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2010 Nanotechnology 21 335601

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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 21 (2010) 335601 (7pp) doi:10.1088/0957-4484/21/33/335601

Chemically synthesized metal–oxide–metal

segmented nanowires with high
ferroelectric response
Edward D Herderick1, Nicholas A Polomoff2 , Bryan D Huey2 and
Nitin P Padture1,3
1
Department of Materials Science and Engineering, Center for Emergent Materials, The Ohio
State University, Columbus, OH 43210, USA
2
Department of Chemical, Materials, and Biomolecular Engineering, Institute of Materials
Science, University of Connecticut, Storrs, CT 06269, USA

E-mail: [email protected]

Received 7 March 2010, in final form 5 July 2010

Published 26 July 2010
Online at stacks.iop.org/Nano/21/335601

Abstract
A chemical synthesis method is presented for the fabrication of high-definition segmented
metal–oxide–metal (MOM) nanowires in two different ferroelectric oxide systems:
Au–BaTiO3 –Au and Au–PbTiO3 –Au. This method entails electrodeposition of segmented
nanowires of Au–TiO2 –Au inside anodic aluminum oxide (AAO) templates, followed by
topotactic hydrothermal conversion of the TiO2 segments into BaTiO3 or PbTiO3 segments.
Two-terminal devices from individual MOM nanowires are fabricated, and their ferroelectric
properties are measured directly, without the aid of scanning probe microscopy (SPM) methods.
The MOM nanowire architecture provides high-quality end-on electrical contacts to the oxide
segments, and allows direct measurement of properties of nanoscale volume, strain-free oxide
segments. Unusually high ferroelectric responses, for chemically synthesized oxides, in these
MOM nanowires are reported, and are attributed to the lack of residual strain in the oxides. The
ability to measure directly the active properties of nanoscale volume, strain-free oxides afforded
by the MOM nanowire architecture has important implications for fundamental studies of not
only ferroelectric nanostructures but also nanostructures in the emerging field of multiferroics.

1. Introduction in particular piezoresponse force microscopy (PFM), is used

almost exclusively to measure the coupled properties of
There is growing interest in nanostructured ferroelectric
nanostructured ferroelectric oxides. In PFM, the substrate
oxides for use in multifunctional integrated nanoelectronics,
serves as the bottom electrode, and an atomic force microscope
primarily as nonvolatile memories, dielectrics, actuators,
(AFM) tip serves as both the top electrode and the detector,
and sensors [1–3]. Much of the research in this area
providing high-resolution domain contrast [12, 13] and
is focused on thin-film-like patterned nanostructures such
switching-dynamics information [14, 15]. However, there
as nanoislands [4, 5], nanotube/nanopillar arrays [6–10],
are several drawbacks in using PFM to measure ferroelectric
and nanodisc/nanoring arrays [11]. However, substrate-
properties [16, 17]: (i) localized substrate charging, (ii) the
induced residual strains can persist in the oxides, degrading
non-uniform, nonlinear electric field applied by the AFM tip,
their ferroelectric properties [1, 5]. Also, as dimensions
(iii) instabilities in induced polarization, and (iv) difficulty in
of the ferroelectric nanostructures continue to shrink,
correcting non-local interactions.
it becomes increasingly difficult to provide high-quality
top electrodes to individual nanofeatures for properties In order to eliminate substrate-induced residual strains
measurement. Therefore, scanning probe microscopy (SPM), in ferroelectric oxides, there have been several efforts in the
area of free-standing ferroelectric all-oxide nanowires, such as
3 Author to whom any correspondence should be addressed.
BaTiO3 [18–25], PbTiO3 [26], and Pb(Zrx Ti1−x )O3 [27–29].

