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Title: Hyperconnected molecular glass network architectures with exceptional elastic properties

Abstract

Hyperconnected network architectures can endow nanomaterials with remarkable mechanical properties that are fundamentally controlled by designing connectivity into the intrinsic molecular structure. For hybrid organic–inorganic nanomaterials, here we show that by using 1,3,5 silyl benzene precursors, the connectivity of a silicon atom within the network extends beyond its chemical coordination number, resulting in a hyperconnected network with exceptional elastic stiffness, higher than that of fully dense silica. The exceptional intrinsic stiffness of these hyperconnected glass networks is demonstrated with molecular dynamics models and these model predictions are calibrated through the synthesis and characterization of an intrinsically porous hybrid glass processed from 1,3,5(triethoxysilyl) benzene. Altogether, the proposed molecular design strategy applies to any materials system wherein the mechanical properties are controlled by the underlying network connectivity.

Authors:
 [1];  [1];  [2];  [2];  [2];  [3];  [1]
+ Show Author Affiliations
  1. Stanford Univ., Stanford, CA (United States)
  2. IBM Almaden Research Center, San Jose, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); IBM Almaden Research Center, San Jose, CA (United States)
Publication Date:
Research Org.:
Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1499684
Grant/Contract Number:  
FG02-07ER46391
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Burg, Joseph A., Oliver, Mark S., Frot, Theo J., Sherwood, Mark, Lee, Victor, Dubois, Geraud, and Dauskardt, Reinhold H. Hyperconnected molecular glass network architectures with exceptional elastic properties. United States: N. p., 2017. Web. doi:10.1038/s41467-017-01305-w.
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Burg, Joseph A., Oliver, Mark S., Frot, Theo J., Sherwood, Mark, Lee, Victor, Dubois, Geraud, & Dauskardt, Reinhold H. Hyperconnected molecular glass network architectures with exceptional elastic properties. United States. https://doi.org/10.1038/s41467-017-01305-w
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Burg, Joseph A., Oliver, Mark S., Frot, Theo J., Sherwood, Mark, Lee, Victor, Dubois, Geraud, and Dauskardt, Reinhold H. Wed . "Hyperconnected molecular glass network architectures with exceptional elastic properties". United States. https://doi.org/10.1038/s41467-017-01305-w. https://www.osti.gov/servlets/purl/1499684.
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@article{osti_1499684,
title = {Hyperconnected molecular glass network architectures with exceptional elastic properties},
author = {Burg, Joseph A. and Oliver, Mark S. and Frot, Theo J. and Sherwood, Mark and Lee, Victor and Dubois, Geraud and Dauskardt, Reinhold H.},
abstractNote = {Hyperconnected network architectures can endow nanomaterials with remarkable mechanical properties that are fundamentally controlled by designing connectivity into the intrinsic molecular structure. For hybrid organic–inorganic nanomaterials, here we show that by using 1,3,5 silyl benzene precursors, the connectivity of a silicon atom within the network extends beyond its chemical coordination number, resulting in a hyperconnected network with exceptional elastic stiffness, higher than that of fully dense silica. The exceptional intrinsic stiffness of these hyperconnected glass networks is demonstrated with molecular dynamics models and these model predictions are calibrated through the synthesis and characterization of an intrinsically porous hybrid glass processed from 1,3,5(triethoxysilyl) benzene. Altogether, the proposed molecular design strategy applies to any materials system wherein the mechanical properties are controlled by the underlying network connectivity.},
doi = {10.1038/s41467-017-01305-w},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {10}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1038/s41467-017-01305-w
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Cited by: 17 works
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Figures / Tables:

