This article has been accepted for publication in a future issue of this journal, but has not been

fully edited. Content may change prior to final publication. Citation information: DOI 10.1109/TNANO.2016.2538798, IEEE
Transactions on Nanotechnology

Impact of Non-Linear Piezoelectricity on the

Piezotronic Effect of ZnO Nanowires
Rodolfo Araneo, Senior Member, IEEE, Fabiano Bini, Marialilia Pea, Andrea Notargiacomo, Antonio Rinaldi, and
Salvatore Celozzi Senior Member, IEEE

Abstract—ZnO is receiving a considerable attention for the de- bandgap (∼ 3.4 eV) with native n-type, high transparency, bio-
velopment of novel cost-effective nanostructures with outstanding compatibility, excellent chemical and thermal stability, large
functional properties for applications in electronics and energy. In exciton binding energy (∼ 60 meV), and room-temperature
this paper, we investigate the effects of the non-linear piezoelec-
tricity, that has been recently observed in ZnO nanostructures, on ferromagnetism. In addition, ZnO can be grown in many
the piezotronic effect of ZnO nanowires. We insert a physically- nanoscale forms [12] (it shows probably the richest variety
based model of the non-linear direct piezoelectric effect into of different nanostructures) without much effort and through
a fully-coupled thermo-mechanical-electric scheme to study the various well-established methods [13] such as vapor-liquid-
current-voltage characteristic of ZnO nanowires under a purely solid (VLS), electrodeposition, hydrothermal growth (HTG),
vertical compressive/tensile strain. Our results show for the first
time that the non-linear piezoelectricity deeply affects the current focused ion beam (FIB) machining, and sol-gel process.
transport processes inside the nanowire and the behavior of Recent observations confirmed the presence of giant size
devices for piezoelectric-piezotronic applications and provides effects at nanoscales where ZnO structures behave in different
remarkable insights into the underlying physics. ways from the conventional bulk samples [14], whose appli-
Index Terms—Nanowire, non-linear piezoelectricity, semicon- cations are limited by their extreme brittleness. This evidence,
ducting materials, zinc-oxide, current-voltage characteristic. along with the inherent properties of ZnO, has allowed the
achievement of various novel 1D nanostructures [15], [16] that
I. I NTRODUCTION overcome the limitations of the bulk material and have paved
new ways to exploit innovative device applications, some of
VER the past recent years, one-dimensional (1D) nano-
O structures, e.g., nanotubes [1], nanowires (NWs) [2],
nanobelts [3] and even nanosprings [4] have attracted a great
which are already under intense research investigation.
The considerable interest in ZnO is due to the opportunity to
use the mechanical strengthening effect at nanoscale to exploit
attention due to their potential applications in a broad range
the intrinsic piezoelectric and semiconductor properties. The
of high-technology innovative devices [5], ranging from light-
ZnO wurtzite crystal is able to produce a piezopotential under
emitting diodes [6], photodetectors [7], and photodiodes [8],
stress, useful for two purposes: either to supply a net current
to gas sensors and solar cells [9]. Generally speaking, 1D
(piezoelectric effect [5], [17]) or to control an external current
nanostructures are most attractive because of interesting in-
flowing through the ZnO material (piezotronic effect [18]).
herent properties that can improve the performance of devices
Existing piezoelectric and piezotronic nanodevices still
[10]: the ease of fabrication, low-temperature process, high
present subtleties that deserve theoretical insight and expla-
crystalline quality, high surface-to-volume ratio and good
nation [19], despite the impressive research efforts done in
carrier confinement are just some representative examples of
just a few years since earlier work [2]. The electro-mechanical
the excellent properties of 1D nanostructures.
characterization of piezoelectric nanostructures remains chal-
Up to now, in the design of novel 1D nanostructures, the
lenging because of inherently complex and multi-physics
interest in ZnO has increased drastically with respect to other
framework [20], [21], along with numerical schemes that
materials of the same wurtzite family, such as GaN, InN,
are not-trivial to resolve due to nonlinearities in fundamental
and CdS, because it is an attractive low-cost II-IV semicon-
equations and boundary conditions (e.g., Schottky contacts,
ductive material that has a wide range of outstanding func-
thermal boundary resistances [22]–[25]).
tional properties [11], that may depend on doping, including
Recently, it has been observed in ZnO nanofilms and NWs
semiconductivity, piezoelectricity, pyroelectricity, direct wide
that the non-linear piezoelectric effect can lead to predictions
R. Araneo and S. Celozzi are with the Electrical Engineering Division of in some cases opposite to those obtained using the widely used
DIAEE, University of Rome “Sapienza”, Rome, via Eudossiana, 18 - 00184 linear model [26]–[29]. Starting from a semiempirical method
Italy.
F. Bini is with the Mechanical and Aerospace Engineering Department – in which a physical model is used to represent the influence
DIMA, University of Rome “Sapienza”, Rome, via Eudossiana, 18 - 00184 of atomic displacement and atomic charge on the creation
Italy. of electrical dipoles in a wurzite crystal, the spontaneous
M. Pea and A. Notargiacomo are with the Institute of Photonics and
Nanotechnology – CNR, via Cineto Romano 42, 00156, Rome , Italy. polarization and second-order coefficients have been computed
A. Rinaldi is with the University of L’Aquila, International Research simultaneously in the same framework [30].
Center for Mathematics & Mechanics of Complex System (MEMOCS), via On the basis of this physical based model of non-linear
S. Pasquale, 04012, Cisterna di Latina (LT), Italy, and with ENEA, Research
Center Casaccia, via Anguillarese 301, Santa Maria di Galeria, 00123, Rome, piezoelectricity that we adopt here integrally, in this paper we
Italy. investigate the effects of the non-linear direct piezoelectricity