0957-4484/10/335601+07$30.00 1 © 2010 IOP Publishing Ltd Printed in the UK & the USA
Nanotechnology 21 (2010) 335601 E D Herderick et al

Also, nanowire research is driven by the ‘bottom up’ paradigm are described elsewhere [35]. The anodic aluminum oxide
in nanoelectronics, where nanowires of diverse functionalities (AAO) templates (diameter 250–300 nm) used here were
can be synthesized in isolation and assembled together into obtained commercially (Anodisc, Whatman Inc., Florham
multifunctional, densely packed nanoelectronic integrated Park, NJ). The last and the most crucial step in this process
devices [30]. is the topotactic hydrothermal conversion. The Au–TiO2 –
While the majority of the ferroelectric nanowire research Au nanowires released from the templates were transferred
is focused on synthesis and characterization [20–23, 26, 28], to a Teflon™-lined stainless steel acid-digestion vessel (Parr
there have been a handful of reports on properties Instrument Company, Moline, IL) for hydrothermal synthesis
measurements of individual all-oxide ferroelectric nanowires treatment. About 70% of the 45 ml capacity of the vessel
[18, 19, 24, 27, 29, 31]. But all those measurements have been was filled with either 0.1 M Ba(OH)2 or 0.3 M Pb(NO3 )2
performed using SPM, which makes accurate quantification solutions, with 0.6 M KOH in CO2 -free deionized water. The
a challenge. Also, there is a lack of direct, quantitative vessel was heated in an oven at 200 ◦ C for 25 min or at
measurements of the ferroelectric properties of individual all- 220 ◦ C for 60 min, for Au–BaTiO3 –Au or Au–PbTiO3 –Au
oxide nanowires using lithographically defined two-electrode nanowires, respectively. Note that the hydrothermal processing
contacts, due to several important issues. First, high- temperature for Au–BaTiO3 –Au nanowires is above the Curie
quality contacts to oxides are notoriously difficult to prepare, temperature (TC ) for BaTiO3 of ∼120 ◦ C [38], while that
especially after the nanowires have been synthesized, as is for the Au–PbTiO3 –Au nanowires is below the PbTiO3 TC
necessary in common self-assembly approaches. Second, of ∼490 ◦ C [38]. The MOM nanowires were then cleaned
the separation between post-fabricated electrodes in the axial using deionized water, ethanol and HCl, and were subsequently
direction generally must be on the order of microns in concentrated by centrifuging. The MOM nanowire dispersion
order to minimize contamination effects near the contacts. in water was drop-cast onto oxidized-Si substrates (SiO2
Consequently, the microns long active length of all-oxide thickness 500 nm; University Wafer, Boston, MA), and heat-
nanowires can have very high resistances, and require treated at 500 ◦ C for 30 min in air.
untenably high electrical fields for measurements. Thus,
transport measurements of truly nanoscale active regions of all- 2.2. Characterization
oxide nanowires, radially and axially, require a new paradigm
As-synthesized MOM nanowires were observed in a scanning
in nanowire architecture.
electron microscope (SEM; Sirion, FEI, Hillsboro, OR)
In this context, a metal–oxide–metal (MOM) nanowire
equipped with field emission source, at 15 kV accelerating
architecture with nanoscale oxide segments [32–37] over-
voltage. Specimens for transmission electron microscopy
comes the aforementioned shortcomings, allowing direct
(TEM) were prepared by dispersing the MOM nanowires on
measurement of the ferroelectric properties of nanoscale
carbon-coated Cu grids, and observed either in a conventional
volume oxides that are strain free. MOM nanowires have been
TEM (CM-200, Philips, Eindhoven, The Netherlands) or a
successfully synthesized in simple binary oxide systems such
high-resolution TEM (Tecnai F20, FEI, Hillsboro, OR), both
as SnO2 [32], NiO [32, 33, 36, 37], and TiO2 [34, 35]. MOM
operated at 200 kV accelerating voltage.
nanowires can range from tens to hundreds of nanometers in
diameter, and have an oxide segment ranging from several
nanometers to microns, sandwiched axially between two 2.3. Device fabrication
noble-metal (e.g. Au) nanowires. Thus, the active nanoscale Prior to drop casting the nanowires on the oxidized-Si
dimension of the oxide segment is precisely defined within substrates, numerous rectangular contact pads (0.5 × 1 mm2 )
the as-synthesized nanowire, and not by the device geometry. of Ni-50 nm/Au-200 nm, with a 50 μm gap between adjacent
This approach provides high-quality, end-on electrical contacts pads, were deposited on the substrates using electron-beam
to nanoscale volume oxides directly, and also eliminates deposition combined with conventional photolithography. The
substrate-induced residual strain. MOM nanowires lying in gaps between adjacent contact pads
Here we report a template-based chemical method for were observed in the SEM mode of the focused ion beam
synthesizing novel, high-quality MOM nanowires in two (FIB) (NOVA 600 DB, FEI, Hillsboro, OR), and high-quality
different ternary ferroelectric oxide systems: Au–BaTiO3 – nanowires were selected for device fabrication. Electrical
Au and Au–PbTiO3 –Au. We also report results from direct connections between the contact pads and the Au end of the
measurements of the ferroelectric properties of these MOM individual MOM nanowires were made using the direct-write
nanowires, where unusually high ferroelectric responses, for procedure in the FIB (see, e.g., [39, 40]). Well-defined Pt
chemically synthesized oxides, are recorded. These are lines (∼300 nm wide, ∼700 nm thick) were deposited on both
attributed to the high-quality end-on contacts and the lack of sides of the MOM nanowires connecting the ends of the MOM
residual strains afforded by the MOM nanowire architecture. nanowires to the contact pads. A low Ga-ion beam current
density (∼4 pA nm−2 ) was used to minimize the extraneous
2. Experimental procedure ‘spatter’ outside the Pt lines. Also, the long Au nanowire
segments on either side of the oxide segments precluded any
2.1. Synthesis possibility of ‘spatter’ encroaching on the oxide segments. The
Figure 1 shows a flow chart of the multi-step process thicknesses of the oxide segments were measured using the
for synthesizing Au–BaTiO3 –Au and Au–PbTiO3 –Au metal– SEM, and were found to be ∼300 nm. The devices were
oxide–metal (MOM) nanowires. Steps (a)–(e) in figure 1 subsequently baked out at 150 ◦ C for 24 h in air.

