All Roads Lead to TiO2: TiO2-Rich Surfaces of Barium and Strontium Titanate Prepared by Hydrothermal Synthesis

Crosby, Lawrence A.; Chen, Bor-Rong; Kennedy, Robert M.; Wen, Jianguo; Poeppelmeier, Kenneth R.; Bedzyk, Michael J.; Marks, Laurence D.

doi:10.1021/acs.chemmater.7b04404

Title: All Roads Lead to TiO₂: TiO₂-Rich Surfaces of Barium and Strontium Titanate Prepared by Hydrothermal Synthesis

Journal Article · Tue Jan 30 00:00:00 EST 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b04404· OSTI ID:1870995

^[1]; Chen, Bor-Rong ^[1];

^[1]; Wen, Jianguo ^[2];

^[1];

^[1]; Marks, Laurence D. ^[1]

Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials

Through high-resolution electron microscopy, the surface structure of barium titanate and strontium titanate nanoparticles are found to be terminated by a TiO₂ double layer. These results confirm prior observations of TiO₂-rich surface reconstructions on strontium titanate nanoparticles made hydrothermally at high pH and single crystals prepared with wet chemical etching. Of all the reconstructions observed on single crystals for these two materials, we report for first time the √13 × √13R33.7° structure on the {001} facets of hydrothermally prepared barium titanate and strontium titanate nanocrystals. The aqueous environment common to the two preparation methods preferentially leaves strontium and barium depleted from the A-sites near the surface and leads to TiO₂-terminated surfaces for both materials. Analysis indicates that the observed structures are the thermodynamic lowest energy structures in aqueous conditions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 1870995

Journal Information:: Chemistry of Materials, Vol. 30, Issue 3; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 25 works

Citation information provided by
Web of Science

References (52)

