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Title: Utilizing TiO2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics

Abstract

Selective synthesis of metastable polymorphs requires a fundamental understanding of the complex energy landscapes in which these phases form. Recently, the development of in situ high temperature and controlled atmosphere transmission electron microscopy has enabled the direct observation of nucleation, growth, and phase transformations with near atomic resolution. In this work, we directly observe the crystallization behavior of amorphous TiO2 thin films grown under different pulsed laser deposition conditions and quantify the mechanisms behind metastable crystalline polymorph stabilization. Films deposited at 10 mTorr chamber oxygen pressure crystallize into nanocrystalline Anatase at 325 degrees C, whereas films deposited at 2 mTorr crystallize into significantly larger needle-like grains of Brookite and Anatase at 270 degrees C. Increasing film deposition rate by a factor of 4 results in a 10x increase in the crystalline growth front velocity as well as a decrease in crystallization temperature from 270 degrees C to 225 degrees C. Engineering the amorphous precursor state through deposition conditions therefore provides routes to microstructure control and the accessibility of higher energy metastable phases.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Colorado School of Mines, Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1598127
Alternate Identifier(s):
OSTI ID: 1580635
Report Number(s):
NREL/JA-5F00-75989
Journal ID: ISSN 0002-7820
Grant/Contract Number:  
AC36-08GO28308; AC3608GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 103; Journal Issue: 4; Journal ID: ISSN 0002-7820
Publisher:
American Ceramic Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; amorphous; crystals/crystallization; thin films; titanium dioxide

Citation Formats

Mangum, John S., Garten, Lauren M., Ginley, David S., and Gorman, Brian P. Utilizing TiO2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics. United States: N. p., 2019. Web. doi:10.1111/jace.16965.
Mangum, John S., Garten, Lauren M., Ginley, David S., & Gorman, Brian P. Utilizing TiO2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics. United States. https://doi.org/10.1111/jace.16965
Mangum, John S., Garten, Lauren M., Ginley, David S., and Gorman, Brian P. Fri . "Utilizing TiO2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics". United States. https://doi.org/10.1111/jace.16965. https://www.osti.gov/servlets/purl/1598127.
@article{osti_1598127,
title = {Utilizing TiO2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics},
author = {Mangum, John S. and Garten, Lauren M. and Ginley, David S. and Gorman, Brian P.},
abstractNote = {Selective synthesis of metastable polymorphs requires a fundamental understanding of the complex energy landscapes in which these phases form. Recently, the development of in situ high temperature and controlled atmosphere transmission electron microscopy has enabled the direct observation of nucleation, growth, and phase transformations with near atomic resolution. In this work, we directly observe the crystallization behavior of amorphous TiO2 thin films grown under different pulsed laser deposition conditions and quantify the mechanisms behind metastable crystalline polymorph stabilization. Films deposited at 10 mTorr chamber oxygen pressure crystallize into nanocrystalline Anatase at 325 degrees C, whereas films deposited at 2 mTorr crystallize into significantly larger needle-like grains of Brookite and Anatase at 270 degrees C. Increasing film deposition rate by a factor of 4 results in a 10x increase in the crystalline growth front velocity as well as a decrease in crystallization temperature from 270 degrees C to 225 degrees C. Engineering the amorphous precursor state through deposition conditions therefore provides routes to microstructure control and the accessibility of higher energy metastable phases.},
doi = {10.1111/jace.16965},
journal = {Journal of the American Ceramic Society},
number = 4,
volume = 103,
place = {United States},
year = {Fri Dec 20 00:00:00 EST 2019},
month = {Fri Dec 20 00:00:00 EST 2019}
}

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Works referenced in this record:

Nanocrystalline Brookite with Enhanced Stability and Photocatalytic Activity: Influence of Lanthanum(III) Doping
journal, January 2012

  • Perego, Céline; Wang, Yu-heng; Durupthy, Olivier
  • ACS Applied Materials & Interfaces, Vol. 4, Issue 2
  • DOI: 10.1021/am201397n

Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization
journal, June 2003


The Johnson-Mehl- Avrami-Kohnogorov model: A brief review
journal, July 1998

  • Fanfoni, M.; Tomellini, M.
  • Il Nuovo Cimento D, Vol. 20, Issue 7-8
  • DOI: 10.1007/BF03185527

Tailored Preparation Methods of TiO 2 Anatase, Rutile, Brookite: Mechanism of Formation and Electrochemical Properties
journal, February 2010

  • Dambournet, Damien; Belharouak, Ilias; Amine, Khalil
  • Chemistry of Materials, Vol. 22, Issue 3
  • DOI: 10.1021/cm902613h

Anatase, Brookite, and Rutile Nanocrystals via Redox Reactions under Mild Hydrothermal Conditions:  Phase-Selective Synthesis and Physicochemical Properties
journal, April 2007

  • Li, Ji-Guang; Ishigaki, Takamasa; Sun, Xudong
  • The Journal of Physical Chemistry C, Vol. 111, Issue 13
  • DOI: 10.1021/jp0673258

Brookite, the Least Known TiO2 Photocatalyst
journal, January 2013

  • Di Paola, Agatino; Bellardita, Marianna; Palmisano, Leonardo
  • Catalysts, Vol. 3, Issue 1
  • DOI: 10.3390/catal3010036

Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs
journal, May 2018


High-fraction brookite films from amorphous precursors
journal, November 2017

  • Haggerty, James E. S.; Schelhas, Laura T.; Kitchaev, Daniil A.
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/s41598-017-15364-y

Formation op Titanic Oxides of Anatase, Brookete and Rutile Types by Aerial Oxidation of Titanous Solutions
journal, January 1972

  • Kiyama, Masao; Akita, Toshikazu; Tsutsumi, Yuji
  • Chemistry Letters, Vol. 1, Issue 1
  • DOI: 10.1246/cl.1972.21

The O−Ti (Oxygen-Titanium) system
journal, April 1987

  • Murray, J. L.; Wriedt, H. A.
  • Journal of Phase Equilibria, Vol. 8, Issue 2
  • DOI: 10.1007/BF02873201

Understanding Polymorphic Phase Transformation Behavior during Growth of Nanocrystalline Aggregates:  Insights from TiO 2
journal, April 2000

  • Zhang, Hengzhong; Banfield, Jillian F.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 15
  • DOI: 10.1021/jp000499j

Growth far from equilibrium: Examples from III-V semiconductors
journal, December 2016

  • Kuech, Thomas F.; Babcock, Susan E.; Mawst, Luke
  • Applied Physics Reviews, Vol. 3, Issue 4
  • DOI: 10.1063/1.4944801

