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 Nanotechnology

Nanotechnology 32 (2020) 025202 (9pp) https://doi.org/10.1088/1361-6528/abb972

Non-linear nanoscale piezoresponse of

single ZnO nanowires affected by
piezotronic effect
Helena Lozano1,4,5, Gustau Catalán2,3, Jaume Esteve1, Neus Domingo2,4,5
and Gonzalo Murillo1,4
1
Instituto de Microelectrónica de Barcelona, Bellaterra 08193, Spain
2
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of
Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain
3
ICREA – Institució Catalana de Recerca i Estudis Avançats, 08010 Barcelona, Spain

E-mail: [email protected] and [email protected]

Received 16 July 2020, revised 31 August 2020

Accepted for publication 17 September 2020
Published 14 October 2020

Abstract
Zinc oxide (ZnO) nanowires (NWs) as semiconductor piezoelectric nanostructures have
emerged as material of interest for applications in energy harvesting, photonics, sensing,
biomedical science, actuators or spintronics. The expression for the piezoelectric properties in
semiconductor materials is concealed by the screening effect of the available carriers and the
piezotronic effect, leading to complex nanoscale piezoresponse signals. Here, we have
developed a metal–semiconductor–metal model to simulate the piezoresponse of single ZnO
NWs, demonstrating that the apparent non-linearity in the piezoelectric coefficient arises from
the asymmetry created by the forward and reversed biased Schottky barriers at the
semiconductor–metal junctions. By directly measuring the experimental I–V characteristics of
ZnO NWs with conductive atomic force microscope together with the piezoelectric vertical
coefficient by piezoresponse force microscopy, and comparing them with the numerical
calculations for our model, effective piezoelectric coefficients in the range
d33eff ∼ 8.6 pm V−1 –12.3 pm V−1 have been extracted for ZnO NWs. We have further
demonstrated via simulations the dependence between the effective piezoelectric coefficient
d33eff and the geometry and physical dimensions of the NW (radius to length ratio), revealing
that the higher d33eff is obtained for thin and long NWs due to the tensor nature proportionality
between electric fields and deformation in NW geometries. Moreover, the non-linearity of the
piezoresponse also leads to multiharmonic electromechanical response observed at the second
and higher harmonics that indeed is not restricted to piezoelectric semiconductor materials but
can be generalized to any type of asymmetric voltage drops on a piezoelectric structure as well
as leaky wide band-gap semiconductor ferroelectrics.

Supplementary material for this article is available online

Keywords: PFM, ZnO, nanowire, piezotronics, C-AFM, nanogenerator, piezoresponse

(Some figures may appear in colour only in the online journal)

