skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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 TiO 2, where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2, 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 TiO 2 growth, contributing to the further development of this promising functional material.

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [5];  [6]; ORCiD logo [7];  [5]; ORCiD logo [8];  [6];  [5];  [9];  [1]
  1. Oregon State Univ., Corvallis, OR (United States). Dept. of Physics
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Programs
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  4. Colorado School of Mines, Golden, CO (United States). Dept. of Metallurgical and Materials Engineering
  5. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  6. 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
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  8. 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)
  9. 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) (SC-22)
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. 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., and Tate, Janet. Thu . "High-fraction brookite films from amorphous precursors". United States. doi: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}
}

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

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

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
  • DOI: 10.1021/cr0500535

Nucleation and growth of magnetite from solution
journal, February 2013

  • Baumgartner, Jens; Dey, Archan; Bomans, Paul H. H.
  • Nature Materials, Vol. 12, Issue 4
  • DOI: 10.1038/nmat3558

A review of focused ion beam milling techniques for TEM specimen preparation
journal, June 1999


Na in selenized Cu(In,Ga)Se2 on Na-containing and Na-free glasses: distribution, grain structure, and device performances
journal, September 2000


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
  • DOI: 10.1021/acs.jpcc.5b05338

Pure brookite titania crystals with large surface area deposited by Plasma Enhanced Chemical Vapour Deposition technique
journal, September 2008


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
  • DOI: 10.1126/science.aaa6760

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
  • DOI: 10.1143/JJAP.30.1008

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

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
  • DOI: 10.1021/jacs.6b11301

Review of the anatase to rutile phase transformation
journal, December 2010


Local order in titania polymorphs
journal, December 2001


In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways
journal, September 2014


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


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
  • DOI: 10.1063/1.1857059

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


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

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
  • DOI: 10.1021/am501656r

Zur hydrothermalen Synthese von Brookit
journal, July 1966


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
  • DOI: 10.1063/1.1849431

Oriented attachment and growth, twinning, polytypism, and formation of metastable phases; insights from nanocrystalline TiO 2
journal, October 1998


Structural, elastic, electronic and optical properties of various mineral phases of TiO 2 from first-principles calculations
journal, May 2014


Polymorph Engineering of TiO 2 : Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination
journal, May 2015


Brookite-rich titania films made by pulsed laser deposition
journal, May 2000


Phase transformation in room temperature pulsed laser deposited TiO2 thin films
journal, February 2003


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
  • DOI: 10.1107/S0108768102006948

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
  • DOI: 10.1021/ja803559b

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
  • DOI: 10.1021/acscatal.7b00131

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
  • DOI: 10.1021/cr500170p

TiO2 pure phase brookite with preferred orientation, synthesized as a spin-coated film
journal, December 2005


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
  • DOI: 10.1021/ja3014049

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
  • DOI: 10.1038/ncomms13799

A Concept for Synthesis Planning in Solid-State Chemistry
journal, October 2002


The thermodynamic scale of inorganic crystalline metastability
journal, November 2016

  • Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping
  • Science Advances, Vol. 2, Issue 11
  • DOI: 10.1126/sciadv.1600225

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
  • DOI: 10.1039/b100435m

Finite-size and pressure effects on the Raman spectrum of nanocrystalline anatase Ti O 2
journal, May 2005