Fig. 1 Fig. 1 : Molecular dynamics simulations predict that hyperconnected glasses have exceptional elastic stiffness. Fully condensed silicon atoms (the condensation degree is q = 1.0) have network connectives of $m$$Si$ = 4 and $m$$Si$ = 5 for (a) ethylene-bridged glasses and (b) 1,3,5-benzene glasses, respectively. c The predicted bulk modulus,more » K, as a function of the predicted mass density, ρ, for model organosilicate glasses with various organic bridges: ethylene, methylene, 1,4-benzene, 1,3-benzene, and 1,3,5-benzene. The 1,3,5-benzene hyperconnected glasses have a higher stiffness but significantly less density than the experimental value for amorphous SiO2 (plotted as the open square)41–43. The simulated value for α-SiO2 shows good agreement with experiment. The error bars denote one standard deviation of the mean of three trials per condition« less
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Works referenced in this record:

Rigidity Transition in Materials: Hardness is Driven by Weak Atomic Constraints
journal, March 2015

  • Bauchy, Mathieu; Qomi, Mohammad Javad Abdolhosseini; Bichara, Christophe
  • Physical Review Letters, Vol. 114, Issue 12
  • DOI: 10.1103/PhysRevLett.114.125502

Cryogenic plasmas for controlled processing of nanoporous materials
journal, January 2011

  • Iacopi, Francesca; Choi, Jai Hyuk; Terashima, Kazuo
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 9
  • DOI: 10.1039/c0cp02660c

An efficient algorith for determining the convex hull of a finite planar set
journal, June 1972

Continuous deformations in random networks
journal, September 1983

Atomic scale foundation of temperature-dependent bonding constraints in network glasses and liquids
journal, July 2011

Topologically disordered networks of rigid polytopes
journal, August 1990

A Manufacturing Grade, Porous Oxycarbosilane Spin-On Dielectric Candidate with K ≤ 2.0
journal, January 2011

  • Volksen, Willi; Magbitang, Teddie P.; Miller, Robert D.
  • Journal of The Electrochemical Society, Vol. 158, Issue 7
  • DOI: 10.1149/1.3591081

Adjusting the Skeleton and Pore Structure of Porous SiCOH Dielectrics
journal, January 2009

  • Gates, S. M.; Dubois, G.; Ryan, E. T.
  • Journal of The Electrochemical Society, Vol. 156, Issue 10
  • DOI: 10.1149/1.3186029

The efficacy of post porosity plasma protection against vacuum-ultraviolet damage in porous low-k materials
journal, March 2015

  • Lionti, K.; Darnon, M.; Volksen, W.
  • Journal of Applied Physics, Vol. 117, Issue 11
  • DOI: 10.1063/1.4915508

Influence of network bond percolation on the thermal, mechanical, electrical and optical properties of high and low-k a-SiC:H thin films
journal, November 2013

Two algorithms for constructing a Delaunay triangulation
journal, June 1980

  • Lee, D. T.; Schachter, B. J.
  • International Journal of Computer & Information Sciences, Vol. 9, Issue 3
  • DOI: 10.1007/BF00977785

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

A topological-dynamical model of amorphycity
journal, October 1980

Toward Successful Integration of Porous Low-k Materials: Strategies Addressing Plasma Damage
journal, October 2014

  • Lionti, K.; Volksen, W.; Magbitang, T.
  • ECS Journal of Solid State Science and Technology, Vol. 4, Issue 1
  • DOI: 10.1149/2.0081501jss

Stiffening of organosilicate glasses by organic cross-linking
journal, January 2011

Molecular Origins of the Mechanical Behavior of Hybrid Glasses
journal, July 2010

  • Oliver, Mark S.; Dubois, Geraud; Sherwood, Mark
  • Advanced Functional Materials, Vol. 20, Issue 17
  • DOI: 10.1002/adfm.201000558

Broken Bond-Bending Constraints and Glass Formation in the Oxides
journal, June 1995

Post Porosity Plasma Protection: Scaling of Efficiency with Porosity
journal, April 2012

  • Frot, Theo; Volksen, Willi; Purushothaman, Sampath
  • Advanced Functional Materials, Vol. 22, Issue 14
  • DOI: 10.1002/adfm.201200152