4
These authors contributed equally
5
Institute for Bioengineering of Catalonia, Barcelona, 08028, Spain

1361-6528/20/025202+9$33.00 1 © 2020 IOP Publishing Ltd Printed in the UK

Nanotechnology 32 (2020) 025202 H Lozano et al

1. Introduction it is able to measure this piezoelectric coefficient in a single

nanostructure. In this work, we have developed a general
Scavenging of ambient mechanical energy for autonomous model to describe nanoscale piezoresponse in piezoelectric
applications is becoming a hot research topic (Harb 2011, semiconductors that deconvolutes the experimental effect-
Duque et al 2019, Torah et al 2018, Kim et al 2018a). Energy ive piezoelectric response from the semiconductor screen-
harvesting relies on a transduction force that converts the ing effect. Moreover, we show how this entanglement leads
ambient mechanical energy into electricity. This mechanical to experimental non-linear piezoresponse signals and we
energy can have different forms such as vibrations, random demonstrate the emergence of multifrequency nanoscale elec-
motions, noise, etc. The most common transduction methods tromechanical responses in the presence of Schottky barriers.
are: electrostatic, electromagnetic, triboelectric and piezoelec- Due to the dual nature of ZnO, acting as semiconductor
tric. A piezoelectric material has the peculiarity of creating and piezoelectric material, in 2007, prof. ZL Wang introduced
an inherent electric field when strained (direct piezoelectric the fundamental principle of piezotronics (Zhong and Wang
effect). Some examples of well-known piezoelectric materi- 2007, Wang 2010, 2012, Wang et al 2010). Piezotronic effect
als are AlN, PVF, PZT, ZnO or quartz (Lee et al 2012, Choi is based on the influence of the piezoelectric potential with
et al 2017, Kim et al 2018b). Among those, zinc oxide (ZnO) the electronic bands in the semiconductor, creating electronic
has a non-central symmetric wurtzite crystal structure and a components that can be triggered with strain. Also, the oppos-
hexagonal unit cell. This structure has polar surfaces that can ite effect can be found, where an external voltage applied to the
be described as a number of alternating planes composed of material can affect its electronic bands and therefore affecting
tetrahedrally coordinated O2− and Zn2+ ions, stacked alternat- the generated strain due to the piezoelectric effect. Here, we
ively along the c-axis as is shown in figure S1 (available online demonstrate that these dual properties of a ZnO nanostructure
at stacks.iop.org/NANO/32/025202/mmedia). The oppositely have to be taken into account because they directly affect the
charged ions produce positively charged (0001)-Zn and neg- piezoresponse at the nanoscale measured by PFM.
atively charged (0001)-O polar surfaces, resulting in a nor-
mal dipole moment and spontaneous polarization along the
c-axis as well as a divergence in surface energy. ZnO has 2. Methods
become very popular in material science over the last few years
because of its wide variety of nanostructures and its dual prop- ZnO can be grown by different bottom-up approaches such
erty of being both a semiconductor and piezoelectric mater- as vapor–liquid–solid, chemical vapor deposition or hydro-
ial (Özgür et al 2005, Janotti and Van De Walle 2009): it has thermal method. However, a crystalline substrate with a sim-
a wide band gap (∼3.37 eV), large exciton binding energy ilar lattice constant is the best choice to obtain aligned and
(∼60 mV), it is relatively biosafe and biocompatible (Stitz high-quality NWs (Vayssieres 2003, Jin et al 2005, Kwon et al
et al 2016) and it exhibits an abundant configuration of nano- 2012). Here, we use a hydrothermal method which is one
structures as nanowires (NWs) (Espinosa et al 2012), nano- of the most powerful low-cost, low-temperature and simple
belts, nanosheets or nanorings (Wang 2009). Thanks to these approaches to grow c-axis-aligned NWs. This method is based
properties, this material has numerous potential applications on an aqueous solution chemical reaction at low temperature
in energy harvesting, photonics, sensing, biomedical science, (<80 ◦ C) directly on the silicon substrate covered by a seed
actuators, spintronics and optoelectronics (Yang et al 2002, layer (Murillo et al 2016, 2017b). The height and diameter of
2012, Özgür et al 2005, Wang et al 2010, Wang 2012, Murillo the NWs is determined by the growth time, temperature and
et al 2017a, Kang et al 2019). One of the most useful nano- concentration. For the ZnO NW growth, a silicon wafer with a
structures that can be utilized to generate energy is the NW seed layer of evaporated gold with a chromium adhesion layer
(Xu et al 2010, Espinosa et al 2012). These nanostructures (50 nm Au/20 nm Cr) is commonly used to favor the nucle-
are commonly referred to as nanogenerators, which have the ation. Every chip is then placed floating face down inside a
advantage of being more flexible and less sensitive to fracture wide-mouth jar containing the aqueous solution consisting of
than generators based on thin films. It was already demon- zinc nitrate hexahydrate (Zn(NO3 )2− hexahydrate) and hexa-
strated that a single ZnO NW can generate a piezoelectric methylenetetramine [1:1] 5 mM each purchased from Sigma-
potential along it when strained. The generated energy output Aldrich. Subsequently, the pot is closed and introduced in an
by one NW in one discharge event is about 0.05 fJ, and the oven at 70 ◦ C for 16 h. A scheme of this process is shown in
output voltage on the load is around 8 mV, for a 5 nN force figure S2 and a more detailed description is presented in the
applied by an atomic force microscope (AFM) tip (Wang and supplementary information. Figure 1 shows scanning electron
Song 2006; Riaz et al 2011). microscopy (SEM) and AFM images of the ZnO NWs. As can
One of the main hindrances in the expression for the piezo- be seen, the gold activation method ensures a well orientation
electric properties in semiconductor materials is the screening and distribution of ZnO NW growth. The average height of the
effect of the available carriers, concealing any piezoelectric obtained NW is h = 1.2 ± 0.2 µm and the average radius is
voltage (Morozovska et al 2007). The entanglement between r = 0.9 ± 0.15 µm (Murillo et al 2017b).
conductivity and piezoelectricity conceals the determination PFM depicted in a scheme in figure 2(a) has become a
of net piezoelectric coefficients as measured by electromech- standard for imaging ferroelectric domain patterns and also for
anical sensing techniques such as piezoresponse force micro- studying the piezoelectricity of certain materials (Kalinin et al
scopy (PFM), which on the other hand, is an ideal tool since 2004). PFM is an extension of contact mode AFM technique