[各種チタン化合物からのブルッカイトの水熱合成とその生成機構について]<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1979-01-01">January 1979</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Oota, Toshitaka; Yamai, Iwao; Saito, Hajime</span> </li> <li> Journal of the Ceramic Association, Japan, Vol. 87, Issue 1010</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.2109/jcersj1950.87.1010_512" class="text-muted" target="_blank" rel="noopener noreferrer">10.2109/jcersj1950.87.1010_512<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1038/nmeth.2019" target="_blank" rel="noopener noreferrer" class="name">Fiji: an open-source platform for biological-image analysis<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2012-06-28">June 2012</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Schindelin, Johannes; Arganda-Carreras, Ignacio; Frise, Erwin</span> </li> <li> Nature Methods, Vol. 9, Issue 7</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1038/nmeth.2019" class="text-muted" target="_blank" rel="noopener noreferrer">10.1038/nmeth.2019<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1080/13642819908214860" target="_blank" rel="noopener noreferrer" class="name">Some electronic and metastability properties of a new nanostructured material: Hydrogenated polymorphous silicon<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1999-07-01">July 1999</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Butté, R.; Meaudre, R.; Meaudre, M.</span> </li> <li> Philosophical Magazine B, Vol. 79, Issue 7</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1080/13642819908214860" class="text-muted" target="_blank" rel="noopener noreferrer">10.1080/13642819908214860<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1021/cm990172z" target="_blank" rel="noopener noreferrer" class="name">Effect of Hydrothermal Treatment of Amorphous Titania on the Phase Change from Anatase to Rutile during Calcination<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1999-10-01">October 1999</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Ovenstone, James; Yanagisawa, Kazumichi</span> </li> <li> Chemistry of Materials, Vol. 11, Issue 10</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1021/cm990172z" class="text-muted" target="_blank" rel="noopener noreferrer">10.1021/cm990172z<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1021/jp802335h" target="_blank" rel="noopener noreferrer" class="name">Different Reactivities of TiO <sub>2</sub> Polymorphs:  Comparative DFT Calculations of Water and Formic Acid Adsorption at Anatase and Brookite TiO <sub>2</sub> Surfaces<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2008-05-01">May 2008</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Li, Wei-Kun; Gong, Xue-Qing; Lu, Guanzhong</span> </li> <li> The Journal of Physical Chemistry C, Vol. 112, Issue 17</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1021/jp802335h" class="text-muted" target="_blank" rel="noopener noreferrer">10.1021/jp802335h<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1088/0957-4484/19/14/145605" target="_blank" rel="noopener noreferrer" class="name">Phase-pure TiO <sub>2</sub> nanoparticles: anatase, brookite and rutile<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2008-03-05">March 2008</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Reyes-Coronado, D.; Rodríguez-Gattorno, G.; Espinosa-Pesqueira, M. E.</span> </li> <li> Nanotechnology, Vol. 19, Issue 14</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1088/0957-4484/19/14/145605" class="text-muted" target="_blank" rel="noopener noreferrer">10.1088/0957-4484/19/14/145605<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1007/s00339-008-4818-2" target="_blank" rel="noopener noreferrer" class="name">In situ transmission electron microscopy observations of the crystallization of amorphous Ge films<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2008-08-01">August 2008</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Cao, Z. H.; Liu, P.; Meng, X. K.</span> </li> <li> Applied Physics A, Vol. 94, Issue 2</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1007/s00339-008-4818-2" class="text-muted" target="_blank" rel="noopener noreferrer">10.1007/s00339-008-4818-2<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1021/cm020072k" target="_blank" rel="noopener noreferrer" class="name">Kinetics of Crystallization and Crystal Growth of Nanocrystalline Anatase in Nanometer-Sized Amorphous Titania<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2002-10-01">October 2002</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Zhang, Hengzhong; Banfield, Jillian F.