Epitaxial Growth Process of La _0.7 Ca _0.3 MnO ₃ Thin Films on SrTiO ₃ (001): Thickness-Dependent Inhomogeneity Caused by Excess Ti Atoms Shimizu, Ryota; Ohsawa, Takeo; Iwaya, Katsuya Crystal Growth & Design, Vol. 14, Issue 4 https://doi.org/10.1021/cg4013119	journal	March 2014
Surface Structures of SrTiO ₃ (001): A TiO ₂ -rich Reconstruction with a c(4 × 2) Unit Cell Erdman, Natasha; Warschkow, Oliver; Asta, Mark Journal of the American Chemical Society, Vol. 125, Issue 33 https://doi.org/10.1021/ja034933h	journal	August 2003
Ferroelectric, dielectric and piezoelectric properties of ferroelectric thin films and ceramics Damjanovic, Dragan Reports on Progress in Physics, Vol. 61, Issue 9 https://doi.org/10.1088/0034-4885/61/9/002	journal	September 1998
Particle-size-induced diffuse phase transition in the fine-particle barium titanate porcelains Park, Yung; Lee, Won-Jae; Kim, Ho-Gi Journal of Physics: Condensed Matter, Vol. 9, Issue 43 https://doi.org/10.1088/0953-8984/9/43/027	journal	October 1997
Synthesis-Dependent First-Order Raman Scattering in SrTiO ₃ Nanocubes at Room Temperature Rabuffetti, Federico A.; Kim, Hack-Sung; Enterkin, James A. Chemistry of Materials, Vol. 20, Issue 17 https://doi.org/10.1021/cm801192t	journal	September 2008
Controlled Carrier Generation at a Polarity-Discontinued Perovskite Heterointerface Nishimura, Jun; Ohtomo, Akira; Ohkubo, Atsushi Japanese Journal of Applied Physics, Vol. 43, Issue No. 8A https://doi.org/10.1143/JJAP.43.L1032	journal	July 2004
Thermal decomposition of strontium hydroxide Dinescu, R.; Preda, M. Journal of Thermal Analysis, Vol. 5, Issue 4 https://doi.org/10.1007/BF01950236	journal	August 1973
The Role of Oleic Acid: From Synthesis to Assembly of Perovskite Nanocuboid Two-Dimensional Arrays Hu, Linhua; Wang, Chuandao; Kennedy, Robert M. Inorganic Chemistry, Vol. 54, Issue 3 https://doi.org/10.1021/ic5011715	journal	August 2014
Transition from Reconstruction toward Thin Film on the (110) Surface of Strontium Titanate Wang, Z.; Loon, A.; Subramanian, A. Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.5b05211	journal	March 2016
Size dependence of the ferroelectric transition of small ${BaTiO}_{3}$ particles: Effect of depolarization Shih, Wan Y.; Shih, Wei-Heng; Aksay, Ilhan A. Physical Review B, Vol. 50, Issue 21 https://doi.org/10.1103/PhysRevB.50.15575	journal	December 1994
Defects on Strontium Titanate Marshall, Matthew S. J.; Becerra-Toledo, Andres E.; Marks, Laurence D. Defects at Oxide Surfaces https://doi.org/10.1007/978-3-319-14367-5_11	book	January 2015
Ferroelectric Ceramics: History and Technology Haertling, Gene H. Journal of the American Ceramic Society, Vol. 82, Issue 4, p. 797-818 https://doi.org/10.1111/j.1151-2916.1999.tb01840.x	journal	April 1999
Complex surface structure of (110) terminated strontium titanate nanododecahedra Crosby, Lawrence A.; Kennedy, Robert M.; Chen, Bor-Rong Nanoscale, Vol. 8, Issue 37 https://doi.org/10.1039/C6NR05516H	journal	January 2016
Oleic acid assisted glycothermal synthesis of cuboidal Ba0.6Sr0.4TiO3 nanocrystals and their ordered architectures via self-assembly Xiaowei, Yang; Yanwei, Zeng; Leiqing, Mo Journal of Colloid and Interface Science, Vol. 357, Issue 2 https://doi.org/10.1016/j.jcis.2011.02.015	journal	May 2011
Ordering of TiO ₂ -Based Nanostructures on SrTiO ₃ (001) Surfaces Deak, David S.; Silly, Fabien; Newell, David T. The Journal of Physical Chemistry B, Vol. 110, Issue 18 https://doi.org/10.1021/jp060954x	journal	April 2006
Morphology and growth modes of metal-oxides deposited on SrTiO3 Wohlwend, Jennifer L.; Behera, Rakesh K.; Jang, Inkook Surface Science, Vol. 603, Issue 6 https://doi.org/10.1016/j.susc.2009.01.035	journal	March 2009
Ferroelectric-Based Catalysis: Switchable Surface Chemistry Kakekhani, Arvin; Ismail-Beigi, Sohrab ACS Catalysis, Vol. 5, Issue 8 https://doi.org/10.1021/acscatal.5b00507	journal	June 2015
The structure and chemistry of the TiO2-rich surface of SrTiO3 (001) Erdman, Natasha; Poeppelmeier, Kenneth R.; Asta, Mark Nature, Vol. 419, Issue 6902 https://doi.org/10.1038/nature01010	journal	September 2002
Scanning tunneling microscopy of reconstructions on the SrTiO3() surface Castell, Martin R. Surface Science, Vol. 505 https://doi.org/10.1016/S0039-6028(02)01393-6	journal	May 2002
Shape-controlled growth of SrTiO3 polyhedral submicro/nanocrystals Dong, Lingqing; Shi, Hui; Cheng, Kui Nano Research, Vol. 7, Issue 9 https://doi.org/10.1007/s12274-014-0495-y	journal	August 2014
A homologous series of structures on the surface of SrTiO3(110) Enterkin, James A.; Subramanian, Arun K.; Russell, Bruce C. Nature Materials, Vol. 9, Issue 3 https://doi.org/10.1038/nmat2636	journal	February 2010
Comparison of acid- and non-acid-based surface preparations of Nb-doped SrTiO ₃ (001) Hatch, Richard C.; Choi, Miri; Posadas, Agham B. Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 33, Issue 6 https://doi.org/10.1116/1.4931616	journal	November 2015
Direct Imaging of Carbon-Covered and Clean Gold (110) Surfaces Marks, L. D. Physical Review Letters, Vol. 51, Issue 11 https://doi.org/10.1103/PhysRevLett.51.1000	journal	September 1983
Universal Ti-rich termination of atomically flat SrTiO3 (001), (110), and (111) surfaces Biswas, A.; Rossen, P. B.; Yang, C. -H. Applied Physics Letters, Vol. 98, Issue 5 https://doi.org/10.1063/1.3549860	journal	January 2011
Atomic Control of the SrTiO₃ Crystal Surface Kawasaki, M.; Takahashi, K.; Maeda, T. Science, Vol. 266, Issue 5190, p. 1540-1542 https://doi.org/10.1126/science.266.5190.1540	journal	December 1994
Weak alkali and alkaline earth metal complexes of low molecular weight ligands in aqueous solution Daniele, Pier G.; Foti, Claudia; Gianguzza, Antonio Coordination Chemistry Reviews, Vol. 252, Issue 10-11 https://doi.org/10.1016/j.ccr.2007.08.005	journal	May 2008
