LETTERS

PUBLISHED ONLINE: 10 AUGUST 2015 | DOI: 10.1038/NMAT4365

Negative-pressure-induced enhancement in a
freestanding ferroelectric
Jin Wang1,2*, Ben Wylie-van Eerd3, Tomas Sluka1, Cosmin Sandu1, Marco Cantoni4, Xian-Kui Wei1,5,
Alexander Kvasov1, Leo John McGilly1, Pascale Gemeiner6, Brahim Dkhil6, Alexander Tagantsev1,
Joe Trodahl3 and Nava Setter1*
Ferroelectrics are widespread in technology1 , being used in
electronics and communications2 , medical diagnostics and
industrial automation. However, extension of their operational
temperature range and useful properties is desired3–5 . Recent
developments have exploited ultrathin epitaxial films on
lattice-mismatched substrates, imposing tensile or compres-
sive biaxial strain, to enhance ferroelectric properties6,7 .
Much larger hydrostatic compression can be achieved by
diamond anvil cells8,9 , but hydrostatic tensile stress is regarded
as unachievable. Theory and ab initio treatments10 predict
enhanced properties for perovskite ferroelectrics under hydro-
static tensile stress. Here we report negative-pressure-driven
enhancement of the tetragonality, Curie temperature and
spontaneous polarization in freestanding PbTiO3 nanowires,
driven by stress that develops during transformation of
the material from a lower-density crystal structure to the
perovskite phase. This study suggests a simple route to obtain
negative pressure in other materials, potentially extending
their exploitable properties beyond their present levels.
Pressure influences the properties of ferroelectrics as a simple
consequence of elasto-electric coupling. Biaxial stress has been
achieved in films on lattice-mismatched substrates, resulting in
strongly enhanced properties, whereas negative pressure is consid-
ered practically unrealizable. However, when a material undergoes
a phase transformation from a low-density structure to a denser
one, the conditions of the transformation can dictate stretching of
the dense structure, resulting in a built-in negative pressure and its
corresponding property tuning. Here we implement this concept for
the prototypical ferroelectric PbTiO3 (PT). We produced freestand-
ing PbTiO3 particles under the appropriate conditions, studied the
structural fingerprints of the negative pressure, and found that these
particles had enhanced tetragonality, spontaneous polarization and
Curie temperature. The experimental work was complemented by
theory, ab initio modelling and numerical simulations.
PbTiO3 exists in two different crystalline structures, the common
ferroelectric perovskite and a body-centred tetragonal structure,
named the ‘PX’ phase11,12 . The unit-cell volume of the PX phase is
approximately nine times that of perovskite, whereas the number of
atoms in the unit cell is eight times that in perovskite. The remainder
of the volume is taken up by a longitudinal central pore along the
c-axis. Thus, the density of perovskite is 13% higher than that of
PX. In perovskites, oxygen octahedra are interconnected by their
corners (Fig. 1a), whereas in the PX phase, oxygen octahedra are
connected by both their corners and their edges (Fig. 1b). Therefore,
although their cation to oxygen ratio is identical, the conversion
from PX to perovskite requires the presence of extra oxygen, which is
absorbed at the beginning of the conversion and released again on
its completion13 . These two features, the difference in density and
the oxygen required for the phase conversion, provide the condition
for negative-pressure creation. When a body of PX phase is heated in
air, the perovskite phase first forms at the surface where the oxygen
is abundant; the released oxygen is gradually supplied to the inner
parts of the body and the conversion proceeds inwards. However,
whereas the outer part accommodates the shrinkage, the inner part,
when transforming, is bound by the rigid outer part, resulting in a
strong tensile stress in the core.
PbTiO3 nanowires were initially prepared in the PX phase
(see Methods and Supplementary Information). The perovskite
nanowires, with thicknesses ranging from 20 to 500 nm (Fig. 1c)
were obtained by annealing the PX nanowires in air at ∼540 ◦ C.
Nearly spherical pores with a typical diameter of around 10 nm
did not break their monocrystallinity (Supplementary Fig. 1a).
Annealed nanowires showed a tetragonal perovskite structure,
confirmed by X-ray diffraction (XRD) and Raman spectroscopy
(Supplementary Fig. 1b,c). The spontaneous polarization direction,
the c axis of the tetragonal perovskite cell, did not adopt any
specific orientation with respect to the nanowire geometry. Bending
occurred in some of the perovskite nanowires and 90◦ domains were
frequently found across the bent regions (Supplementary Fig. 1d).
The c/a ratio of individual nanowires was investigated by
high-resolution transmission electron microscopy (HR-TEM)
for nanowires thinner than 120 nm and selected area electron
diffraction (SAED) for thicker wires. Remarkably, in a small range
of diameters near 110 nm, there was an enormously enhanced
tetragonality (c/a − 1) up to ∼0.13 (Fig. 1d), almost doubling the
tetragonality from bulk PbTiO3 (ref. 14). Both thinner and thicker
wires exhibited c/a ratios similar to the bulk PbTiO3 value.
Polarization switching under an applied field confirmed
ferroelectricity of the wires. Supplementary Fig. 2 demonstrates
polarization switching with a scanning probe in a wire of diameter
∼105 nm. Off-centring of Ti with respect to the four nearest
Pb columns in a wire of 116 nm diameter was about twice the
bulk value as shown by the high-resolution high-angle annular
dark-field (HAADF) measurement, and a spontaneous polarization