</span> </li> <li> Chemistry of Materials, Vol. 14, Issue 10</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1021/cm020072k" class="text-muted" target="_blank" rel="noopener noreferrer">10.1021/cm020072k<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1126/sciadv.1700270" target="_blank" rel="noopener noreferrer" class="name">Novel phase diagram behavior and materials design in heterostructural semiconductor alloys<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2017-06-01">June 2017</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Holder, Aaron M.; Siol, Sebastian; Ndione, Paul F.</span> </li> <li> Science Advances, Vol. 3, Issue 6</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1126/sciadv.1700270" class="text-muted" target="_blank" rel="noopener noreferrer">10.1126/sciadv.1700270<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1016/j.jnoncrysol.2018.10.049" target="_blank" rel="noopener noreferrer" class="name">Selective brookite polymorph formation related to the amorphous precursor state in TiO2 thin films<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2019-02-01">February 2019</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Mangum, John S.; Agirseven, Okan; Haggerty, James E. S.</span> </li> <li> Journal of Non-Crystalline Solids, Vol. 505</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1016/j.jnoncrysol.2018.10.049" class="text-muted" target="_blank" rel="noopener noreferrer">10.1016/j.jnoncrysol.2018.10.049<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1063/1.1750631" target="_blank" rel="noopener noreferrer" class="name">Kinetics of Phase Change. II Transformation‐Time Relations for Random Distribution of Nuclei<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1940-02-01">February 1940</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Avrami, Melvin</span> </li> <li> The Journal of Chemical Physics, Vol. 8, Issue 2</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1063/1.1750631" class="text-muted" target="_blank" rel="noopener noreferrer">10.1063/1.1750631<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1016/j.msec.2005.08.032" target="_blank" rel="noopener noreferrer" class="name">Titanium alloys for biomedical applications<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2006-09-01">September 2006</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Rack, H. J.; Qazi, J. I.</span> </li> <li> Materials Science and Engineering: C, Vol. 26, Issue 8</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1016/j.msec.2005.08.032" class="text-muted" target="_blank" rel="noopener noreferrer">10.1016/j.msec.2005.08.032<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.2465/minerj.9.236" target="_blank" rel="noopener noreferrer" class="name">Brookite formation from precipitates containing calcium ions.<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1978-01-01">January 1978</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Mitsuhashi, T.; Watanabe, M.</span> </li> <li> Mineralogical Journal, Vol. 9, Issue 4</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.2465/minerj.9.236" class="text-muted" target="_blank" rel="noopener noreferrer">10.2465/minerj.9.236<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1063/1.356014" target="_blank" rel="noopener noreferrer" class="name">Mode of growth and microstructure of polycrystalline silicon obtained by solid‐phase crystallization of an amorphous silicon film<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1994-04-15">April 1994</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Haji, L.; Joubert, P.; Stoemenos, J.</span> </li> <li> Journal of Applied Physics, Vol. 75, Issue 8</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1063/1.356014" class="text-muted" target="_blank" rel="noopener noreferrer">10.1063/1.356014<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1246/cl.1999.911" target="_blank" rel="noopener noreferrer" class="name">Hydrothermal Synthesis of Brookite<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1999-09-01">September 1999</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Nagase, Takako; Ebina, Takeo; Iwasaki, Takashi</span> </li> <li> Chemistry Letters, Vol. 28, Issue 9</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1246/cl.1999.911" class="text-muted" target="_blank" rel="noopener noreferrer">10.1246/cl.1999.911<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1063/1.4958674" target="_blank" rel="noopener noreferrer" class="name">Influence of amorphous structure on polymorphism in vanadia<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2016-07-01">July 2016</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Stone, Kevin H.; 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G.; Harker, A. B.