Abstract
A novel, low-temperature synthesis method for producing BaxSr(1−x)TiO3 (BST) thin films patterned in the form of nanotubes (“honeycomb”) on Ti substrates is reported. In this two-step method, the Ti substrate is first anodized to produce a surface layer (∼300 nm thickness) of amorphous titanium oxide nanotube (∼100 nm diameter) arrays. In the second step, the anodized substrate is subjected to hydrothermal treatment in aqueous Ba(OH)2 + Sr(OH)2 at 200 °C, where the nanotube arrays serve as templates for their topotactic (shape-preserving) hydrothermal conversion to polycrystalline BST nanotubes. A simple geometrical model is proposed to elucidate the mechanism of the hydrothermal growth of BST nanotubes. This opens the possibility of tailoring the titanium oxide nanotube arrays and of using various precursor solutions and their combinations in the hydrothermal bath to produce ordered, patterned thin-film structures of various Ti-containing ceramics. These could find use not only in a variety of electronic, optoelectronic, and sensor device applications but also in biomedical and catalysis applications, where patterned thin films are desirable.
Similar content being viewed by others
References
C.D.E. Lakeman and D.A. Payne: Sol-gel processing of electrical and magnetic ceramics. Mater. Chem. Phys. 38, 305 (1994).
O. Auciello and R. Ramesh: Electroceramic thin films. Part I: Processing. MRS Bull. 21(6), 21 (1996).
N. Setter and R. Waser: Electroceramic materials. Acta Mater. 48, 151 (2000).
Y. Luo, I. Szafraniak, N.D. Zakharov, V. Nagarajan, M. Steinhart, R.B. Wehrspohn, J.H. Wendorff, R. Ramesh, and M. Alexe: Nanoshell tubes of ferroelectric lead zirconate titanate and barium titanate. Appl. Phys. Lett. 83, 440 (2003).
R.D. Morrison, L. Ramsay, and J.F. Scott: High Aspect ratio piezoelectric strontium-bismuth-tantalate nanotubes. J. Phys.-Condens. Matter 15, L527 (2003).
V. Nagarajan, C.S. Ganpule, A. Stanishevsky, B.T. Liu, and R. Ramesh: Nanoscale phenomena in synthetic functional oxide heterostructures. Microsc. Microanal. 8, 333 (2002).
V. Nagarajan, A.L. Roytburd, A. Stanishevsky, S. Prasertchoung, T. Zhou, L. Chen, J. Melngailis, O. Auciello, and R. Ramesh: Dynamics of ferroelastic domains in ferroelectric thin films. Nat. Mater. 2, 43 (2003).
W.M. Moreau: Semiconductor Lithography: Principles and Materials (Plenum, New York, 1988).
C.S. Ganpule, A. Stanishevsky, Q. Su, S. Aggarwal, J. Melngailis, E. Williams, and R. Ramesh: Scaling of ferroelectric properties in thin films. Appl. Phys. Lett. 75, 409 (1999).
A.L. Roytburd, S.P. Alpay, V. Nagarajan, C.S. Ganpule, S. Aggarwal, E.D. Williams, and R. Ramesh: Measurement of internal stresses via the polarization in epitaxial ferroelectric thin films. Phys. Rev. Lett. 85, 190 (2000).
Y.N. Xia and G.M. Whitesides: Soft lithography. Ann. Rev. Mater. Sci. 28, 153 (1998).
D.A. Payne and P.G. Clem: Monolayer-mediated patterning of integrated electroceramics. J. Electroceram. 3, 163 (1999).
P.M. Moran and F.F. Lange: Microscale lithography via channel stamping: Relationships between capillarity, channel filling and debonding. Appl. Phys. Lett. 74, 1332 (1999).
N.P. Padture and X. Wei: Hyrothermal synthesis of thin films of barium titanate ceramic nanotubes at 200 °C. J. Am. Ceram. Soc. 86, 2215 (2003).
V. Zwilling, E. Darque-Ceretti, A. Boutry-Forveille, D. David, M.Y. Perrin, and M. Aucouturier: Structure and physicochemistry of anodic oxide films on titatnium and TA6V alloy. Surf. Interf. Anal. 27, 629 (1999).
D. Gong, C.A. Grimes, O.K. Varghese, W. Hu, R.S. Singh, Z. Chen, and E.C. Dickey: Titanium oxide nanotube arrays prepared by anodic oxidation. J. Mater. Res. 16, 3331 (2001).
D.E. Bornside, C.W. Macosko, and L.E. Scriven: On the modeling of spin coating. J. Imag. Technol. 13, 122 (1987).
R.K. Roeder and E.B. Slamovich: Stoichiometry control and phase selection in hydrothermally derived BaxSr(1−x)TiO3 powders. J. Am. Ceram. Soc. 82, 1665 (1999).
X. Wei and N.P. Padture: Hydrothermal synthesis of tetragonal BaxSr(1−x)TiO3 powders. J. Ceram. Proc. Res. 5, 175 (2004).
M.M. Lencka and R.E. Riman: Hydrothermal synthesis of perovskite materials: Thermodynamic modeling and experimental verification. Ferroelectrics 151, 159 (1994).
F. Jona, and G. Shirane: Ferroelectric Crystals (Dover Publications, New York, 1993).
A. Bendavid, P.J. Martin, and H. Takikawa: Deposition and modification of titanium dioxide thin films by filtered arc deposition. Thin Solid Films 360, 241 (2000).
K.H. Hellwege and A.M. Hellwege: Landolt-Bornstein New Series: Group III, Volume 16, Oxides (Springer-Verlag, New York, 1981), p. 64.
H. Masuda and K. Fakuda: Ordered metal nanohole arrays made by a two-step replication of honeycomb structures of anodic alumina. Science 268, 1466 (1995).
H. Masuda, H. Yamada, M. Satoh, and H. Asoh: Highly ordered nanochannel-array architecture in anodic alumina. Appl. Phys. Lett. 71, 2770 (1997).
A.P. Li, F. Muller, A. Birner, N. Kielsch, and U. Gosele: Hexagonal pore arrays with a 50–420 nm interpore distance formed by self-organization in anodic alumina. J. Appl. Phys. 84, 6023 (1998).
J. Li, C. Papadopoulos, and J.M. Xu: Highly-ordered carbon nanotube arrays for electronics applications. Appl. Phys. Lett. 75, 367 (1999).
T. Kokubo, F. Miyaji, H-M. Kim, and T. Nakamura: Spontaneous formation of bonelike apatite on chemically treated metals. J. Am. Ceram. Soc. 79, 1127 (1996).
Author information
Authors and Affiliations
Corresponding author
Additional information
This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/publications/jmr/policy.html.
Rights and permissions
About this article
Cite this article
Wei, X., Vasiliev, A.L. & Padture, N.P. Nanotubes patterned thin films of barium-strontium titanate. Journal of Materials Research 20, 2140–2147 (2005). https://doi.org/10.1557/JMR.2005.0264
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/JMR.2005.0264