1 CeramicsLaboratory, Swiss Federal Institute of Technology (EPFL), 1015 Lausanne, Switzerland. 2 Graduate School at Shenzhen, Tsinghua University,
518055 Shenzhen, China. 3 MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, PO Box 600,
Wellington 6140, New Zealand. 4 Interdisciplinary Centre for Electron Microscopy, Swiss Federal Institute of Technology (EPFL), 1015 Lausanne,
Switzerland. 5 Peter Grünberg Institute and Ernst Ruska Center for Microscopy and Spectroscopy with Electrons, Research Center Jülich, 52425 Jülich,
Germany. 6 Laboratoire Structures, Propriétés et Modélisation des Solides, CNRS-UMR8580, Ecole Centrale Paris, Grande Voie des Vignes,
92290 Châtenay-Malabry, France. *e-mail: wang.jin@sz.tsinghua.edu.cn; nava.setter@epfl.ch

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LETTERS NATURE MATERIALS DOI: 10.1038/NMAT4365

a b

b b

a a
c c

c d
1.14

1.12

1.10

c/a
1.08

1.06
c/a in bulk PT
1.04
200 nm 0 25 50 75 100 125 150 175 200
Thickness (nm)

Figure 1 | Crystalline structure and microstructure of the PbTiO3 nanowires. a, The crystalline structure of the perovskite phase viewed along the c axis.
b, The crystalline structure of the PX phase viewed along the c axis. c, Scanning electron microscopy image of perovskite PbTiO3 nanowires. d, c/a versus
the thickness of the nanowires. The error bars reflect uncertainty in determining c/a values and their spatial variation on given wires.