</span> </li> <li> Journal of Materials Research, Vol. 2, Issue 2</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1557/JMR.1987.0201" class="text-muted" target="_blank" rel="noopener noreferrer">10.1557/JMR.1987.0201<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1063/1.1750380" target="_blank" rel="noopener noreferrer" class="name">Kinetics of Phase Change. I General Theory<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="1939-12-01">December 1939</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Avrami, Melvin</span> </li> <li> The Journal of Chemical Physics, Vol. 7, Issue 12, p. 1103-1112</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1063/1.1750380" class="text-muted" target="_blank" rel="noopener noreferrer">10.1063/1.1750380<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> <div> <h2 class="title" style="margin-bottom:0;" data-apporder=""> <a href="https://doi.org/10.1016/j.scriptamat.2016.07.010" target="_blank" rel="noopener noreferrer" class="name">Thin film phase transformation kinetics: From theory to experiment<span class="fa fa-external-link" aria-hidden="true"></span></a> <small class="text-muted" style="text-transform:uppercase; font-size:0.75rem;"><br/> <span class="type">journal</span>, <span class="date" data-date="2016-11-01">November 2016</span></small> </h2> <ul class="small references-list" style="list-style-type:none; margin-top: 0.5em; padding-left: 0; line-height:1.8em;"> <li> <span style="color:#5C7B2D;"> Moghadam, M. 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S.</span> </li> <li> AIP Advances, Vol. 10, Issue 2</li> <li> <span class="text-muted related-url">DOI: <a href="https://doi.org/10.1063/1.5140368" class="text-muted" target="_blank" rel="noopener noreferrer">10.1063/1.5140368<span class="fa fa-external-link" aria-hidden="true"></span></a></span> </li> </ul> <hr/> </div> </div> <div class="pagination-container small"> <a class="pure-button prev page" href="#" rel="prev"><span class="sr-only">Previous Page</span><span class="fa fa-angle-left"></span></a> <ul class="pagination d-inline-block" style="padding-left:.2em;"></ul> <a class="pure-button next page" href="#" rel="next"><span class="sr-only">Next Page</span><span class="fa fa-angle-right"></span></a> </div> </div> </div> <div class="col-sm-3 order-sm-3"> <ul class="nav nav-stacked"> <li class="active"><a href="" class="reference-type-filter tab-nav" data-filter="type" data-pattern="*"><span class="fa fa-angle-right"></span> All Cited By</a></li> <li class="small" style="margin-left:.75em; text-transform:capitalize;"><a href="" class="reference-type-filter tab-nav" data-filter="type" data-pattern="journal"><span class="fa fa-angle-right"></span> journal<small class="text-muted"> (1)</small></a></li> </ul> <div style="margin-top:2em;"> <form class="pure-form small text-muted citation-search"> <label for="citation-search-text" class="sr-only">Search</label> <input class="search form-control pure-input-1" id="citation-search-text" placeholder="Search" style="margin-bottom:10px;" /> <fieldset aria-label="Sort By"> <legend class="legend-filters sr-only">Sort by:</legend> <div style="margin-left:1em; font-weight:normal; line-height: 1.6em;"><input type="radio" class="sort" name="references-sort" data-sort="name" style="position:relative;top:2px;" id="citation-search-sort-name"><label for="citation-search-sort-name" style="margin-left: .3em;">Sort by title</label></div> <div style="margin-left:1em; font-weight:normal; line-height: 1.6em;"><input type="radio" class="sort" name="references-sort" data-sort="date" data-order="desc" style="position:relative;top:2px;" id="citation-search-sort-date"><label for="citation-search-sort-date" style="margin-left: .3em;">Sort by date</label></div> </fieldset> <div class="text-left" style="margin-left:1em;"> <a href="" class="filter-clear clearfix" title="Clear filter / sort" style="font-weight:normal; float:none;">[ × clear filter / sort ]</a> </div> <input type="submit" id="sort_submit_citations" name="submit" aria-label="submit" style="display: none;"/> </form> </div> </div> </div> </section> <section id="biblio-related" class="tab-content tab-content-sec " data-tab="biblio"> <div class="row"> <div class="col-sm-9 order-sm-9"> <section id="biblio-similar" class="tab-content tab-content-sec active" data-tab="related"> <div class="padding"> <p class="lead text-muted" style="font-size: 18px; margin-top:0px;">Similar Records in DOE PAGES and OSTI.GOV collections:</p> <aside> <ul class="item-list" itemscope itemtype="http://schema.org/ItemList" style="padding-left:0; list-style-type: none;"> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="0" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/1485571-selective-brookite-polymorph-formation-related-amorphous-precursor-state-tio2-thin-films" itemprop="url">Selective Brookite Polymorph Formation Related to the Amorphous Precursor State in TiO<sub>2</sub> Thin Films</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Mangum, John S.</span> ; <span class="author">Agirseven, Okan</span> ; <span class="author">Haggerty, James E. S.