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Nanotechnology 21 (2010) 335601 E D Herderick et al

Figure 1. Schematic diagram showing flow chart of the multi-step process for template-based chemical synthesis of Au–BaTiO3 –Au and
Au–PbTiO3 –Au nanowires.

2.4. Ferroelectric properties measurement 3. Results and discussion

The positive-up–negative-down (PUND) test [41] was used to The key to the synthesis of the Au–BaTiO3 –Au and Au–
measure polarization in the MOM nanowire devices at room PbTiO3 –Au metal–oxide–metal (MOM) nanowire process is
temperature in air. Macroscopic contacts to the Au pads were the topotactic (shape-preserving) hydrothermal conversion of
made using a probe station, connected to a function generator the amorphous TiO2 segment (figure 1(e)) to crystalline
(Model 33250A, Agilent Technologies, Santa Clara, CA). A BaTiO3 or PbTiO3 segment (figure 1(f)). This process is
square wave with a frequency of 10 kHz was used, with inspired by the synthesis of BaTiO3 [42] and (Ba, Sr)TiO3 [43]
ramp and dwell times for each pulse of 100 ns and 10 μs, vertical nanotubes arrays from anodic TiO2 templates.
respectively. The magnitude of the peak voltage was varied Hydrothermal synthesis of BaTiO3 and PbTiO3 is typically
from 0.5 to 4.0 V to vary the maximum applied field E max . carried out in highly basic conditions (pH > 13), and
The drive voltage was monitored and the current response at moderate temperatures (150–250 ◦ C) and pressures (1–
measured using an oscilloscope (Model DPO4140, Tektronix, 10 atm.) [44, 45]. At those high pH values the TiO2 has
Richardson, TX). The current response was then analyzed to virtually no solubility [45]. Therefore, Ba2+ or Pb2+ nutrients
extract the Pr polarization values. Briefly, in a PUND test, in the solution react with the amorphous TiO2 segments in situ,
the up pulse current is subtracted from the positive pulse and converting them to crystalline BaTiO3 or PbTiO3 , respectively,
similarly the down pulse current from the negative pulse. Once which are the stable phases under those conditions [46]. (It
the difference in current is established, the current is integrated was found that the amorphous nature of the TiO2 assists in
over time to give total measured charge. That charge profile rapid topotactic conversion [42, 43].) In other words, if TiO2
is then evaluated to extract the current due to polarization. were soluble at the hydrothermal conditions, then the structure
The polarization values for the positive and negative directions of the Au–TiO2 –Au precursor nanowires would be destroyed,
are averaged and the final P value at each electric field is resulting in just powder of BaTiO3 or PbTiO3 and bits of Au
calculated. nanowires.