2
Nanotechnology 32 (2020) 025202 H Lozano et al

Figure 1. (a) and (b) SEM image of the ZnO NWs. (c) AFM 3D topography image of several ZnO NWs and (d) one single NW.

and it is based on the converse piezoelectric effect of the mater- AFM tip (Abdollahi et al 2019). In fact, piezoelectricity can
ial under test. A conductive AFM probe tip is used as a top also be found in semiconductor crystals with non-central sym-
electrode to simultaneously measure the mechanical response metry, especially those who have a wurtzite structure such as
when an electrical voltage is being applied to the sample sur- ZnO. One of the major issues when measuring piezoelectri-
face. Then, in response to the electrical stimulus, the sample city in semiconductors is that for an adequate charge separ-
locally expands or contracts linearly according to the material ation generated by piezoelectricity during an applied stress,
piezoelectric coefficient. Usually an ac voltage (Vac ) is used to free carriers must not be allowed to travel through the semicon-
excite the sample, because it allows the use of a lock-in amp- ductor (in our case ZnO NW), otherwise the generated electric
lifier to read-out the tiny motion generated by the converse field across the semiconductor will be partly neutralized. On
piezoelectric effect. In this case, if Vac is the voltage applied another hand, semiconductors under a voltage drop can indeed
by the tip and d33 is the piezoelectric coefficient in the z-axes, carry a current depending on the doping and the electrical con-
the amplitude of the vibration as measured by an AFM tip in nections or junctions. For the case of piezoelectric semicon-
the vertical direction is described by equation (1): ductors, when a voltage is applied, current can flow through
the NW reducing the effective electric field inside the nano-
APFM = d33 Vac (1) structure. Electronic characteristics of semiconductor materi-
als such as I–V curves can be measured by conductive AFM
3. Results and discussion (C-AFM) thanks to the operational amplifier located in the
tip holder that is used to measure the small currents passing
Following this relationship, it is possible to determine the through the tip-sample contact area (see supporting informa-
effective d33eff coefficient of a piezoelectric dielectric material tion for experimental details) (Wen et al 2019). In this sense,
by measuring the linear change in PFM amplitude as a func- the simultaneous determination of the current profile as a func-
tion of the applied Vac voltage magnitude. Most of the mater- tion of the applied voltage will allow us to stablish the effect-
ials that exhibit piezoelectricity are insulators for which the ive voltage drop at the semiconductor that will promote the net
applied voltage between the AFM probe tip and sample sub- effective electromechanical response.
strate is fixed and well known. However, still quantification of The current–voltage (I–V) characteristic of a semiconduct-
piezoelectric coefficients by PFM is still a controversial issue ing device depends on a range of parameters of the semicon-
due to several factors such as (i) the real distribution of electric ductor material, such as its resistivity, doping concentration
field through the sample, (ii) undesired crosstalk between the and carrier mobility, but in our case we will specially focus
tip and the sample due to electrostatic coupling, (iii) instru- on the dependence of the geometry and the electrical prop-
mental artifacts and (iv) possible flexoelectric effects due to erties of its contacts. From the electronic point of view, our
the presence of strain and electric field gradients around the system is composed by a gold seed layer, a ZnO NW and

3
Nanotechnology 32 (2020) 025202 H Lozano et al

equation (2): according to the:

[ ( ) ]
qVF VF
IF = I01 exp −1 + (2)
kT Rsh1

where
( )
qϕb1
I01 = A1 A∗ T2 exp − (3)
kT

In this case, ϕb1 is the barrier height at the zero bias, A∗ =

4πem∗ k2 /h3 is the Richardson constant, k is the Boltzmann
constant, T is the absolute temperature, m* is the hole effect-
ive mass, h is Planck’s constant, q is the magnitude of the elec-
tronic charge and A1 is the contact area. On the other hand, the
reverse current density of the Schottky diode results on:
[ ( ) ]
q∆ϕb VR
IR = I02 exp −1 + (4)
kT Rsh2

where
( )
∗ 2 qϕb2
I01 = A2 A T exp − (5)
kT

Figure 2. (a) Scheme of the PFM setup. (b) Schematic diagram of where, ϕb2 is the barrier height and A2 is the contact area for the
the equivalent circuit of the Pt/ZnO/Au corresponding to an M–S–M reverse-biased Schottky barrier and ∆ϕb is the barrier lower-
structure, where Rsh1 and Rsh2 are the shunt resistors associated with ing due to the maximum electric field strength, E0 . The Schot-
both Schottky contacts. VF is the voltage drop across the
forward-biased Schottky barrier, VR is the voltage drop across the
tky effect barrier lowering due to the image force is given by:
reversed-biased Schottky barrier and VSC is the voltage on the
semiconductor, this is, the ZnO NW. √
qE0
e∆ϕb = (6)
4πεS

a tip with a Pt coating (figure 2(a)) and can be described as and

a metal–semiconductor–metal (M–S–M) structure (Elhadidy √
et al 2012). This fact is essential to understand the piezore- 2qNA (VR + Vi2 − kT/q)
E0 = (7)
sponse signals in semiconductor piezoelectrics since an M– εS
S–M structure will show different I–V characteristics as a
function of the type of metal–semiconductor contacts: while where NA is the carrier density in the semiconductor and
Ohmic contacts lead to linear characteristics, the inclusion of ε is the semiconductor permittivity. The reverse current of
a Schottky contact will lead to a rectifying I–V curve (Panda ideal Schottky contacts should saturate at a very low value,
et al 2013, Lee et al 2016, Lord et al 2017). In this case, as independent of the applied voltage. However, there are sev-
shown in figure 2(b) we have modeled the ZnO NW embed- eral causes of deviation from this ideal behavior: tunneling
ded between two electrodes as two Schottky barriers head- through the barrier becomes the dominating component under
to-head in series with a resistor (RSC ) that originates from the reverse bias in low-dimensional systems while for semi-
the undepleted part of the semiconductor. When one applies conductor devices with a low carrier concentration working
a bias voltage to this structure, one of the Schottky contacts at room temperature, the lack of saturation of the reverse cur-
is forward biased and the other one is reverse biased, and rent could be also explained by the barrier lowering at the M–
thus the total I–V characteristic is neither linear nor rectifying, S interface. It is necessary to mention that the nature of the
but instead it becomes almost symmetric due to the resulting Schottky barrier in ZnO structures has also a relevant effect on
electric field dependence of the barrier height (Elhadidy et al the piezotronic applications of this material (Keil et al 2017,
2012). The current–voltage relationships of the three series Li et al 2017).
are: (i) forward-biased Schottky barrier (IF –VF ), (ii) semicon- Finally, assuming that the undepleted part of the semicon-
ductor/piezo material (ISC –VSC ) and (iii) reverse-biased Schot- ductor is homogeneous and has a constant resistance, RSC , the
tky barrier (IR —VR ) (‘image force’ effect) leading to a full ISC –VSC relationship for the semiconductor is simply:
voltage drop V = VF + VR + VSC (Elhadidy et al 2012).
In the framework of the thermionic emission theory, the IF – VSC
ISC = (8)
VF curve at the forward-biased Schottky junction is given by RSC

4
Nanotechnology 32 (2020) 025202 H Lozano et al

Table 1. List of parameters used in the simulations for the voltage

drop at the semiconductor.
Parameter Symbol Value

Work function of the platinum ΦPt 5.65 eV

Work function of the gold ΦAu 5.80 eV
Electron affinity of ZnO χZnO 3.70 eV
ZnO NW resistivity RZnO 60 MΩ
Electrical permittivity of ZnO εZnO 5.70
Diffusion potential at the contact Vi2 0.40 V