</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Journal of Non-Crystalline Solids</span> </span> </div> <div class="abstract">A wide variety of brookite TiO<sub>2</sub> synthesis methods have been published over the past several decades, but few studies discuss the underlying mechanism that stabilizes brookite over its stable counterparts, rutile and anatase. Here in this study, we investigate of the effect of pulsed laser deposition parameters on the as-deposited amorphous precursor titania thin films, which subsequently crystallize into stable and metastable TiO<sub>2</sub> polymorphs upon annealing. We find that oxygen pressure in the deposition chamber strongly influences the non-equilibrium state of the amorphous precursor, which ultimately allows for selective polymorph formation. Rutile forms as the dominant phase at low pO<sub>2</sub><a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> < 0.1 mTorr, while anatase is favored at high pO<sub>2</sub> > 5 mTorr. Brookite forms primarily at intermediate pO<sub>2</sub> (0.5-1.0 mTorr). Controlling the amorphous structure (i.e. Ti - O bonding and polyhedral arrangement) of the precursors via oxygen deficiency is therefore likely for the selective formation of crystalline TiO<sub>2</sub> polymorphs from sub-stoichiometric amorphous precursors. Lastly, directing phase selectivity by manipulating the structure and internal energy of the precursor amorphous state may have tremendous potential for synthesis of metastable crystalline phases that exhibit more desirable properties in comparison to their stable counterparts.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <span class="fa fa-book text-muted" aria-hidden="true"></span> Cited by 7<div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc doi-link " href="https://doi.org/10.1016/j.jnoncrysol.2018.10.049" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="1485571" data-product-type="Journal Article" data-product-subtype="AM" >https://doi.org/10.1016/j.jnoncrysol.2018.10.049</a></span></li> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc fulltext-link " href="/pages/servlets/purl/1485571" title="Link to document media" target="_blank" rel="noopener" data-ostiid="1485571" data-product-type="Journal Article" data-product-subtype="AM" >Full Text Available</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="1" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/biblio/282223-solid-state-diffusive-amorphization-tio-sub-zro-sub-bilayers" itemprop="url">Solid-state diffusive amorphization in TiO{sub 2}/ZrO{sub 2} bilayers</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Shin, H</span> ; <span class="author">Agarwal, M</span> ; <span class="author">De Guire, M R</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Journal of the American Ceramic Society</span> </span> </div> <div class="abstract">Thin films of crystalline TiO{sub 2} were deposited on self-assembled organic monolayers from aqueous TiCl{sub 4} solutions at 80 C; partially crystalline ZrO{sub 2} films were deposited on top of the TiO{sub 2} layers from Zr(SO{sub 4}){sub 2} solutions at 70 C. In the absence of a ZrO{sub 2} film, the TiO{sub 2} films had the anatase structure and underwent grain coarsening on annealing at temperatures up to 800 C; in the absence of a TiO{sub 2} film, the ZrO{sub 2} films crystallized to the tetragonal polymorph at 500 C. However, the TiO{sub 2} and ZrO{sub 2} bilayers underwent solid-state<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> diffusive amorphization at 500 C, and ZrTiO{sub 4} crystallization could be observed only at temperatures of 550 C or higher. This result implies that metastable amorphous ZrTiO{sub 4} is energetically favorable compared to two-phase mixtures of crystalline TiO{sub 2} and ZrO{sub 2}, but that crystallization of ZrTiO{sub 4} involves a high activation barrier.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc doi-link " href="https://doi.org/10.1111/j.1151-2916.1996.tb08023.x" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="282223" data-product-type="Journal Article" data-product-subtype="AC" >https://doi.org/10.1111/j.1151-2916.1996.tb08023.x</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="2" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/biblio/22215486-synthesis-tio-sub-thin-films-using-single-molecular-precursors-mocvd-method-dye-sensitized-solar-cells-application-study-film-growth-mechanism" itemprop="url">Synthesis of TiO{sub 2} thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Nam, Sang Hun</span> ; <span class="author">Hyun, Jae-Sung</span> ; <span class="author">Boo, Jin-Hyo</span> <span class="text-muted pubdata"> - Materials Research Bulletin</span> </span> </div> <div class="abstract">For dye-sensitized solar cells application, in this study, we have synthesized TiO{sub 2} thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, (TIP, Ti(O{sup i}Pr){sub 4}) and Bis(dimethylamido)titanium diisopropoxide, (BTDIP, (Me{sub 2}N){sub 2}Ti(O{sup i}Pr){sub 2}) were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO{sub 2} polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO{sub<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> 2} thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO{sub 2} thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO{sub 2} film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO{sub 2} film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO{sub 2} film synthesized with BTDIP precursor to apply dye-sensitized solar cell.