High-fraction brookite films from amorphous precursors
Abstract
Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO2, where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO2, a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO2 growth, contributing to the further development of this promising functional material.
- Authors:
-
[3];
[7];
[8];
- Oregon State Univ., Corvallis, OR (United States). Dept. of Physics
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Programs
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
- Colorado School of Mines, Golden, CO (United States). Dept. of Metallurgical and Materials Engineering
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Programs; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Colorado School of Mines, Golden, CO (United States). Dept. of Metallurgical and Materials Engineering
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1409492
- Alternate Identifier(s):
- OSTI ID: 1410515; OSTI ID: 1418211; OSTI ID: 1419455
- Report Number(s):
- NREL/JA-5K00-70535
Journal ID: ISSN 2045-2322
- Grant/Contract Number:
- AC36-08GO28308; AC02-76SF00515; ACI-1548562; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 36 MATERIALS SCIENCE; brookite; thin films; precursors; Materials for energy and catalysis; Surfaces, interfaces and thin films
Citation Formats
Haggerty, James E. S., Schelhas, Laura T., Kitchaev, Daniil A., Mangum, John S., Garten, Lauren M., Sun, Wenhao, Stone, Kevin H., Perkins, John D., Toney, Michael F., Ceder, Gerbrand, Ginley, David S., Gorman, Brian P., and Tate, Janet. High-fraction brookite films from amorphous precursors. United States: N. p., 2017.
Web. doi:10.1038/s41598-017-15364-y.
Haggerty, James E. S., Schelhas, Laura T., Kitchaev, Daniil A., Mangum, John S., Garten, Lauren M., Sun, Wenhao, Stone, Kevin H., Perkins, John D., Toney, Michael F., Ceder, Gerbrand, Ginley, David S., Gorman, Brian P., & Tate, Janet. High-fraction brookite films from amorphous precursors. United States. https://doi.org/10.1038/s41598-017-15364-y
Haggerty, James E. S., Schelhas, Laura T., Kitchaev, Daniil A., Mangum, John S., Garten, Lauren M., Sun, Wenhao, Stone, Kevin H., Perkins, John D., Toney, Michael F., Ceder, Gerbrand, Ginley, David S., Gorman, Brian P., and Tate, Janet. Thu .
"High-fraction brookite films from amorphous precursors". United States. https://doi.org/10.1038/s41598-017-15364-y. https://www.osti.gov/servlets/purl/1409492.
@article{osti_1409492,
title = {High-fraction brookite films from amorphous precursors},
author = {Haggerty, James E. S. and Schelhas, Laura T. and Kitchaev, Daniil A. and Mangum, John S. and Garten, Lauren M. and Sun, Wenhao and Stone, Kevin H. and Perkins, John D. and Toney, Michael F. and Ceder, Gerbrand and Ginley, David S. and Gorman, Brian P. and Tate, Janet},
abstractNote = {Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO2, where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO2, a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO2 growth, contributing to the further development of this promising functional material.},
doi = {10.1038/s41598-017-15364-y},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = {2017},
month = {11}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 1 work
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications
journal, July 2007
- Chen, Xiaobo; Mao, Samuel S.
- Chemical Reviews, Vol. 107, Issue 7
Nucleation and growth of magnetite from solution
journal, February 2013
- Baumgartner, Jens; Dey, Archan; Bomans, Paul H. H.
- Nature Materials, Vol. 12, Issue 4
A review of focused ion beam milling techniques for TEM specimen preparation
journal, June 1999
- Giannuzzi, L. A.; Stevie, F. A.
- Micron, Vol. 30, Issue 3
Na in selenized Cu(In,Ga)Se2 on Na-containing and Na-free glasses: distribution, grain structure, and device performances
journal, September 2000
- Rockett, A.; Britt, J. S.; Gillespie, T.
- Thin Solid Films, Vol. 372, Issue 1-2
Investigating the Energetic Ordering of Stable and Metastable TiO 2 Polymorphs Using DFT+ U and Hybrid Functionals
journal, August 2015
- Curnan, Matthew T.; Kitchin, John R.
- The Journal of Physical Chemistry C, Vol. 119, Issue 36
Pure brookite titania crystals with large surface area deposited by Plasma Enhanced Chemical Vapour Deposition technique
journal, September 2008
- Srivatsa, K. M. K.; Bera, Mrinmoyee; Basu, A.
- Thin Solid Films, Vol. 516, Issue 21
Crystallization by particle attachment in synthetic, biogenic, and geologic environments
journal, July 2015
- De Yoreo, J. J.; Gilbert, P. U. P. A.; Sommerdijk, N. A. J. M.