of ∼160 µC cm−2 was obtained according to the relative cationic
displacements (Supplementary Information and Supplementary
Fig. 3). The ferroelectric–paraelectric phase transition was
investigated in individual nanowires by temperature-dependent
Raman spectroscopy. Figure 2a shows spectra for three wires with
thicknesses of 650, 250 and 125 nm, at temperatures that span
the bulk Curie temperature of 490 ◦ C (refs 15–17). There are no
Raman active modes in the paraelectric cubic phase, and thus the
thickest wire loses all Raman bands above the bulk TC . However,
the signal from the ferroelectric tetragonal phase persists to higher
temperatures in thinner wires, and is still clearly seen in the 125 nm
nanowire at 600 ◦ C in the top panel of Fig. 2b.
The E(1TO) mode below 100 cm−1 provides a convenient
signature of the impending ferroelectric–paraelectric transition. In
bulk PbTiO3 it is a narrow line near 90 cm−1 at ambient temperature,
and it softens and broadens as TC is approached, disappearing after
reaching ∼55 cm−1 at TC (refs 15,16). Figure 2b shows its frequency
dependence on temperature, compared with single-crystal PbTiO3
(ref. 15). Data for the 650 nm nanowire agree with bulk PbTiO3 ,
whereas the 250 nm nanowire exhibits a frequency shifted by
∼40 ◦ C relative to bulk PbTiO3 , with TC ∼ 520–530 ◦ C. The 125 nm
nanowire with c/a ≈ 1.08 (Fig. 1d) has an enormously enhanced TC ,
with the signal seen well above 55 cm−1 in spectra at the 600 ◦ C limit
above which Pb starts to be lost.
An enhanced TC is corroborated by XRD on a multiple-wire
sample compared in Fig. 3a,b with standard bulk data14,18 . The
lattice parameter c and c/a are larger than in the bulk over the
whole measured temperature range, and the Curie temperature
is enhanced by ∼40 ◦ C. As shown in Supplementary Fig. 4, the
volume-weighted average diameter of the wires is 220–270 nm,
bringing TC enhancement into agreement with that measured on the
250 nm single wire. The enhancement is stable with time: samples
showed the same increased tetragonality after having been stored
for more than two years.
It is untenable that the enhancements are related to a purely size
effect, which can appear only on a much shorter length scale19–22 .
On the other hand, the expanded unit-cell volume relative to bulk
PT shown in Fig. 3a seems to be a fingerprint of tensile stress; indeed,
negative pressure provides a natural scenario in which the entire
data set is understood. Within the Landau–Ginzburg–Devonshire
(LGD) phenomenological description, the effect of the hydrostatic
stress on tetragonality and the shift of Curie temperature 1TC (see
Methods and Supplementary Information) are plotted in Fig. 3c.
The measured 1TC of 40 ◦ C in the 250 nm wire and the multiple-
wire samples corresponds to a hydrostatic tensile stress ∼0.4 GPa,
which agrees also with the tetragonality (c/a − 1 = 0.07) determined
by multiple-wire XRD. Similar agreement is found near 2 GPa for
the enhanced tetragonality (c/a − 1 = 0.08, Fig. 1d) and Curie
temperature (1TC > 100 ◦ C, Fig. 2b) in 125 nm wires.
Temperature-dependent lattice parameters measured for the
multiple-wire sample also agree well with the predictions of the
LGD expansion (solid curves in Fig. 3a,b). Note that the only
input parameter is the hydrostatic stress σ , which is ∼0.4 GPa
as extracted from the measured shift of TC of this sample. It
is clear that the experimental data are in full agreement with a
negative-pressure scenario as determined by the semi-empirical
LGD description in these moderately stressed wires. The different
deformation characteristics under hydrostatic tension in the c and a
axes due to an anisotropic electrostriction effect are exactly observed
in the experimental data.

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NATURE MATERIALS DOI: 10.1038/NMAT4365 LETTERS
a b 90
600 °C
3 80

2 70 125 nm

1 60

0 90
500 °C
Raman intensity (a.u.)

3 80

Frequency (cm−1)
2 125 nm 70
250 nm
250 nm
1 60
650 nm

0 90
475 °C

3 80

2 70
650 nm

1 60

50
0 100 200 300 400 100 200 300 400 500 600
Frequency (cm−1) Temperature (°C)

Figure 2 | Curie temperature of single wires probed by Raman spectroscopy. a, Spectra on single wires of diameters 125, 250 and 650 nm, at
temperatures spanning the Curie temperature of bulk PT. The lowest frequency E(1TO) feature was followed to investigate the diameter-dependent TC .
The occasional peaks around 40–50 cm−1 are substrate lines. b, The frequency of the lowest E(1TO) line plotted versus temperature for the three wires,
with the temperature dependence of the pure E(1TO) mode in bulk PT (ref. 15; red dashed lines) for comparison. The uncertainty bars marked are based on
several spectra on the same wire at fixed T as well as the uncertainties associated with fitting lines on a background that rises towards low frequency.