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc doi-link " href="https://doi.org/10.1016/J.MATERRESBULL.2012.04.039" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="22215486" data-product-type="Journal Article" data-product-subtype="AC" >https://doi.org/10.1016/J.MATERRESBULL.2012.04.039</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="3" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/pages/biblio/1388336-interfacial-stabilization-metastable-tio2-films" itemprop="url">Interfacial Stabilization of Metastable TiO<sub>2</sub> Films</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Gregory, Daniel G.</span> ; <span class="author">Lu, Li</span> ; <span class="author">Kiely, Christopher J.</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - Journal of Physical Chemistry. C</span> </span> </div> <div class="abstract">This work demonstrates a phenomenon that preserves the traditionally metastable anatase crystal structure of thin titania (TiO<sub>2</sub>) films along a two-dimensional oxide interface at temperatures well in excess of those that normally trigger a full polymorphic transformation to rutile in higher dimensionality crystalline powders. Whereas atomic surface mobility appears to dominate polymorph transformation processes within bulk TiO<sub>2</sub> powders, a simple reduction in dimensionality to a two-dimensional TiO<sub>2</sub> film (ca. 50–200 nm thick), supported upon a substrate, leads to a remarkable resistance to the calcination-induced anatase-to-rutile transformation. This stabilization does not appear to be specifically reliant on substrate character given its<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> persistence for TiO<sub>2</sub> films prepared on amorphous silica (SiO<sub>2</sub>) as well as crystalline TiO<sub>2</sub> substrates. Instead, interface-mediated coordination of the TiO<sub>2</sub> film with the substrate, and the inherent confinement of crystallites in two dimensions, is believed to resist polymorph transformation by mitigation of the atomic surface mobility. Furthermore, only when temperatures (i.e., >800 °C) that are conducive to bulk atomic mobilization are reached does reconstructive grain growth convert the film into the thermodynamically stable rutile crystal structure.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <span class="fa fa-book text-muted" aria-hidden="true"></span> Cited by 8<div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc doi-link " href="https://doi.org/10.1021/acs.jpcc.6b12943" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="1388336" data-product-type="Journal Article" data-product-subtype="AM" >https://doi.org/10.1021/acs.jpcc.6b12943</a></span></li> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc fulltext-link " href="/pages/servlets/purl/1388336" title="Link to document media" target="_blank" rel="noopener" data-ostiid="1388336" data-product-type="Journal Article" data-product-subtype="AM" >Full Text Available</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> <li> <div class="article item document" itemprop="itemListElement" itemscope itemtype="http://schema.org/WebPage"><meta itemprop="position" content="4" /><div class="item-info"> <h2 class="title" itemprop="name headline"><a href="/biblio/1257063-computational-approach-epitaxial-polymorph-stabilization-through-substrate-selection" itemprop="url">Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection</a></h2> <div class="metadata"> <small class="text-muted" style="text-transform:uppercase;display:block;line-height:2.5em;">Journal Article</small><span class="authors"> <span class="author">Ding, Hong</span> ; <span class="author">Dwaraknath, Shyam S.</span> ; <span class="author">Garten, Lauren</span> ; <span class="author">...</span> <span class="text-muted pubdata"> - ACS Applied Materials and Interfaces</span> </span> </div> <div class="abstract">With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO2 compounds which provides a rich chemical and structural polymorph space. We find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO2 substrates, where the VO2 brookite phase would be preferentially grown on the a-c TiO2 brookite plane while the columbite and anatase structures<a href='#' onclick='$(this).hide().next().show().next().show();return false;' style='margin-left:10px;'>more »</a><span style='display:none;'> favor the a-b plane on the respective TiO2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. These criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.