Selective Brookite Polymorph Formation Related to the Amorphous Precursor State in TiO2 Thin Films

Mangum, John S.; Agirseven, Okan; Haggerty, James E. S.; Perkins, John D.; Schelhas, Laura T.; Kitchaev, Daniil A.; Garten, Lauren M.; Ginley, David S.; Toney, Michael F.; Tate, Janet; Gorman, Brian P.

doi:10.1016/j.jnoncrysol.2018.10.049

Selective Brookite Polymorph Formation Related to the Amorphous Precursor State in TiO₂ Thin Films

Journal Article · Wed Nov 07 23:00:00 EST 2018 · Journal of Non-Crystalline Solids

DOI:https://doi.org/10.1016/j.jnoncrysol.2018.10.049· OSTI ID:1485571

Mangum, John S. ^[1]; Agirseven, Okan ^[2]; Haggerty, James E. S. ^[2]; Perkins, John D. ^[3]; Schelhas, Laura T. ^[4]; Kitchaev, Daniil A. ^[5]; Garten, Lauren M. ^[3]; Ginley, David S. ^[3]; Toney, Michael F. ^[4]; Tate, Janet ^[2]; Gorman, Brian P. ^[1]

Colorado School of Mines, Golden, CO (United States)
Oregon State Univ., Corvallis, OR (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

A wide variety of brookite TiO₂ 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 TiO₂ 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 pO₂ < 0.1 mTorr, while anatase is favored at high pO₂ > 5 mTorr. Brookite forms primarily at intermediate pO₂ (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 TiO₂ 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.

View Accepted Manuscript (DOE)

Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1485571

Alternate ID(s):: OSTI ID: 1635947

Report Number(s):: NREL/JA--5K00-72918

Journal Information:: Journal of Non-Crystalline Solids, Journal Name: Journal of Non-Crystalline Solids Journal Issue: C Vol. 505; ISSN 0022-3093

