechanism of large size organic corrosion inhibitors on an Fe(110) surface using the DFTB method
journal, January 2017

  • Guo, Lei; Qi, Chengwei; Zheng, Xingwen
  • RSC Advances, Vol. 7, Issue 46
  • DOI: 10.1039/c7ra04120a

Hyperspectral mapping of anisotropy
journal, January 2019

  • Ryu, Meguya; Honda, Reo; Balčytis, Armandas
  • Nanoscale Horizons, Vol. 4, Issue 6
  • DOI: 10.1039/c9nh00340a

Nanoscale mapping of chemical composition in organic-inorganic hybrid perovskite films
journal, October 2019

  • Szostak, R.; Silva, J. C.; Turren-Cruz, S. -H.
  • Science Advances, Vol. 5, Issue 10
  • DOI: 10.1126/sciadv.aaw6619

Infrared electric field sampled frequency comb spectroscopy
journal, June 2019

  • Kowligy, Abijith S.; Timmers, Henry; Lind, Alexander J.
  • Science Advances, Vol. 5, Issue 6
  • DOI: 10.1126/sciadv.aaw8794

Ultrafast structural molecular dynamics investigated with 2D infrared spectroscopy methods
book, October 2017


Scanning Probe Microscopy in Materials Science
journal, July 2004

  • Meyer, Ernst; Jarvis, Suzanne P.; Spencer, Nicholas D.
  • MRS Bulletin, Vol. 29, Issue 7
  • DOI: 10.1557/mrs2004.137

Thin Film Analysis by Nanomechanical Infrared Spectroscopy
journal, April 2019


Hyperspectral infrared nanoimaging of organic samples based on Fourier transform infrared nanospectroscopy
journal, February 2017

  • Amenabar, Iban; Poly, Simon; Goikoetxea, Monika
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14402

Infrared nano-spectroscopy of ferroelastic domain walls in hybrid improper ferroelectric Ca3Ti2O7
journal, November 2019