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Title: Nanoscale Q -Resolved Phonon Dynamics in Block Copolymers

Abstract

Recently, responsive polymer-based structures have been researched extensively due to their unique ability to alter their physical properties upon exposure to external stimuli. Despite this, the nanoscale Q-resolved dynamic properties of these materials have barely been explored, which is limiting the development and applications of these materials. To address this issue, we used inelastic X-ray scattering (IXS) and found evidence for van der Waals mediated molecular vibration-responsive rattling dynamics in bulk poly(isoprene-block-styrene) (SI) and poly(styrene-block-ethylene oxide) (SO) stacked thin film block copolymers. Their cylinder-forming hexagonally arranged static structures were characterized using small-angle X-ray scattering (SAXS) and grazing incidence small-angle X-ray scattering (GISAXS), complemented by scanning electron microscopy (SEM). Specifically, we observed that the longitudinal vibrational mode in bulk SI experiences a strong phonon attenuation as temperature increases from 30 to 90 °C, while the transverse phonon excitations are nonexistent in the measured Q-range due to anharmonicity-mediated symmetry breaking in phonon interactions. Additionally, the emergent transverse acoustic phonon modes in both the bulk SI and SO thin films exhibited a nondispersive behavior with a nearly zero slope in the hydrodynamic limit (Q → 0), mimicking optical phonon excitations (i.e., standing waves). In summary, these findings point to the use of polymericmore » materials for Q-resolved nanoacoustic sensing, and the visualization of THz phonons.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [2]; ORCiD logo [4];  [5];  [5]; ORCiD logo [2]; ORCiD logo [5]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Cornell Univ., Ithaca, NY (United States)
  3. Joint Inst. for Nuclear Research (JINR), Dubna (Russian Federation); NAS of Ukraine, Kyiv (Ukraine); Moscow Inst. of Physics and Technology (MIPT), Moscow (Russian Federation)
  4. Harvard Univ., Cambridge, MA (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1561602
Grant/Contract Number:  
AC05-00OR22725; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Nano Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 9; Journal ID: ISSN 2574-0970
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block copolymers; Q-resolved polymer dynamics; emergent transverse phonons; phonon Q-gap; Q-resolved nanoacoustic polymer sensing

Citation Formats

Bolmatov, Dima, Zhang, Qi, Soloviov, Dmytro, Li, Yuk Mun, Werner, Jörg G., Suvorov, Alexey, Cai, Yong Q., Wiesner, Ulrich, Zhernenkov, Mikhail, and Katsaras, John. Nanoscale Q -Resolved Phonon Dynamics in Block Copolymers. United States: N. p., 2018. Web. doi:10.1021/acsanm.8b01087.
Bolmatov, Dima, Zhang, Qi, Soloviov, Dmytro, Li, Yuk Mun, Werner, Jörg G., Suvorov, Alexey, Cai, Yong Q., Wiesner, Ulrich, Zhernenkov, Mikhail, & Katsaras, John. Nanoscale Q -Resolved Phonon Dynamics in Block Copolymers. United States. doi:10.1021/acsanm.8b01087.
Bolmatov, Dima, Zhang, Qi, Soloviov, Dmytro, Li, Yuk Mun, Werner, Jörg G., Suvorov, Alexey, Cai, Yong Q., Wiesner, Ulrich, Zhernenkov, Mikhail, and Katsaras, John. Tue . "Nanoscale Q -Resolved Phonon Dynamics in Block Copolymers". United States. doi:10.1021/acsanm.8b01087. https://www.osti.gov/servlets/purl/1561602.
@article{osti_1561602,
title = {Nanoscale Q -Resolved Phonon Dynamics in Block Copolymers},
author = {Bolmatov, Dima and Zhang, Qi and Soloviov, Dmytro and Li, Yuk Mun and Werner, Jörg G. and Suvorov, Alexey and Cai, Yong Q. and Wiesner, Ulrich and Zhernenkov, Mikhail and Katsaras, John},
abstractNote = {Recently, responsive polymer-based structures have been researched extensively due to their unique ability to alter their physical properties upon exposure to external stimuli. Despite this, the nanoscale Q-resolved dynamic properties of these materials have barely been explored, which is limiting the development and applications of these materials. To address this issue, we used inelastic X-ray scattering (IXS) and found evidence for van der Waals mediated molecular vibration-responsive rattling dynamics in bulk poly(isoprene-block-styrene) (SI) and poly(styrene-block-ethylene oxide) (SO) stacked thin film block copolymers. Their cylinder-forming hexagonally arranged static structures were characterized using small-angle X-ray scattering (SAXS) and grazing incidence small-angle X-ray scattering (GISAXS), complemented by scanning electron microscopy (SEM). Specifically, we observed that the longitudinal vibrational mode in bulk SI experiences a strong phonon attenuation as temperature increases from 30 to 90 °C, while the transverse phonon excitations are nonexistent in the measured Q-range due to anharmonicity-mediated symmetry breaking in phonon interactions. Additionally, the emergent transverse acoustic phonon modes in both the bulk SI and SO thin films exhibited a nondispersive behavior with a nearly zero slope in the hydrodynamic limit (Q → 0), mimicking optical phonon excitations (i.e., standing waves). In summary, these findings point to the use of polymeric materials for Q-resolved nanoacoustic sensing, and the visualization of THz phonons.},
doi = {10.1021/acsanm.8b01087},
journal = {ACS Applied Nano Materials},
number = 9,
volume = 1,
place = {United States},
year = {2018},
month = {9}
}

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

Figures / Tables:

Figure 1 Figure 1: Schematic illustrating block copolymer film fabrication. The SI bulk sample most likely consists of "grains" with random orientation of hexagonally-arranged cylinders between different grains. The x-ray probes many different orientations of the cylinders at the same time. In the case of SO thin films, cylinders are aligned alongmore » the film normal with solvent annealing, hence, both structure and phonon dynamics of SO samples were studied in the plane orthogonal to hexagonallyarranged cylinders.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.