On the relationship between surface reconstructions and step edge stability on BaTiO3 (001) Morales, Erie H.; Bonnell, Dawn A. Surface Science, Vol. 609 https://doi.org/10.1016/j.susc.2012.11.006	journal	March 2013
Thermal decomposition of the hydrates of barium hydroxide Habashy, G. M.; Kolta, G. A. Journal of Inorganic and Nuclear Chemistry, Vol. 34, Issue 1 https://doi.org/10.1016/0022-1902(72)80361-0	journal	January 1972
Surface determination through atomically resolved secondary-electron imaging Ciston, J.; Brown, H. G.; D’Alfonso, A. J. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8358	journal	June 2015
Synthesis-Dependent Atomic Surface Structures of Oxide Nanoparticles Lin, Yuyuan; Wen, Jianguo; Hu, Linhua Physical Review Letters, Vol. 111, Issue 15 https://doi.org/10.1103/PhysRevLett.111.156101	journal	October 2013
A-site surface termination in strontium titanate single crystals Schrott, A. G.; Misewich, J. A.; Copel, M. Applied Physics Letters, Vol. 79, Issue 12 https://doi.org/10.1063/1.1404129	journal	September 2001
c(6×2) and c(4×2) reconstruction of SrTiO 3 (001) Jiang, Q. D.; Zegenhagen, J. Surface Science, Vol. 425, Issue 2-3 https://doi.org/10.1016/S0039-6028(99)00223-X	journal	April 1999
Cationic Surface Segregation in Donor-Doped SrTiO3 Under Oxidizing Conditions Meyer, René; Waser, Rainer; Helmbold, Julia Journal of Electroceramics, Vol. 9, Issue 2, p. 101-110 https://doi.org/10.1023/A:1022898104375	journal	November 2002
Bonding and structure of a reconstructed (001) surface of SrTiO3 from TEM Zhu, Guo-zhen; Radtke, Guillaume; Botton, Gianluigi A. Nature, Vol. 490, Issue 7420 https://doi.org/10.1038/nature11563	journal	October 2012
Direct surface imaging in small metal particles Marks, L. D.; Smith, David J. Nature, Vol. 303, Issue 5915 https://doi.org/10.1038/303316a0	journal	May 1983
Surface electronic structure for various surface preparations of Nb-doped SrTiO ₃ (001) Hatch, Richard C.; Fredrickson, Kurt D.; Choi, Miri Journal of Applied Physics, Vol. 114, Issue 10 https://doi.org/10.1063/1.4821095	journal	September 2013
ALD synthesis of platinum nanoparticles on single-crystal SrTiO3 pretreated with wet chemical etching Wang, Chuandao; Koirala, Pratik; Stair, Peter Applied Surface Science, Vol. 422 https://doi.org/10.1016/j.apsusc.2017.05.187	journal	November 2017
Electronic structure and thermodynamic stability of double-layered $Sr Ti O_{3} (001)$ surfaces: Ab initio simulations Heifets, Eugene; Piskunov, Sergei; Kotomin, Eugene A. Physical Review B, Vol. 75, Issue 11 https://doi.org/10.1103/PhysRevB.75.115417	journal	March 2007
Comparative Adsorption of Saturated and Unsaturated Fatty Acids at the Iron Oxide/Oil Interface Wood, Mary H.; Casford, M. T.; Steitz, R. Langmuir, Vol. 32, Issue 2 https://doi.org/10.1021/acs.langmuir.5b04435	journal	January 2016
Epitaxial Growth Mechanism of Chemical-Vapor-Deposited Anatase on Strontium Titanate Substrate Saitoh, Hidetoshi; Sunayama, Hideki; Tanaka, Norio Journal of the Ceramic Society of Japan, Vol. 106, Issue 1239 https://doi.org/10.2109/jcersj.106.1051	journal	January 1998
A simple and controllable hydrothermal route for the synthesis of monodispersed cube-like barium titanate nanocrystals Cai, Wen; Rao, Tingke; Wang, Aiwu Ceramics International, Vol. 41, Issue 3 https://doi.org/10.1016/j.ceramint.2014.11.146	journal	April 2015
Atomically flat SrO-terminated SrTiO3(001) substrate Bachelet, R.; Sánchez, F.; Palomares, F. J. Applied Physics Letters, Vol. 95, Issue 14 https://doi.org/10.1063/1.3240869	journal	October 2009
Crystal Structure and the Paraelectric-to-Ferroelectric Phase Transition of Nanoscale BaTiO ₃ Smith, Millicent B.; Page, Katharine; Siegrist, Theo Journal of the American Chemical Society, Vol. 130, Issue 22 https://doi.org/10.1021/ja0758436	journal	June 2008
Grain-size effect on structure and phase transformations for barium titanate Frey, M. H.; Payne, D. A. Physical Review B, Vol. 54, Issue 5 https://doi.org/10.1103/PhysRevB.54.3158	journal	August 1996
Facet-Dependent Electrical Conductivity Properties of Cu ₂ O Crystals Tan, Chih-Shan; Hsu, Shih-Chen; Ke, Wei-Hong Nano Letters, Vol. 15, Issue 3 https://doi.org/10.1021/acs.nanolett.5b00150	journal	February 2015
Synthesis and facet-dependent photocatalytic activity of strontium titanate polyhedron nanocrystals Li, Junfang; Bai, Hua; Yi, Wencai Nano Research, Vol. 9, Issue 5 https://doi.org/10.1007/s12274-016-1048-3	journal	May 2016
Thermodynamics of the Hydrothermal Synthesis of Calcium Titanate with Reference to Other Alkaline-Earth Titanates Lencka, Malgorzata M.; Riman, Richard E. Chemistry of Materials, Vol. 7, Issue 1 https://doi.org/10.1021/cm00049a006	journal	January 1995
SrTiO3(001) reconstructions: the (2×2) to c(4×4) transition Silly, Fabien; Newell, David T.; Castell, Martin R. Surface Science, Vol. 600, Issue 17 https://doi.org/10.1016/j.susc.2006.05.043	journal	September 2006
SrTiO ₃ Nanocuboids from a Lamellar Microemulsion Hu, Linhua; Wang, Chuandao; Lee, Sungsik Chemistry of Materials, Vol. 25, Issue 3 https://doi.org/10.1021/cm303303x	journal	January 2013
Vacant-Site Octahedral Tilings on ${SrTiO}_{3}$ (001), the $(\sqrt{13} \times \sqrt{13}) R 33.7 °$ Surface, and Related Structures Kienzle, D. M.; Becerra-Toledo, A. E.; Marks, L. D. Physical Review Letters, Vol. 106, Issue 17 https://doi.org/10.1103/PhysRevLett.106.176102	journal	April 2011
Hydrothermal synthesis of perovskite materials: Thermodynamic modeling and experimental verification Lencka, Malgorzata M.; Riman, Richard E. Ferroelectrics, Vol. 151, Issue 1 https://doi.org/10.1080/00150199408244737	journal	January 1994
Quasi-ideal strontium titanate crystal surfaces through formation of strontium hydroxide Koster, Gertjan; Kropman, Boike L.; Rijnders, Guus J. H. M. Applied Physics Letters, Vol. 73, Issue 20 https://doi.org/10.1063/1.122630	journal	November 1998