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

Tartaric acid-assisted preparation and photocatalytic performance of titania nanoparticles with controllable phases of anatase and brookite Shen, Xiaojun; Zhang, Jinlong; Tian, Baozhu Journal of Materials Science, Vol. 47, Issue 15 https://doi.org/10.1007/s10853-012-6465-4	journal	April 2012
Highly active semiconductor photocatalyst: Extra-fine crystallite of brookite TiO2 for redox reaction in aqueous propan-2-ol and / or silver sulfate solution Ohtani, Bunsho; Handa, Jun-ichi; Nishimoto, Sei-ichi Chemical Physics Letters, Vol. 120, Issue 3 https://doi.org/10.1016/0009-2614(85)87060-3	journal	October 1985
Vanadium — an element in search of a role Macara, Ian G. Trends in Biochemical Sciences, Vol. 5, Issue 4 https://doi.org/10.1016/0968-0004(80)90256-X	journal	April 1980
Atomic-scale structure of amorphous TiO2 by electron, X-ray diffraction and reverse Monte Carlo simulations Petkov, V.; Holzhüter, G.; Tröge, U. Journal of Non-Crystalline Solids, Vol. 231, Issue 1-2 https://doi.org/10.1016/S0022-3093(98)00418-9	journal	July 1998
A review of focused ion beam milling techniques for TEM specimen preparation Giannuzzi, L. A.; Stevie, F. A. Micron, Vol. 30, Issue 3 https://doi.org/10.1016/S0968-4328(99)00005-0	journal	June 1999
A stabilization mechanism of zirconia based on oxygen vacancies only Fabris, S. Acta Materialia, Vol. 50, Issue 20 https://doi.org/10.1016/S1359-6454(02)00385-3	journal	December 2002
Brookite→rutile phase transformation of TiO2 studied with monodispersed particles Li, Ji-Guang; Ishigaki, Takamasa Acta Materialia, Vol. 52, Issue 17 https://doi.org/10.1016/j.actamat.2004.07.020	journal	October 2004
Tailored preparation of titania with controllable phases of anatase and brookite by an alkalescent hydrothermal route Shen, Xiaojun; Tian, Baozhu; Zhang, Jinlong Catalysis Today, Vol. 201 https://doi.org/10.1016/j.cattod.2012.04.038	journal	March 2013
Preparation, characterization and photocatalytic activity of optically transparent titanium dioxide particles Štengl, Václav; Bakardjieva, Snejana; Murafa, Nataliya Materials Chemistry and Physics, Vol. 105, Issue 1 https://doi.org/10.1016/j.matchemphys.2007.04.037	journal	September 2007
Summary of “IAEA intercomparison of IBA software” Barradas, N. P.; Arstila, K.; Battistig, G. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 266, Issue 8 https://doi.org/10.1016/j.nimb.2007.10.043	journal	April 2008
Model based quantification of EELS spectra Verbeeck, J.; Van Aert, S. Ultramicroscopy, Vol. 101, Issue 2-4 https://doi.org/10.1016/j.ultramic.2004.06.004	journal	November 2004
Correlative Raman spectroscopy and focused ion beam for targeted phase boundary analysis of titania polymorphs Mangum, John S.; Chan, Lisa H.; Schmidt, Ute Ultramicroscopy, Vol. 188 https://doi.org/10.1016/j.ultramic.2018.02.007	journal	May 2018
Nanocrystalline Brookite with Enhanced Stability and Photocatalytic Activity: Influence of Lanthanum(III) Doping Perego, Céline; Wang, Yu-heng; Durupthy, Olivier ACS Applied Materials & Interfaces, Vol. 4, Issue 2 https://doi.org/10.1021/am201397n	journal	January 2012
Tailored Preparation Methods of TiO ₂ Anatase, Rutile, Brookite: Mechanism of Formation and Electrochemical Properties ^† Dambournet, Damien; Belharouak, Ilias; Amine, Khalil Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902613h	journal	February 2010
Anatase, Brookite, and Rutile Nanocrystals via Redox Reactions under Mild Hydrothermal Conditions: Phase-Selective Synthesis and Physicochemical Properties Li, Ji-Guang; Ishigaki, Takamasa; Sun, Xudong The Journal of Physical Chemistry C, Vol. 111, Issue 13 https://doi.org/10.1021/jp0673258	journal	April 2007
Different Reactivities of TiO ₂ Polymorphs: Comparative DFT Calculations of Water and Formic Acid Adsorption at Anatase and Brookite TiO ₂ Surfaces Li, Wei-Kun; Gong, Xue-Qing; Lu, Guanzhong The Journal of Physical Chemistry C, Vol. 112, Issue 17 https://doi.org/10.1021/jp802335h	journal	May 2008
On the stabilizing behavior of zirconia: A Combined experimental and theoretical study Foschini, C. R.; Filho, O. Treu; Juiz, S. A. Journal of Materials Science, Vol. 39, Issue 6 https://doi.org/10.1023/B:JMSC.0000017755.45305.84	journal	March 2004
High-fraction brookite films from amorphous precursors Haggerty, James E. S.; Schelhas, Laura T.; Kitchaev, Daniil A. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-15364-y	journal	November 2017
Understanding the anatase–rutile phase junction in charge separation and transfer in a TiO ₂ electrode for photoelectrochemical water splitting Li, Ailong; Wang, Zhiliang; Yin, Heng Chemical Science, Vol. 7, Issue 9 https://doi.org/10.1039/C6SC01611A	journal	January 2016