Figure 3(a) shows the characteristic I–V curve of a single

ZnO NW as measured by C-AFM using a Pt-coated tip as a
mobile top electrode. Since in our configuration the voltage
is applied to the sample, the I–V characteristics at the positive
voltages corresponds to the Pt–ZnO junction, while at the neg-
ative voltages is assigned to the Au–ZnO junction. Computer
simulations, using an ad-hoc MATLAB code, based on the
M–S–M model were performed to calculate the real voltage
drop at the semiconductor ZnO NW structure. First, the exper-
imental I–V curve is simulated considering the M–S–M struc-
ture and equations (2)–(9). The parameters used in the simu-
lations were initially taken from the literature and adjusted to
our model based on the right fitting to the experimental I–V
curves, and are listed in table 1. The fitting process was per-
formed by using an ad-hoc routine to minimize the minimum
square error. Figure 3(a) shows the simulated pseudo symmet-
rical total I–V curve resulting from our structure superimposed
to the experimental measurement. The obtained asymmetry
is due to the difference in the work function of the platinum
(ΦPt = 5.6 eV) and gold (ΦAu = 5.8 eV), non-identical area of
contacts (the ZnO NW–Au substrate contact area corresponds
to the NW diameter while the ZnO NW–PtIr5 tip contact area
is smaller than the tip radius), shunt resistances, pinning of
the Fermi energy levels by the surface states and the existence
Figure 3. (a) I–V curve of a single ZnO NW as measured by of the interfacial insulating layers at both electrode contacts.
C-AFM (red line) and simulated I–V curve for an M–S–M structure Notice that the simulation curves are in well agreement with
(black line) as explained in the text using parameters shown in the experimental measurements.
table 1. The breaking point is not the same due to the difference
between the Au–ZnO junction and the Pt–ZnO junction, producing Assuming an ideal sinusoidal function for the Vac voltage
the asymmetry in the I–V curve. The inset shows the scheme of the applied to the tip (green line in figure 3(b) inset), and consid-
C-AFM set up, where the voltage is applied to the bottom electrode. ering the I–V characteristics measured by C-AFM (as shown
(b) Transfer function of two different symmetric and asymmetric in figure 3(a)), the resulting simulated voltage along the piezo
functions (shown in the inset) into the frequency space, showing VSC is presented in figure 3(b) (inset, red line). As observed,
their contribution to different harmonics. For an ideal sinusoidal
function as used in excitation bias Vac , there is only a contribution the effective voltage drop in the NW is no longer symmetric
in the first harmonic (green line). Instead, for an asymmetric but shows a threshold value together with a strong asymmetry.
excitation voltage as that calculated for the semiconductor voltage This fact is very relevant to the interpretation of the piezore-
drop VSC using equations (2)–(9) (potential difference along the sponse signal since (i) this will lead to non-linear piezore-
ZnO NW), there is a relevant contribution to multiple higher sponse as a function of the applied voltage and (ii) it will
harmonics (green line).
originate electromechanical responses at the higher harmon-
ics of the excitation frequency leading to multiharmonic PFM
response. As opposite to an ideal piezoelectric response under
and since the current flowing through each part of the M–S– a symmetric applied voltage, where the electromechanical sig-
M structure is the same as for a steady current (Elhadidy et al nal is only in the first harmonic, the frequency response of the
2012), we have: signal shown in figure 3(b) will also show contributions into
higher harmonics of the signal. Beyond the present case for a
M–S–M structure, the multifrequency piezoresponse is indeed
I = IR = IF = ISC (9) a general phenomenon that can be found in any piezoelectric