Oxidative Polymerization of 1,4-Diethynylbenzene into Highly Conjugated Poly(phenylene butadiynylene) within the Channels of Surface-Functionalized Mesoporous Silica and Alumina Materials
journal, August 2002

  • Lin, Victor S. -Y.; Radu, Daniela R.; Han, Mi-Kyung
  • Journal of the American Chemical Society, Vol. 124, Issue 31
  • DOI: 10.1021/ja025925o

Low Dielectric Constant Materials
journal, January 2010

  • Volksen, Willi; Miller, Robert D.; Dubois, Geraud
  • Chemical Reviews, Vol. 110, Issue 1
  • DOI: 10.1021/cr9002819

Topology of covalent non-crystalline solids I: Short-range order in chalcogenide alloys
journal, October 1979

Hybrid low dielectric constant thin films for microelectronics
journal, March 2014

High-Modulus Spin-On Organosilicate Glasses for Nanoporous Applications
journal, March 2007

Phase-change materials and rigidity
journal, January 2017

  • Piarristeguy, Andrea; Pradel, Annie; Raty, Jean-Yves
  • MRS Bulletin, Vol. 42, Issue 01
  • DOI: 10.1557/mrs.2016.302

Topological engineering of doped photonic glasses
journal, January 2017

Heteronuclear decoupling in rotating solids
journal, October 1995

  • Bennett, Andrew E.; Rienstra, Chad M.; Auger, Michèle
  • The Journal of Chemical Physics, Vol. 103, Issue 16
  • DOI: 10.1063/1.470372

Glassy materials with enhanced thermal stability
journal, January 2017

Mechanical Fatigue of Hybrid Glasses
journal, August 2010

Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism
journal, October 1992

  • Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.
  • Nature, Vol. 359, Issue 6397, p. 710-712
  • DOI: 10.1038/359710a0

Superior mechanical properties of dense and porous organic/inorganic hybrid thin films
journal, May 2008

  • Dubois, Geraud; Volksen, Willi; Magbitang, Teddie
  • Journal of Sol-Gel Science and Technology, Vol. 48, Issue 1-2
  • DOI: 10.1007/s10971-008-1776-2

Investigation of plasma etch damage to porous oxycarbosilane ultra low- k dielectric
journal, June 2013

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

  • Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
  • Journal of the American Chemical Society, Vol. 118, Issue 45
  • DOI: 10.1021/ja9621760

Short-ranged structural rearrangement and enhancement of mechanical properties of organosilicate glasses induced by ultraviolet radiation
journal, March 2006

  • Iacopi, F.; Travaly, Y.; Eyckens, B.
  • Journal of Applied Physics, Vol. 99, Issue 5
  • DOI: 10.1063/1.2178393

Tetrahedron report number 273
journal, January 1990

Application of the Protection/Deprotection Strategy to the Science of Porous Materials
journal, April 2011

  • Frot, Theo; Volksen, Willi; Purushothaman, Sampath
  • Advanced Materials, Vol. 23, Issue 25
  • DOI: 10.1002/adma.201100569

Constraint theory, vector percolation and glass formation
journal, February 1985

Intrinsic nanoscale phase separation of bulk As 2 S 3 glass
journal, September 2003

The quickhull algorithm for convex hulls
journal, December 1996

  • Barber, C. Bradford; Dobkin, David P.; Huhdanpaa, Hannu
  • ACM Transactions on Mathematical Software, Vol. 22, Issue 4
  • DOI: 10.1145/235815.235821

Topological engineering of glasses using temperature-dependent constraints
journal, January 2017

  • Smedskjaer, Morten M.; Hermansen, Christian; Youngman, Randall E.
  • MRS Bulletin, Vol. 42, Issue 01
  • DOI: 10.1557/mrs.2016.299

Material functionalities from molecular rigidity: Maxwell’s modern legacy
journal, January 2017