- Science, Vol. 349, Issue 6247
Enhancement of the optically activated NO2 gas sensing response of brookite TiO2 nanorods/nanoparticles thin films deposited by matrix-assisted pulsed-laser evaporation
journal, January 2012
- Manera, M. G.; Taurino, A.; Catalano, M.
- Sensors and Actuators B: Chemical, Vol. 161, Issue 1
Interference-Free Determination of the Optical Absorption Coefficient and the Optical Gap of Amorphous Silicon Thin Films
journal, May 1991
- Hishikawa, Yoshihiro; Nakamura, Noboru; Tsuda, Shinya
- Japanese Journal of Applied Physics, Vol. 30, Issue Part 1, No. 5
Brookite, the Least Known TiO2 Photocatalyst
journal, January 2013
- Di Paola, Agatino; Bellardita, Marianna; Palmisano, Leonardo
- Catalysts, Vol. 3, Issue 1
Thermodynamics of Phase Selection in MnO 2 Framework Structures through Alkali Intercalation and Hydration
journal, February 2017
- Kitchaev, Daniil A.; Dacek, Stephen T.; Sun, Wenhao
- Journal of the American Chemical Society, Vol. 139, Issue 7
Review of the anatase to rutile phase transformation
journal, December 2010
- Hanaor, Dorian A. H.; Sorrell, Charles C.
- Journal of Materials Science, Vol. 46, Issue 4
Local order in titania polymorphs
journal, December 2001
- Bokhimi, X.
- International Journal of Hydrogen Energy, Vol. 26, Issue 12
In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways
journal, September 2014
- Nielsen, M. H.; Aloni, S.; De Yoreo, J. J.
- Science, Vol. 345, Issue 6201
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Na incorporation into Cu(In,Ga)Se2 for high-efficiency flexible solar cells on polymer foils
journal, April 2005
- Rudmann, D.; Brémaud, D.; Zogg, H.
- Journal of Applied Physics, Vol. 97, Issue 8
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
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
Brookite TiO 2 Thin Film Epitaxially Grown on (110) YSZ Substrate by Atomic Layer Deposition
journal, July 2014
- Kim, Dai-Hong; Kim, Won-Sik; Kim, Sungtae
- ACS Applied Materials & Interfaces, Vol. 6, Issue 15
Zur hydrothermalen Synthese von Brookit
journal, July 1966
- Keesmann, I.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 346, Issue 1-2
Synthesis and characterization of mixed phase anatase TiO 2 and sodium-doped TiO 2 (B) thin films by low pressure chemical vapour deposition (LPCVD)
journal, January 2014
- Chimupala, Yothin; Hyett, Geoffrey; Simpson, Robert
- RSC Adv., Vol. 4, Issue 89
Optimization techniques for the estimation of the thickness and the optical parameters of thin films using reflectance data
journal, February 2005
- Ventura, S. D.; Birgin, E. G.; Martínez, J. M.
- Journal of Applied Physics, Vol. 97, Issue 4
Oriented attachment and growth, twinning, polytypism, and formation of metastable phases; insights from nanocrystalline TiO 2
journal, October 1998
- Penn, R. Lee; Banfield, Jillian F.
- American Mineralogist, Vol. 83, Issue 9-10
Structural, elastic, electronic and optical properties of various mineral phases of TiO 2 from first-principles calculations
journal, May 2014
- Liu, Qi-Jun; Zhang, Ning-Chao; Liu, Fu-Sheng
- Physica Scripta, Vol. 89, Issue 7
Synthesis, characterization and dye adsorption studies of porous brookite and mixed brookite with rutile TiO 2 using PEG assisted sol-gel synthesis process
journal, July 2017
- Balaganapathi, T.; KaniAmuthan, B.; Vinoth, S.
- Materials Research Bulletin, Vol. 91
Polymorph Engineering of TiO 2 : Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination
journal, May 2015
- Buckeridge, John; Butler, Keith T.; Catlow, C. Richard A.
- Chemistry of Materials, Vol. 27, Issue 11
Brookite-rich titania films made by pulsed laser deposition
journal, May 2000
- Moret, Mona P.; Zallen, Richard; Vijay, Dilip P.
- Thin Solid Films, Vol. 366, Issue 1-2
Phase transformation in room temperature pulsed laser deposited TiO2 thin films
journal, February 2003
- Sharma, A. K.; Thareja, R. K.; Willer, Ulrike
- Applied Surface Science, Vol. 206, Issue 1-4
New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design
journal, May 2002
- Belsky, Alec; Hellenbrandt, Mariette; Karen, Vicky Lynn
- Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3
Nonhydrolytic Synthesis of High-Quality Anisotropically Shaped Brookite TiO2 Nanocrystals
journal, August 2008
- Buonsanti, Raffaella; Grillo, Vincenzo; Carlino, Elvio
- Journal of the American Chemical Society, Vol. 130, Issue 33, p. 11223-11233
Trapping-Induced Enhancement of Photocatalytic Activity on Brookite TiO 2 Powders: Comparison with Anatase and Rutile TiO 2 Powders
journal, March 2017
- Vequizo, Junie Jhon M.; Matsunaga, Hironori; Ishiku, Tatsuya
- ACS Catalysis, Vol. 7, Issue 4
Solution-Phase Synthesis of Titanium Dioxide Nanoparticles and Nanocrystals
journal, May 2014
- Cargnello, Matteo; Gordon, Thomas R.; Murray, Christopher B.