The maximal measured tetragonality, (c/a = 1.130 in the 115 nm
wire versus 1.065 at zero pressure), however, cannot be reconciled
with the results of the LGD expansion; it extends into the region
above 2 GPa which is certain to violate the LGD linear stress–
strain curve in Fig. 3c. Thus, to understand these very highly
stressed wires we appeal to the ab initio results10 . The blue nonlinear
curve in Fig. 3c is the result of that calculation, shifted by 0.36 to
align it with the experimental zero-pressure tetragonality14 , as local-
density approximation (LDA) calculations are known to give an
underestimated tetragonality in PbTiO3 (ref. 10). The tensile stress
corresponding to c/a = 1.13 is ≈4.5 GPa, at the foot of the ab initio
nonlinearity. As ab initio calculations of the dielectric permittivity
of PT show no significant variation of the dielectric permittivity as
a function of negative pressure (see Methods and Supplementary
Fig. 5), the lattice softness and the ferroelectricity of PT are expected
to be maintained beyond the nonlinear regime of the negative-
pressure effect.
The data above clearly indicate that the wires are under strong
hydrostatic tensile stress; we now demonstrate that such a negative-
pressure build-up is signalled also by both the nanopore formation
and the cross-sectional deformation of the wires. Turning first to
the distribution of approximately spherical voids shown in Fig. 4a–c,
there is a clear signature that the cores of the wires need to
accommodate a volume deficit. In particular, the image of a 115 nm
nanowire, with a c/a about 1.13, shows a remarkable density of
∼10 nm voids separated by about two to three times their diameter.
The voids account for less than 10% of the net 13% deficit, and the
remaining few per cent is provided by tensile stress in the range
of a few GPa. These cavitation voids are formed by a strongly
tensile isotropic component of the stress tensor during the PX to
perovskite transformation23–25 . An analogous situation is found in
the solidification of glasses, where cavitation occurs, although at
much larger scales26 . In that case the phase front proceeds from
the surface inwards, and the outermost regions form a rigid shell
which then prevents the core from collapse. When the phase front
propagates further inwards, large negative pressure is built up,
resulting in cavitation—that is, the appearance of voids, or even
fractures26 . A similar transformation from the surface inwards is also
a feature of the present system, because the transformation from
the PX phase to the perovskite phase cannot proceed without the
assistance of catalytic oxygen13 .
Traces of a different phase transformation history in small and
large diameters can be seen in the characteristic shapes of wires in
the cross-sectional TEM (Supplementary Fig. 6). The square profile
in the PX phase12 transforms to circular in the thinnest wires. At the
other extreme, for larger wires, we find either a large central void
or cracks (Supplementary Fig. 7). These larger wires retain much of
their square cross-section, and many show inward bowing of the flat
surface, which can no longer maintain the inner tensile stress. Such
convex bowing, the first step of failure, is already seen in wires within
the band of maximal stress, as shown in Fig. 4d.
To obtain a quantitative view, the negative pressure build-up is
simulated by a plane-strain elasto-plastic model (see Supplementary
Information for details) which considers 13% volume shrinkage at
a defined phase transition. The simulation (Fig. 4e) confirms that
the negative pressure can result solely from the volume shrinkage

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LETTERS NATURE MATERIALS DOI: 10.1038/NMAT4365

a 4.20 b 1.07

1.06
4.15

1.05
4.10
Lattice parameter (Å)

1.04
c axis of nanowires
4.05
a axis of nanowires
1.03

c/a
c axis of bulk (work of ref. 18) Nanowires
4.00 Bulk (work of ref. 18)
a axis of bulk (work of ref. 18) 1.02
Simulated
Simulated c axis
3.95
Simulated a axis 1.01

3.90 1.00

3.85 0.99
0 150 300 450 600 0 150 300 450 600
Temperature (°C) Temperature (°C)

c 1.35 700

1.30 600

1.25 500

1.20 400

ΔTC (°C)
c/a

1.15 300

1.10 200

1.05 100

1.00 0
0 1 2 3 4 5 6 7 8
Hydrostatic tensile stress (GPa)

Figure 3 | Temperature-dependent lattice parameters and tetragonality of the multiple-wire sample and predicted effect of hydrostatic tensile stress by
LGD phenomenology and first-principles calculations. a,b, Temperature dependence of lattice constants (a) and c/a (b) of the multiple-wire sample
compared with the bulk (the powder data from ref. 18 is used as the reference for bulk PbTiO3 , as the temperature dependence of lattice parameters
measured on PbTiO3 single-crystal13 is in good agreement with that measured on PbTiO3 bulk powders18 ). The simulated lattice constants and c/a of PT
under 0.4 GPa hydrostatic tensile stress are also included (see the text for further discussions). c, TC (black curve) and c/a at room temperature (red curve)
under hydrostatic tensile stress predicted by the LGD theory. c/a of PbTiO3 under hydrostatic tensile stress simulated by first-principles calculations (blue
curve, reconstructed according to the data in ref. 10 and shifted up to fit the measured c/a value of bulk PT at atmospheric pressure). The dashed parts
above 2 GPa in the LGD results are considered less reliable owing to the limited length of the expansion series used.