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Nanotechnology 21 (2010) 335601 E D Herderick et al

Figure 2. (a) Bright-field TEM image of a Au–TiO2 –Au precursor Figure 4. (a) Bright-field TEM image of a Au–PbTiO3 –Au nanowire
nanowire and (b) corresponding SAEDP from the TiO2 segment. and (b) corresponding indexed SAEDP.
(From [35].)

Figure 5. SEM micrographs of (a) Au–BaTiO3 –Au and

(b) Au–PbTiO3 –Au nanowires.

shows a SAEDP from the oxide segment, confirming the

presence of polycrystalline BaTiO3 . Since the c/a ratio for
tetragonal BaTiO3 is low (1.01) [46], the SAEDP is not able to
discern between cubic or tetragonal phases of the BaTiO3 . But,
as will be shown later, ferroelectric behavior in the BaTiO3
segment confirms the tetragonal phase, as the cubic phase is
not ferroelectric. Figure 3(c) is a high-resolution TEM image
showing the sharp BaTiO3 /Au interface.
Figure 4(a) is a bright-field TEM image of a Au–PbTiO3 –
Au nanowire. The high definition of the heterostructure
Figure 3. (a) Bright-field TEM image of a Au–BaTiO3 –Au is also clear in this MOM nanowire. The oxide segment
nanowire, (b) corresponding indexed SAEDP from the BaTiO3 is ∼200 nm long, and is somewhat recessed diametrically
segment, and (c) high-resolution TEM image of the Au/BaTiO3 from the Au segments, possibly due to dissolution during
interface. hydrothermal synthesis. The SAEDP from the oxide segment
shown in figure 4(b) confirms polycrystalline PbTiO3 . Since
the c/a ratio for tetragonal PbTiO3 is higher (1.06) [47],
Figure 2(a) is a bright-field TEM image of a Au–TiO2 – the tetragonality in the PbTiO3 segment can be discerned in
Au precursor nanowire, and figure 2(b) is the corresponding the SAEDP. A c/a ratio of 1.05 estimated from the SAEDP
selected area electron diffraction pattern (SAEDP), from an compares well with the ideal c/a of 1.06.
earlier study [35]. The ‘halo’ in the SAEDP confirms the Figures 5(a) and (b) are SEM images showing represen-
amorphous nature of the TiO2 segment. Note the high tative Au–BaTiO3 –Au and Au–PbTiO3 –Au nanowires, respec-
definition of the segmented structure of this nanowire. tively, in their entirety. The MOM nanowires are ∼250 nm in
Figure 3(a) is a bright-field TEM image of a Au–BaTiO3 – diameter, and the Au segments are 3–8 μm in length. Unlike
Au nanowire, with a ∼300 nm long oxide segment. Note the template-free methods, the template-based chemical synthesis
preservation of the MOM heterostructure during hydrothermal method described here allows the production of a very large
treatment by comparing figures 2(a) and 3(a). Figure 3(b) number of nearly identical nanowires at a time.

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Nanotechnology 21 (2010) 335601 E D Herderick et al

Figure 6. SEM micrograph of an example of a single MOM nanowire (Au–PbTiO3 –Au) device showing Au contact pads to the extreme left
and right, and the FIB Pt lines connecting the Au contact pads to Au ends of the MOM nanowire. Two small square features at the Au pads
are extra Pt ‘tack welds’ to ensure good electrical contact. The substrate is oxidized Si.