- Chemical Reviews, Vol. 114, Issue 19
Investigation of the Origin of the Empirical Relationship between Refractive Index and Density on the Basis of First Principles Calculations for the Refractive Indices of Various TiO 2 Phases
journal, April 2004
- Rocquefelte, Xavier; Goubin, Fabrice; Koo, Hyun-Joo
- Inorganic Chemistry, Vol. 43, Issue 7
TiO2 pure phase brookite with preferred orientation, synthesized as a spin-coated film
journal, December 2005
- Kuznetsova, I. N.; Blaskov, V.; Stambolova, I.
- Materials Letters, Vol. 59, Issue 29-30
Synthesis of High-Quality Brookite TiO 2 Single-Crystalline Nanosheets with Specific Facets Exposed: Tuning Catalysts from Inert to Highly Reactive
journal, May 2012
- Lin, Haifeng; Li, Liping; Zhao, Minglei
- Journal of the American Chemical Society, Vol. 134, Issue 20
Evaluating structure selection in the hydrothermal growth of FeS2 pyrite and marcasite
journal, December 2016
- Kitchaev, Daniil A.; Ceder, Gerbrand
- Nature Communications, Vol. 7, Issue 1
A Concept for Synthesis Planning in Solid-State Chemistry
journal, October 2002
- Jansen, Martin
- Angewandte Chemie International Edition, Vol. 41, Issue 20
The thermodynamic scale of inorganic crystalline metastability
journal, November 2016
- Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping
- Science Advances, Vol. 2, Issue 11
Synthesis of brookite TiO2 nanoparticles by thermolysis of TiCl4 in strongly acidic aqueous media
journal, January 2001
- Pottier, Agnès; Chanéac, Corinne; Tronc, Elisabeth
- Journal of Materials Chemistry, Vol. 11, Issue 4
Synthesis and characterization of structural and optical properties of heteroepitaxial brookite TiO2 single crystalline films
journal, April 2016
- Wang, Weiguang; Wang, Mingxian; Li, Zhao
- Scripta Materialia, Vol. 115
Strongly Constrained and Appropriately Normed Semilocal Density Functional
journal, July 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- Physical Review Letters, Vol. 115, Issue 3
Finite-size and pressure effects on the Raman spectrum of nanocrystalline anatase
journal, May 2005
- Swamy, Varghese; Kuznetsov, Alexei; Dubrovinsky, Leonid S.
- Physical Review B, Vol. 71, Issue 18
Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications
journal, October 2007
- Chen, Xiaobo; Mao, Samuel S.
- ChemInform, Vol. 38, Issue 41
Energetics of nanocrystalline TiO2
journal, March 2002
- Ranade, M. R.; Navrotsky, A.; Zhang, H. Z.
- Proceedings of the National Academy of Sciences, Vol. 99, Issue Supplement 2
A Concept for Synthesis Planning in Solid-State Chemistry
journal, January 2003
- Jansen, Martin
- ChemInform, Vol. 34, Issue 3
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
Seeing crystal formation one particle at a time
journal, March 2020
- Han, Yilong
- Nature Materials, Vol. 19, Issue 4
Strongly Constrained and Appropriately Normed Semilocal Density Functional
preprint, January 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- arXiv
Works referencing / citing this record:
Understanding crystallization pathways leading to manganese oxide polymorph formation
journal, June 2018
- Chen, Bor-Rong; Sun, Wenhao; Kitchaev, Daniil A.
- Nature Communications, Vol. 9, Issue 1
Crystallization of TiO 2 polymorphs from RF-sputtered, amorphous thin-film precursors
journal, February 2020
- Agirseven, O.; Rivella, D. T.; Haggerty, J. E. S.
- AIP Advances, Vol. 10, Issue 2
Utilizing TiO 2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics
journal, December 2019
- Mangum, John S.; Garten, Lauren M.; Ginley, David S.
- Journal of the American Ceramic Society, Vol. 103, Issue 4
Visible-Light Active Titanium Dioxide Nanomaterials with Bactericidal Properties
journal, January 2020
- Liao, Chengzhu; Li, Yuchao; Tjong, Sie Chin
- Nanomaterials, Vol. 10, Issue 1