</span><a href='#' onclick='$(this).hide().prev().hide().prev().show();return false;' style='margin-left:10px;display:none;'>« less</a></div><div class="metadata-links small clearfix text-muted" style="margin-top:15px;"> <div class="pure-menu pure-menu-horizontal pull-right" style="width:unset;"> <ul class="pure-menu-list"> <li class="pure-menu-item"><span class="item-info-ftlink"><a class="misc doi-link " href="https://doi.org/10.1021/acsami.6b01630" target="_blank" rel="noopener" title="Link to document DOI" data-ostiid="1257063" data-product-type="Journal Article" data-product-subtype="AC" >https://doi.org/10.1021/acsami.6b01630</a></span></li> </ul> </div> </div> </div> <div class="clearfix"></div> </div> </li> </ul> </aside> </div> </section> </div> <div class="col-sm-3 order-sm-3"> <ul class="nav nav-stacked"> <li class="active"><a class="tab-nav disabled" data-tab="related" style="color: #636c72 !important; opacity: 1;"><span class="fa fa-angle-right"></span> Similar Records</a></li> </ul> </div> </div> </section> </div></div> </div> </div> </section> <footer class="" style="background-color:#f9f9f9;"> <div class="footer-minor"> <div class="container"> <hr class="footer-separator"/> <br/> <div class="col text-center mt-3"> <div class="pure-menu pure-menu-horizontal"> <ul class="pure-menu-list" id="footer-org-menu"> <li class="pure-menu-item"> <a href="https://energy.gov" target="_blank" rel="noopener noreferrer"> <img src="data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==" class="sprite sprite-footer-us-doe-min" alt="U.S. Department of Energy" /> </a> </li> <li class="pure-menu-item"> <a href="https://www.energy.gov/science/office-science" target="_blank" rel="noopener noreferrer"> <img src="data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==" class="sprite sprite-footer-office-of-science-min" alt="Office of Science" /> </a> </li> <li class="pure-menu-item"> <a href="https://www.osti.gov" target="_blank" rel="noopener noreferrer"> <img src="data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==" class="sprite sprite-footer-osti-min" alt="Office of Scientific and Technical Information" /> </a> </li> </ul> </div> </div> <div class="col text-center small" style="margin-top: 0.5em;margin-bottom:2.0rem;"> <div class="row justify-content-center" style="color:white"> <div class="pure-menu pure-menu-horizontal" style='white-space:normal'> <ul class="pure-menu-list"> <li class="pure-menu-item"><a href="https://www.osti.gov/disclaim" class="pure-menu-link" target="_blank" ref="noopener noreferrer"><span class="fa fa-institution"></span> Website Policies <span class="d-none d-sm-inline d-print-none" style="color:#737373;">/ Important Links</span></a></li> <li class="pure-menu-item" style='float:none;'><a href="/pages/contact" class="pure-menu-link"><span class="fa fa-comments-o"></span>Contact Us</a></li> <li class="d-block d-md-none mb-1"></li> <li class="pure-menu-item" style='float:none;'><a target="_blank" title="Vulnerability Disclosure Program" class="pure-menu-link" href="https://doe.responsibledisclosure.com/hc/en-us" rel="noopener noreferrer">Vulnerability Disclosure Program</a></li> <li class="d-block d-lg-none mb-1"></li> <li class="pure-menu-item" style="float:none;"><a href="https://www.facebook.com/ostigov" target="_blank" class="pure-menu-link social ext fa fa-facebook" rel="noopener noreferrer"><span class="sr-only" style="background-color: #fff; color: #333;">Facebook</span></a></li> <li class="pure-menu-item" style="float:none;"><a href="https://twitter.com/OSTIgov" target="_blank" class="pure-menu-link social ext fa fa-twitter" rel="noopener noreferrer"><span class="sr-only" style="background-color: #fff; color: #333;">Twitter</span></a></li> <li class="pure-menu-item" style="float:none;"><a href="https://www.youtube.com/user/ostigov" target="_blank" class="pure-menu-link social ext fa fa-youtube-play" rel="noopener noreferrer"><span class="sr-only" style="background-color: #fff; color: #333;">Youtube</span></a></li> </ul> </div> </div> </div> </div> </div> </footer> <link href="/pages/css/pages.fonts.240327.0205.css" rel="stylesheet"> <script src="/pages/js/pages.240327.0205.js"></script><noscript></noscript> <script defer src="/pages/js/pages.biblio.240327.0205.js"></script><noscript></noscript> <script defer src="/pages/js/lity.js"></script><noscript></noscript> <script async type="text/javascript" src="/pages/js/Universal-Federated-Analytics-Min.js?agency=DOE" id="_fed_an_ua_tag"></script><noscript></noscript> </body> <!-- DOE PAGES v.240327.0205 --> </html>