bulk polycrystalline BaTiO3 ceramics [47] and single-crystal

BaTiO3 [38], respectively. In comparison, the maximum
reported Pr value for chemically synthesized polycrystalline
BaTiO3 thin films (1.5 μm thickness) on metal substrates is
very low, Pr ∼ 4 μC cm−2 at E max = 200 kV cm−1 [48],
demonstrating the benefits of the MOM nanowire approach.
The maximum Pr value for the Au–PbTiO3 –Au
nanowires is 82 μC cm−2 (at E max = 133 kV cm−1 ). This
is consistent with the more pronounced ferroelectric effect
in PbTiO3 relative to BaTiO3 . This value is lower than
that reported for bulk polycrystalline PbTiO3 of Pr =
114 μC cm−2 [47]. But the Pr for the Au–PbTiO3 –Au
nanowire reported here is much higher than the maximum Pr
reported for chemically synthesized polycrystalline PbTiO3
thin films (420 nm thickness) on metal substrates: Pr ∼
36 μC cm−2 at E max of 500 kV cm−1 [49].
Considering that the BaTiO3 and the PbTiO3 oxide
Figure 7. Remnant polarization (Pr ) as a function of maximum segments in the MOM nanowires are polycrystalline, and
applied electric field ( E max ) (defined in the inset) for individual that they are synthesized via a soft-solution chemical method,
Au–BaTiO3 –Au and Au–PbTiO3 –Au nanowires. the remnant polarization values achieved at such low applied
fields are unusually high. The Pr value of 82 μC cm−2 (at
E max = 133 kV cm−1 ) measured directly for the Au–PbTiO3 –
Figure 6 is an SEM micrograph showing an example of Au nanowire in this study rivals the Pr value of 76 μC cm−2
devices fabricated for measuring ferroelectric properties of (at E max = 250 kV cm−1 ) for single-crystal PbZr0.2 Ti0.8 O3
individual MOM nanowires. Macroscopic Au contact pads (PZT) continuous thin films (1 μm thick) deposited epitaxially
are shown on the extreme left and right in figure 6. Pt lines using pulsed laser deposition [5].
deposited by the focused ion beam (FIB) direct-write method Given the low temperatures (200–220 ◦ C) used in the
connect the Au segments of the MOM nanowire to Au pads on synthesis of the MOM nanowires, residual strain in the oxide
the substrate for external connections. segments due to the thermal-expansion mismatches between
Figure 7 shows ferroelectric responses measured from the oxides and the Au is expected to be negligible, a benefit
individual Au–BaTiO3 –Au and Au–PbTiO3 –Au nanowires, not afforded by most thin-film deposition techniques. More
using the widely implemented PUND test [41]. This test importantly, the situation in the MOM nanowire is entirely
is designed for quantitative ferroelectric measurements in different compared to the conventional thin films in terms of
circumstances where significant parasitic capacitances exist, built-in strain. For typical oxide films, significant strain can be
which is the case in the devices studied here due to the large sustained due to substrate constraints, as the lateral dimension
Au pads (figure 7). The PUND test works by subtracting of the substrate is several orders of magnitude greater than
the charge which flows for a switched device (i.e. due the film thicknesses [50]. In the MOM nanowire case, on the
to capacitance) from that which flows during switching other hand, the lateral dimension is comparable to the oxide
(representing both the switching current and the capacitance). segment thickness providing little constraint. Moreover, Au, a
However, this precludes mapping full polarization–field ( P – soft metal even in submicron free-standing structures [51], in
E ) hysteresis loops, but the PUND test provides an accurate the MOM nanowires is likely to relieve any strain that may be
measure of remnant polarization (Pr ) values. These values present. Also, the post-synthesis 500 ◦ C heat treatment is likely
are reported in figure 7 as a function of maximum applied to anneal out any strain. Note that during synthesis and heat
electric field ( E max ), as defined in the inset in figure 7. treatment, the MOM nanowires are not mechanically attached
The maximum Pr value for Au–BaTiO3 –Au nanowire to the substrate they are lying upon, and are considered to
is 46 μC cm−2 (at E max = 133 kV cm−1 ). This compares be free-standing. Lastly, partial dissolution of part of the
favorably with the Pr values of 50 and 52 μC cm−2 for oxide segment (figure 4(a)) is also likely to alleviate any

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Nanotechnology 21 (2010) 335601 E D Herderick et al

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