5
Nanotechnology 32 (2020) 025202 H Lozano et al

Figure 4. (a) Simulated voltage amplitudes along the different parts of the M–S–M structure as a function of the excitation bias amplitude
Vac : forward-biased Schottky junction (VR —grey dotted line), reversed-biased Schottky junction (VF —black dash line) and semiconductor
ZnO NW (VSC —red line). The voltage drop along the piezoelectric material VSC is lower than the bias voltage Vac due to the current that
flows through the NW. (b) PFM amplitude signal as a function of the excitation bias: the black line shows an ideal d33 curve with a slope
corresponding to d33eff = 9.6 pm V−1 . Measured piezoresponse signal APFM (1 ω) plotted in green showing a non-linear behavior with
apparent lower slope together with a relevant multifrequency response as shown by the PFM signal at the second harmonic (2ω), plotted in
purple. From this measurement, the apparent effective piezoelectric coefficient d33eff would be lower than the theoretical d33 . However, the
red line shows the simulated piezoresponse signal APFM (1ω) taking a piezoelectric coefficient of d33eff = 9.6 pm V−1 and assuming the
M–S–M model, in full agreement with the experimental curve. (c) PFM amplitude signal measured on a NW covered by an insulating layer
of 5 nm of alumina. In this case, the sample shows a linear response and the corresponding fitting gives a value of d33eff = 4.5 pm V−1 . The
inset shows the new electronics configuration for the structure of Pt/Al2 O3 /ZnO/Au, which can be described as a capacitor included in series
between the forward Schottky barrier and the semiconductor, breaking the M–S–M structure.

material arising from the application of asymmetric excitation to an apparent lower than real value. In addition, a measurable
voltages e.g. due to the use of non-equivalent electrodes. PFM signal appears in the second harmonic.
In addition, the effective electromechanical signal in the The multiharmonic response for the PFM amplitude as a
first harmonic will be reduced by this effect. Due to the asym- function of Vac measured for ZnO NW is presented in fig-
metrical I–V curve and the modulated voltage applied in the ure 4(b). The effective piezoelectric coefficient has been cal-
NW, the real voltage drop at the NW is not linear. In order to culated by fitting the experimental data with the simulations
calculate the voltage distribution along the M–S–M structure giving a value of d33eff = 9.6 ± 2.5 pm V−1 . The variabil-
(VF , VR and VSC from figure 2(b)) and their variation with the ity on the experimental results is attributed to the tip dam-
applied voltage, the equations (2–9) are numerically solved. age, alteration of the surface states that may modify surface
The results are shown in figure 4(a), taking the parameters charge and carriers (Yang et al 2019) or the changes in the
presented in table 1. Figure 4(a) shows that, as the excitation ac contact area between the tip and the NW, and is in good
bias voltage magnitude (Vac ) increases, the voltage drop across agreement with previously reported results using similar tech-
the reversed-biased Schottky barrier (VR ) increases rapidly and niques (Tamvakos et al 2015, Su 2017, Fortunato et al 2018,
becomes dominating until the voltage on the semiconductor Lim et al 2018). This d33eff coefficient has been calculated
bulk (VSC ) becomes notable. At the same time, the voltage by assuming a capacitor like structure in which the elec-
drop across the forward-biased Schottky barrier (VF ), remains tric field can be taken as homogeneous. Still, this assump-
negligible. It is clear that the range in which the voltage drop tion is far from the real electric field lines around an AFM
across the reverse-biased Schottky barrier (VR ) is dominant tip, which is closer to a radial distribution. In the limitingb
depends on the value of the resistance of the semiconductor, in case of considering an electric field distribution as that cre-
this case, the ZnO NW (RZnONW ). As the VR increases, RZnONW ated by a punctual charge, the voltage drop along the sample
decreases and vice versa. At a large bias and in the case of a would differ by a factor of 2 with respect to the nominal
high value of RZnONW the voltage VR starts to saturate, while the one (Kalinin and Bonnell 2002, Stitz et al 2016). This leads
voltage VSC across the semiconductor bulk increases almost to an effective piezoelectric coefficient that would double
linearly. Also, VF starts to increase slowly. In this large bias the one calculated here, that can be taken as a lower limit
regime, the change of the voltage across the semiconductor value.
bulk is responsible for the change of the bias. Finally, in order to avoid the current flow through the NW
Because the generated piezoelectric displacement (APFM ) thus cancelling the Schottky barrier effect, an insulator layer
is linearly related to the voltage applied to the piezoelectric of 5 nm of alumina (Al2 O3 ) was deposited over the NWs by
material (VSC ) (equation 1), a PFM signal with two differen- atomic layer deposition. The presence of the alumina layer
tiated regions should also be expected. The PFM amplitude is changes the configuration of the system breaking the M–S–
simulated using equation (1) by substituting Vac by VSC . As can M structure by adding a capacitor that eliminates the behavior
be seen from figure 4(b), the real PFM signal in the first har- of the two Schottky confronted diodes. Figure 4(c) shows the
monic has a non-linear behavior, as expected from the effect- electronic configuration for this system and the measured PFM
ive voltage drop VSC at the semiconductor (figure 4(a)). The amplitude response as a function of the Vac for the ZnO NW
linear part of the response has a lower slope as compared to the under the alumina layer. In this case, the response recovers the
ideal signal obtained for a pure dielectric piezoelectric, leading linear behavior but the linear fitting gives a lower coefficient