Cited By (1)

Upcycling Single-Use Polyethylene into High-Quality Liquid Products Celik, Gokhan; Kennedy, Robert M.; Hackler, Ryan A. ACS Central Science, Vol. 5, Issue 11 https://doi.org/10.1021/acscentsci.9b00722	journal	September 2019

Similar Records

All Roads Lead to TiO ₂ : TiO ₂ -Rich Surfaces of Barium and Strontium Titanate Prepared by Hydrothermal Synthesis

Journal Article · Tue Jan 30 00:00:00 EST 2018 · Chemistry of Materials · OSTI ID:1870995

Crosby, Lawrence A.; Chen, Bor-Rong; Kennedy, Robert M.; +4 more

The influences of mole composition of strontium (x) on properties of barium strontium titanate (Ba{sub 1−x}Sr{sub x}TiO{sub 3}) prepared by solid state reaction method

Journal Article · Mon Feb 08 00:00:00 EST 2016 · AIP Conference Proceedings · OSTI ID:1870995

Sandi, Dianisa Khoirum; Supriyanto, Agus; Iriani, Yofentina; +1 more

Simple oxalate precursor route for the preparation of barium-strontium titanate: Ba{sub 1-x}Sr{sub x}TiO{sub 3} powders

Journal Article · Sat Jan 15 00:00:00 EST 2005 · Materials Characterization · OSTI ID:1870995

Khollam, Y B; Deshpande, S B; Potdar, H S; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE

Title: All Roads Lead to TiO2: TiO2-Rich Surfaces of Barium and Strontium Titanate Prepared by Hydrothermal Synthesis

Citation Formats

References (52)

Cited By (1)

Similar Records

Related Subjects

Title: All Roads Lead to TiO₂: TiO₂-Rich Surfaces of Barium and Strontium Titanate Prepared by Hydrothermal Synthesis