progressing from the surface inwards (Supplementary Fig. 8) and
that the key difference between individual nanowires is the ratio
of their diameter to the phase-boundary width. In thicker wires,
the progressing shrinkage develops larger local stresses and plastic
deformation, and the phase-boundary region occupies a smaller
volume fraction than in thinner wires. As a result, the simulated
built-in negative pressure grows with the wire diameter (Supple-
mentary Fig. 9), inducing also enhancement of the average c/a ratio
(Supplementary Fig. 10). The negative pressure in real wires cannot
grow without limit, leading to central pore formation and wire
splitting at specific stress thresholds, and the corresponding sharp
drop of c/a back to the normal bulk value (Fig. 1d).
In summary, we have reported the preparation of PbTiO3
nanowires formed by oxygen-mediated transformation from the
PX phase, which has a 13% larger specific volume than the
final ferroelectric perovskite phase. The wires with diameters of
∼100–125 nm show strongly enhanced tetragonality, spontaneous
polarization and Curie temperature, in accordance with ab initio
modelling and semi-empirical LGD theory for tensile stress of a
few GPa. The negative-pressure scenario is further signalled by the
appearance of ∼10 nm cavitation voids seen in TEM images of the
wires. Negative pressure is developed in the wire interiors as the
transformation front migrates inwards. It is technically important
that effective hydrostatic tensile stress is created in freestanding
nanowires. The technique is not limited to lead titanate, but can
develop in any transformation from a low- to high-density phase
that proceeds inwards from the surface. The PX to perovskite
transformation is possible also in other widely used ferroelectrics;
a similar approach might also be applied to a large number of
other materials with controlled transformations: for example, from
pyrochlore phases (such as Na2 Nb2 O6 ) to the denser perovskite
phase. Amorphous phases of many useful oxides are typically some
10–30% less dense than their corresponding crystalline phases27 ,
therefore extension to materials useful in diverse functionalities
might be reached. Negative pressure seems to be a feasible way to
modify materials and to extend their exploitable properties.