6
Nanotechnology 32 (2020) 025202 H Lozano et al

Figure 5. Total deformation of a single ZnO NW under an applied voltage of 10 V due to the piezoelectric effect for (a) a ZnO NW of 5 µm
of height and 500 nm of radius and (b) a ZnO NW of 600 nm of height and 500 nm of radius. (c) 3D plot of the calculated effective
piezoelectric coefficient d33eff (color scale) as a function of the length (x-axis) and the radius (y-axis) of a ZnO NW. The calculation shows
that for thick and short NW the d33eff is lower than for thin and long NW.

of d33eff = 4.5 pm V−1 (lower slope), probably due to effect voltage, stays constant over a fixed radius to length ratio.
of the insulating layer. This evidences the fact that the piezoelectric effect is indeed
To conclude, we have analyzed the dependence between including the whole volume of the NW through the tensor
the effective piezoelectric coefficient d33eff and the geometry proportionality between deformation and applied field. The
(Kim et al 2012) and dimensions of the NW using the piezo- obtained experimental results of d33eff ∼ 9 pm V−1 for ZnO
electric module of COMSOL Multiphysics to simulate the NW of 1.2 µm of length and 900 nm of radius falls within the
piezoelectric response for different ZnO NWs dimensions. expected range.
The geometry of the simulated model is an hexagonal column
of 500 nm of radius and 5 µm and 600 nm of height
that represents the ZnO NW shown in figures 5(a) and (b) 4. Conclusion
respectively. The Au substrate is designed as a block of
2 µm × 2 µm × 0.6 µm at the bottom of the NW and at the top In summary, in this work we have developed a full elec-
of the NW a cylinder of 100 nm of height and 50 nm of radius tromechanical response model for piezoelectric semiconduct-
emulates the Pt tip. Following the experimental configuration, ors with asymmetric electrodes based on an M–S–M piezo-
the Au block is defined as a terminal and the tip as ground tronic structure, also suitable for leaky ferroelectrics that
in the COMSOL piezoelectric module. Figures 5(a) and (b) behave as wide band-gap semiconductors. We have demon-
show the total displacement of the NW due to the piezoelec- strated that the apparent non-linearity in the piezoelectric coef-
tric effect: after applying 10 V the NWs show a deformation of ficient is generated by (i) the asymmetry created by the Schot-
108 pm and 75 pm respectively. Notice that the total displace- tky barrier at the semiconductor–metal junctions and (ii) the
ment is higher for a long thin NW than for thick and short effective voltage drop at the ZnO NW due to partial screening
NW. To study the NW radius effect, we perform a sweep in of the electric field by the semiconductor carriers. Moreover,
the NWs dimensions. Figure 5(c) shows a 3D plot of the beha- this non-linearity leads also to multiharmonic electromech-
vior of the effective piezoelectric coefficient as the length and anical response generating a PFM signal at the second and
the radius of the NW is changed and the color range shows the higher harmonics. Multifrequency PFM response is indeed
piezoelectric coefficient. For thick and short NW, the d33eff is not restricted to piezoelectric semiconductor materials but is
lower than for thin and long NW and the obtained piezoelectric general phenomenon that can be found in any piezoelectric
coefficient values are in the range between 1 and 11 pm V−1 . material arising from the application of asymmetric excita-
The decrease of d33eff for thicker geometries can be explained tion voltages as those created by different top and bottom
taking into account two different effects: (i) the radial distri- electrodes materials. By directly measuring the experimental
bution of the electric field due to the small tip size as com- I–V characteristics of ZnO NWs with C-AFM together with
pared to the NW geometry is bigger for higher radius, increas- the piezoelectric vertical coefficient by PFM, and comparing
ing the divergence of the real electric field distribution from them with simulations, effective piezoelectric coefficients in
that of a parallel plate capacitor, leading to a lower effective the range d33eff ∼ 8.6 pm V−1 –12.3 pm V−1 have been extrac-
d33 coefficient corresponding to a deformation in the NW axis ted for ZnO NWs which perfectly match the simulations res-
direction; (ii) for bigger radius, there is stronger lateral con- ulting from the proposed theoretical model. Finally, a useful
strain that prevents vertical expansion of the samples around computational tool to predict the piezoresponse of semicon-
the point of application of the electrical field. Moreover, since ducting NWs measured by PFM has been generated, revealing
the piezoelectric coefficient is itself a tensor, one can observe the strong effect of tensor nature proportionality between elec-
that the sample deformation, after the application of a fixed tric fields and deformation in NW geometries, demonstrating

