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RESEARCH ARTICLE
Copyright © 2013 American Scientific Publishers
All rights reserved
Printed in the United States of America
Journal of
Nanoscience and Nanotechnology
Vol. 13, 2885–2891, 2013
Transparent Anodic TiO
2
Nanotube Arrays on
Plastic Substrates for Disposable Biosensors
and Flexible Electronics
Samira Farsinezhad
1
, Arash Mohammadpour
1
, Ashley N. Dalrymple
1
,
Jared Geisinger
1
, Piyush Kar
1
, Michael J. Brett
1 2
, and Karthik Shankar
1 ∗
1
Department of Electrical and Computer Engineering, University of Alberta, Edmonton, AB, T6G 2V4, Canada
2
National Institute for Nanotechnology, National Research Council, 11421 Saskatchewan Drive, Edmonton,
AB, T6G 2M9, Canada
Exploitation of anodically formed self-organized TiO
2
nanotube arrays in mass-manufactured, dis-
posable biosensors, rollable electrochromic displays and flexible large-area solar cells would greatly
benefit from integration with transparent and flexible polymeric substrates. Such integration requires
the vacuum deposition of a thin film of titanium on the desired substrate, which is then anodized in
suitable media to generate TiO
2
nanotube arrays. However the challenges associated with control
of Ti film morphology, nanotube array synthesis conditions, and film adhesion and transparency,
have necessitated the use of substrate heating during deposition to temperatures of at least 300
C
and as high as 500
C to generate highly ordered open-pore nanotube arrays, thus preventing the
use of polymeric substrates. We report on a film growth technique that exploits atomic peening
to achieve high quality transparent TiO
2
nanotube arrays with lengths up to 5.1 m at room tem-
perature on polyimide substrates without the need for substrate heating or substrate biasing or a
Kauffman ion source. The superior optical quality and uniformity of the nanotube arrays was evi-
denced by the high specular reflectivity and the smooth pattern of periodic interferometric fringes
in the transmission spectra of the nanotube arrays, from which the wavelength-dependent effec-
tive refractive index was extracted for the air-TiO
2
composite medium. A fluorescent immunoassay
biosensor constructed using 5.1 m-long transparent titania nanotube arrays (TTNAs) grown on
Kapton substrates detected human cardiac troponin I at a concentration of 0.1 g ml
-1
.
Keywords: Transparent, Metal Oxide, Anodization, Self-Organized, Thin Film Deposition,
Polymer Substrates, Atomic Peening, Troponin Biomarker Assay.
1. INTRODUCTION
The three major classes of porous nanomaterials that
are curently the subject of intense research activity are:
microporous metal-organic frameworks (MOFs), which
primarily consist of pore sizes < 2 nm,
1
mesoporous
materials with pore-sizes in the range 2–50 nm
2 3
and
nanoporous materials which consist of pores 20–200 nm
in size. Among nanoporous materials, anodically formed
self-organized TiO
2
nanotube arrays have an extremely
versatile application spectrum
4–6
ranging from biomedical
devices through electrochromic and photovoltaic devices
to catalysts, separation membranes and chemical sen-
sors, enabled by the following properties: a high surface
∗
Author to whom correspondence should be addressed.
area, ordered pore architecture, n-type semiconductive
behavior when crystallized, well-defined percolation path-
ways for charge carriers and tunability of the diameter,
7 8
tube-length, wall-thickness and effective refractive index
over a wide size range, and high refractive index. Specific
applications for titania nanotube arrays include stem-cell
differentiators,
9 10
drug-eluting osteogenic impants,
11
ultra-
sensitive immunoassays,
12 13
amperometric sensors,
14–16
biofiltration membranes,
17
electrochromic displays,
18 19
oxidative photocatalysts for the degradation of organic
contaminants,
20
reductive photocatalysts for conversion of
CO
2
into hydrocarbon fuels,
21 22
photoanodes for sunlight-
driven water splitting,
23 24
supercapacitor electrodes in
energy storage devices
25
and electron-collection scaffolds
for dye-sensitized and ordered bulk heterojunction solar
cells.
26–28
Several of the above mentioned applications rely
J. Nanosci. Nanotechnol. 2013, Vol. 13, No. 4 1533-4880/2013/13/2885/007 doi:10.1166/jnn.2013.7409 2885