Synthesis of brookite-type titanium oxide nano-crystals in organic media Kominami, Hiroshi; Kohno, Masaaki; Kera, Yoshiya Journal of Materials Chemistry, Vol. 10, Issue 5 https://doi.org/10.1039/a908528i	journal	January 2000
Transformation of brookite-type TiO2 nanocrystals to rutile: correlation between microstructure and photoactivity Bakardjieva, Snejana; Stengl, Vaclav; Szatmary, Lorant Journal of Materials Chemistry, Vol. 16, Issue 18 https://doi.org/10.1039/b514632a	journal	January 2006
Toward high surface area TiO2 brookite with morphology control Dambournet, Damien; Belharouak, Ilias; Ma, Jiwei Journal of Materials Chemistry, Vol. 21, Issue 9 https://doi.org/10.1039/c0jm03258a	journal	January 2011
Amorphous and highly nonstoichiometric titania (TiOx) thin films close to metal-like conductivity Leichtweiss, Thomas; Henning, Ralph A.; Koettgen, Julius Journal of Materials Chemistry A, Vol. 2, Issue 18 https://doi.org/10.1039/c3ta14816e	journal	January 2014
Growth far from equilibrium: Examples from III-V semiconductors Kuech, Thomas F.; Babcock, Susan E.; Mawst, Luke Applied Physics Reviews, Vol. 3, Issue 4 https://doi.org/10.1063/1.4944801	journal	December 2016
Manganese oxide minerals: Crystal structures and economic and environmental significance Post, J. E. Proceedings of the National Academy of Sciences, Vol. 96, Issue 7 https://doi.org/10.1073/pnas.96.7.3447	journal	March 1999
Phase stability of TiO ₂ polymorphs from diffusion Quantum Monte Carlo Luo, Ye; Benali, Anouar; Shulenburger, Luke New Journal of Physics, Vol. 18, Issue 11 https://doi.org/10.1088/1367-2630/18/11/113049	journal	November 2016
Defect structure of yttria-stabilized zirconia and its influence on the ionic conductivity at elevated temperatures Goff, J. P.; Hayes, W.; Hull, S. Physical Review B, Vol. 59, Issue 22 https://doi.org/10.1103/PhysRevB.59.14202	journal	June 1999
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
Monodispersed Spherical Particles of Brookite-Type TiO2: Synthesis, Characterization, and Photocatalytic Property Li, Ji-Guang; Tang, Chengchun; Li, Di Journal of the American Ceramic Society, Vol. 87, Issue 7 https://doi.org/10.1111/j.1151-2916.2004.tb07735.x	journal	July 2004
Novel phase diagram behavior and materials design in heterostructural semiconductor alloys Holder, Aaron M.; Siol, Sebastian; Ndione, Paul F. Science Advances, Vol. 3, Issue 6 https://doi.org/10.1126/sciadv.1700270	journal	June 2017
Formation op Titanic Oxides of Anatase, Brookete and Rutile Types by Aerial Oxidation of Titanous Solutions Kiyama, Masao; Akita, Toshikazu; Tsutsumi, Yuji Chemistry Letters, Vol. 1, Issue 1 https://doi.org/10.1246/cl.1972.21	journal	January 1972
Hydrothermal Synthesis of Brookite Nagase, Takako; Ebina, Takeo; Iwasaki, Takashi Chemistry Letters, Vol. 28, Issue 9 https://doi.org/10.1246/cl.1999.911	journal	September 1999
[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] Oota, Toshitaka; Yamai, Iwao; Saito, Hajime Journal of the Ceramic Association, Japan, Vol. 87, Issue 1010 https://doi.org/10.2109/jcersj1950.87.1010_512	journal	January 1979
The effect of valence state and site geometry on Ti L3,2 and O K electron energy-loss spectra of TixOy phases Stoyanov, E.; Langenhorst, F.; Steinle-Neumann, G. American Mineralogist, Vol. 92, Issue 4 https://doi.org/10.2138/am.2007.2344	journal	April 2007
Brookite formation from precipitates containing calcium ions. Mitsuhashi, T.; Watanabe, M. Mineralogical Journal, Vol. 9, Issue 4 https://doi.org/10.2465/minerj.9.236	journal	January 1978
Brookite, the Least Known TiO2 Photocatalyst Di Paola, Agatino; Bellardita, Marianna; Palmisano, Leonardo Catalysts, Vol. 3, Issue 1 https://doi.org/10.3390/catal3010036	journal	January 2013

Cited By (2)

Crystallization of TiO ₂ polymorphs from RF-sputtered, amorphous thin-film precursors Agirseven, O.; Rivella, D. T.; Haggerty, J. E. S. AIP Advances, Vol. 10, Issue 2 https://doi.org/10.1063/1.5140368	journal	February 2020
Utilizing TiO ₂ amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics Mangum, John S.; Garten, Lauren M.; Ginley, David S. Journal of the American Ceramic Society, Vol. 103, Issue 4 https://doi.org/10.1111/jace.16965	journal	December 2019

Similar Records

Crystallization of TiO₂ polymorphs from RF-sputtered, amorphous thin-film precursors

Journal Article · Wed Feb 05 23:00:00 EST 2020 · AIP Advances · OSTI ID:1602697

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

Journal Article · Thu Dec 19 23:00:00 EST 2019 · Journal of the American Ceramic Society · OSTI ID:1598127

Kinetics study on phase transformation from titania polymorph brookite to rutile

Journal Article · Sat Mar 15 00:00:00 EDT 2008 · Journal of Solid State Chemistry · OSTI ID:21043918

Related Subjects

36 MATERIALS SCIENCE
TiO2
amorphous precursors
oxygen deficiency
polymorphs
selective crystallization
thin films