Molecular Network Reinforcement of Sol–Gel Glasses
journal, November 2007

Optimization of amorphous semiconductors and low-/high-k dielectrics through percolation and topological constraint theory
journal, January 2017

  • Paquette, Michelle M.; Nordell, Bradley J.; Caruso, Anthony N.
  • MRS Bulletin, Vol. 42, Issue 01
  • DOI: 10.1557/mrs.2016.297

Nanoengineering of concrete via topological constraint theory
journal, January 2017

Ramped-Amplitude Cross Polarization in Magic-Angle-Spinning NMR
journal, October 1994

  • Metz, G.; Wu, X. L.; Smith, S. O.
  • Journal of Magnetic Resonance, Series A, Vol. 110, Issue 2
  • DOI: 10.1006/jmra.1994.1208

Arylene- and alkylene-bridged polysilsesquioxanes
journal, August 1993

Elastic and thermal expansion asymmetry in dense molecular materials
journal, June 2016

  • Burg, Joseph A.; Dauskardt, Reinhold H.
  • Nature Materials, Vol. 15, Issue 9
  • DOI: 10.1038/nmat4674

Determining the Poisson’s ratio of thin film materials using resonant method
journal, February 2003

Reversibly erasable nanoporous anti-reflection coatings from polyelectrolyte multilayers
journal, September 2002

  • Hiller, Jeri'Ann; Mendelsohn, Jonas D.; Rubner, Michael F.
  • Nature Materials, Vol. 1, Issue 1
  • DOI: 10.1038/nmat719

Selective Deposition of Compositionally Graded Hybrid Adhesive Films
journal, September 2015

  • Giachino, Marta; Watson, Brian L.; Dubois, Geraud
  • Advanced Materials Interfaces, Vol. 2, Issue 17
  • DOI: 10.1002/admi.201500262

Highly Transparent Multifunctional Bilayer Coatings on Polymers Using Low-Temperature Atmospheric Plasma Deposition
journal, June 2014

  • Cui, Linying; Lionti, Krystelle; Ranade, Alpana
  • ACS Nano, Vol. 8, Issue 7
  • DOI: 10.1021/nn502161p

Ultra Low- k Films Derived from Hyperbranched Polycarbosilanes (HBPCS)
journal, December 2008

  • Rathore, Jitendra S.; Interrante, Leonard V.; Dubois, Geraud
  • Advanced Functional Materials, Vol. 18, Issue 24
  • DOI: 10.1002/adfm.200801197

VMD: Visual molecular dynamics
journal, February 1996

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    Works referencing / citing this record:

    Design of Ultrastiff Organosilicate Hybrid Glasses
    journal, August 2019

    • Kilic, Karsu I.; Dauskardt, Reinhold H.
    • Advanced Functional Materials, Vol. 29, Issue 44
    • DOI: 10.1002/adfm.201904890

    Optically Transparent Protective Coating for Plastics Using Dual Spray and Atmospheric Plasma Deposition
    journal, February 2018

    • Ding, Yichuan; Dong, Siming; Han, Jiahao
    • Advanced Materials Interfaces, Vol. 5, Issue 9
    • DOI: 10.1002/admi.201701433

    Review of methods for the mitigation of plasma‐induced damage to low‐dielectric‐constant interlayer dielectrics used for semiconductor logic device interconnects
    journal, June 2019

    • Miyajima, Hideshi; Ishikawa, Kenji; Sekine, Makoto
    • Plasma Processes and Polymers, Vol. 16, Issue 9
    • DOI: 10.1002/ppap.201900039

    Theoretical search for heterogeneously architected 2D structures
    journal, July 2018

    • Yang, Weizhu; Liu, Qingchang; Gao, Zongzhan
    • Proceedings of the National Academy of Sciences, Vol. 115, Issue 31
    • DOI: 10.1073/pnas.1806769115
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