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Nanotechnology 32 (2020) 025202 H Lozano et al

the dependence of the piezoelectric coefficient with the radius Kang Z et al 2019 Interface engineering for modulation of charge
to length ratio. carrier behavior in ZnO photoelectrochemical water splitting
Adv. Funct. Mater. 29 1808032
Keil P et al 2017 Piezotronic effect at Schottky barrier of a
metal-ZnO single crystal interface J. Appl. Phys. 121 155701
Acknowledgments Kim D Y et al 2018a Floating buoy-based triboelectric
nanogenerator for an effective vibrational energy harvesting
Financial support was obtained under projects from the Span- from irregular and random water waves in wild sea Nano
ish Ministerio de Economía y Competitividad (MINECO) Energy 45 247–254
under project FIS2015-73932-JIN, H2020 ECSEL-JU under Kim H S, Lee D, Kim D, Kong D, Choi J, Lee M, Murillo G and
Jung J 2018b Dominant role of Young’s modulus for electric
EnSO project (Energy for Smart Objetcs) (Contract no. power generation in PVDF–BaTiO3 composite-based
692482) and La Caixa Foundation under the Junior Leader piezoelectric nanogenerator Nanomaterials 8 777
Retaining program (LCF/BQ/PR19/11700010). In addition, Kim S M et al 2012 Radially dependent effective piezoelectric
this work was partially funded by 2017-SGR-579 from the coefficient and enhanced piezoelectric potential due to
Generalitat de Catalunya. ICN2 is supported by the Severo geometrical stress confinement in ZnO nanowires/nanotubes
Appl. Phys. Lett. 101 13104
Ochoa program from Spanish MINECO (Grant Nos. SEV- Kwon B J et al 2012 Synthesis of vertical arrays of ultra long ZnO
2017-0706). nanowires on noncrystalline substrates Mater. Sci. Eng. B
177 132–9
Lee J A et al 2016 Schottky nanocontact of one-dimensional
Conflict of interest
semiconductor nanostructures probed by using conductive
atomic force microscopy Nanotechnology 27 425711
The authors declare no competing financial interest. Lee M et al 2012 A hybrid piezoelectric structure for wearable
nanogenerators Adv. Mater. 24 1759–64
Li Y et al 2017 Analysis on the piezotronic effect in a strained
ORCID iDs piezo-Schottky junction with AC impedance spectroscopy
Nano Energy 36 118–25
Helena Lozano  https://orcid.org/0000-0002-8609-003X Lim T et al 2018 Crystal growth and piezoelectric characterization
Gustau Catalán  https://orcid.org/0000-0003-0214-4828 of mechanically stable ZnO nanostructure arrays
CrystEngComm 20 5688–94
Jaume Esteve  https://orcid.org/0000-0001-9440-7984
Lord A M, Ramasse Q M, Kepaptsoglou D M, Periwal P, Ross F M
Neus Domingo  https://orcid.org/0000-0002-5229-6638 and Wilks S P 2017 Stability of Schottky and Ohmic Au
Gonzalo Murillo  https://orcid.org/0000-0002-0368-1900 nanocatalysts to ZnO nanowires Nano Lett. 17 6626–36
10.1021/acs.nanolett.7b02561
Morozovska A N et al 2007 Piezoresponse force spectroscopy of
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