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NATURE MATERIALS DOI: 10.1038/NMAT4365
a b
D = 20 nm
20 nm
d e
20 nm
Figure 4 | Pore profile at different wire thicknesses and simulation of the hydrostatic pressure during the PX–perovskite phase transition. a–c, TEM
images showing the pore distribution in the 20 nm (a), 35 nm (b) and 115 nm (c) nanowires. d, Cross-section of a 116-nm-thick nanowire. e, Simulated
distribution of hydrostatic pressure in a 100-nm-thick nanowire after transformation from PX to the perovskite phase.
Methods
Methods and any associated references are available in the online
version of the paper.
Received 5 May 2015; accepted 26 June 2015;
published online 10 August 2015
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Acknowledgements
The research leading to these results has received funding from the European Research
Council under the European Union’s Seventh Framework Programme
(FP7/2007-2013)/ERC grant agreement no. [268058]. Research within the MacDiarmid
Institute is supported under the New Zealand Centres of Research Excellence fund.
J. Wang acknowledges the National Natural Science Foundation of China (Grant
No. 51302143) for financial support. Additional financial support was received from the
989
LETTERS
Swiss National Science Foundation (Grant No. 200020_153177). We thank
K. Vaideeswaran for sample preparation using focused ion beam and A. Duncan for
nano-beam electron diffraction experiments using the JEOL 2200FS electron microscope.
Author contributions
J.W. prepared the samples and merged the theory/modelling with experimental results.
B.W.-v.E. and J.T. performed Raman spectroscopy on single wires. T.S. and A.T.
conducted the modelling. C.S., X.-K.W. and M.C. characterized the sample by TEM. A.K.
performed ab initio calculations advised by A.T. L.J.M. conducted piezoresponse
measurements on individual wires. P.G. and B.D. carried out XRD measurements. J.W.
and J.T. developed the concept of the paper. J.W., J.T. and N.S. wrote the manuscript with
990
NATURE MATERIALS DOI: 10.1038/NMAT4365
inputs from T.S. and A.T. N.S. was responsible for overall direction and coordination. All
authors contributed to the manuscript and the interpretation of the data.
Additional information
Supplementary information is available in the online version of the paper. Reprints and
permissions information is available online at www.nature.com/reprints.
Correspondence and requests for materials should be addressed to J.W. or N.S.
Competing financial interests
The authors declare no competing financial interests.
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NATURE MATERIALS DOI: 10.1038/NMAT4365
Methods
Wires used here were prepared initially as PX (ref. 11), with the same stoichiometry
as perovskite PT but a crystalline structure that has a reduced density (by 13%).
When annealed in air at 540 ◦ C for 30 min they transformed into conventional
perovskite PT. Raman spectroscopy was performed with a Horiba Jobin-Yvon
T64000 spectrometer, excited with the 514.5 nm line from an Ar+ ion laser.
Measurements were performed on single wires of 125, 250 and 650 nm diameter,
previously selected by scanning electron microscopy. The samples were supported
on sapphire substrates placed on the hearth of a Linkam variable-temperature
microscope stage capable of being heated to 600 ◦ C. The power
used was reduced to avoid heating the wire, and carefully checked to establish that
increasing it by factors of two did not affect the results. The temperature-dependent
XRD measurements on the multiple-wire sample were performed using
a high-resolution two-axis X-ray diffractometer in the Bragg–Brentano geometry
with Cu Kβ radiation (λ = 1.3922 Å). The {200}, {220} and {222} family peaks were
recorded in the temperature range between 25 ◦ C and 640 ◦ C in temperature steps
of 10 ◦ C. After correction of the zero shift, the lattice parameters in both tetragonal
and cubic phases were extracted. The local piezoelectric and ferroelectric
activity of the PT wires were examined by a piezoresponse force microscope
(Cypher, Asylum Research) with a Ti/Ir-coated tip (3 N m−1 in force constant). The
spontaneous polarization (PS ) in the d = 116 nm nanowire was estimated based
on a high-resolution HAADF image following the linear relationship between
PS and the relative displacements of the B-site cations in displacive ferroelectrics. In
LDG calculations, the coefficients of the free-energy expansion of PbTiO3 are taken
from ref. 18. Note that the LGD predictions are based on the classic expansion
series in ref. 18, where only lowest-order coupling between σ and P was taken into
NATURE MATERIALS | www.nature.com/naturematerials
LETTERS
account. As a result, they are not expected to give a good description of the effect
of the hydrostatic enhancement in the proximity of the critical region (above 2 GPa,
dashed lines in Fig. 3c) where, according to the ab initio results, an anomalous
variation of structural parameters occurs. The TEM cross-sectional specimens
were prepared using a focused ion beam system. The high-resolution STEM image
was obtained on a probe-corrected FEI Titan-80-300 microscope with an operating
voltage of 300 kV. Ab initio calculations were performed using the Quantum
ESPRESSO (QE) ab initio package to study the dielectric properties of perovskite PT
under negative pressure. For the structural full-relaxation calculations, the PWscf
code, which is a set of programs for electronic structure calculations within density
functional theory (DFT), was exploited. The PWscf calculations are made within
the generalized gradient approximation (GGA) with the Perdew–Burke–Ernzerhof
(PBE) exchange–correlation functional using the ultrasoft pseudopotential from
PSLibrary 0.3.1. An automatically generated uniform Monkhorst–Pack 10×10×10
grid of k-points was used, and the kinetic energy cutoff for wavefunctions is 80 Ry.
The atomic positions are allowed to relax until the forces on atoms are smaller than
10−5 Ry/bohr (0.3 meV A−1 ). The process of negative-pressure formation during
the structural phase transition from PX to the perovskite phase was simulated
with a two-dimensional numerical model of an elasto-plastic material whose
spontaneous strain is coupled (through a phase parameter) with the concentration
of diffusing catalytic oxygen. The simulation domain has a square shape of varying
size. The boundary conditions are set as stress-free with the influx of oxygen.
The phase change is defined at a specified oxygen concentration which induces the
change of spontaneous strain. The model was implemented in the finite-element
method software COMSOL 4.3a by modification of its standard packages. More
detailed descriptions on the methods can be found in Supplementary Information.