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on the piezotronic effect of ZnO nanowires (NWs) under a F F

pure axial tensile/compressive strain which is a stress condi- V- c o m p r e s s iv e V+
tion that occurs in most typical arrangements for piezotronic
devices. To resolve this issue we insert the non-linear model
of the piezoelectricity into a fully-coupled thermo-mechanical- V+ tensile V-
F F
electric scheme and we study the current-voltage (I-V) char-
acteristic of piezoelectric ZnO NWs.
Fig. 1. Set-up for the ZnO nanowire under compressive or tensile strain.
Our results show that considering the non-linear piezo-
electricity in the NW has a great impact on the theoreti-
cal predictions of the behavior of piezoelectric-piezotronic where σij is the stress tensor, Di is the electric displacement
devices. Remarkably, our physically based simulations can vector, ND+ − NA+ are the net ionized impurity concentrations
deliver unique insights into the device final behavior. of donors and acceptors, n and p are the free electron and hole
The remainder of the paper is structured as follows. Section concentrations in the conduction and valence band (q is the
II reports the theory and details of the physically-based model positive electric charge), Jn i and Jp i are the electron and hole
and briefly explain the numerical scheme that we used to solve current densities, Un = Gn − Rn and Up = Gp − Rp are the
it. Finally, Sec. III presents comprehensive comparisons be- net generation (G) – recombination (R) rates for the charge
tween the predictions of linear and non-linear piezoelectricity carriers, T is the temperature, qs i is the source thermal flux
giving valued insights into the underling physics. vector, and kij is the heat conduction tensor. The constitutive
relations for a linear piezoelectric material are [32]
II. T HEORY σij = Cijkl εkl − ekji Ek − βij θ (2a)
The considered set-up is reported in Fig. 1: it consists in Di = Pipiezo + κ0 κij Ej + γi θ (2b)
fixing (e.g., by means of a silver paste) the two ends of
parallel NWs on a flexible substrate which can be bent to where Cijkl is the elastic stiffness tensor, Pipiezo is the
generate an almost purely tensile/compressive strain on NWs, polarization vector in which the contribution of both linear
assuming that the substrate radius of curvature is much larger and non-linear piezoelectric effects are taken into account, βij
than the NW length. To model the thermo-electro-mechanical is the tensor of stress-temperature moduli, γi is the (primary)
behavior of the piezoelectric semiconductor NW, we refer pyroelectric coefficient vector, and κij is the relative dielectric
to the classical continuum approach that has been shown to tensor (κ0 is the vacuum permittivity). Furthermore, εij is the
give a successful description of many nanodevice in previous strain tensor, Ei is the electric field vector, and θ = (T − T0 )
works [17], [20], [31]. Our choice is motivated by mainly is the temperature deviation from the reference temperature T0
two reasons: the classical approach is based on the continuum assumed equal to 20o C.
modelling of the matter without the need for more complex Even though derived in the framework of a classical con-
physical methods, e.g., methods based on the Boltzmann tinuum matter theory, the set of fundamental equations (1)
transport equation (BTE) or atomic-level/molecular-dynamics and the set of constitutive relations (2) allow to account for
simulations, thus providing the desired response properties all relevant physical phenomena, i.e., the elastic behavior, the
in a way more suitable for engineering approach; it leads dielectric properties, the thermal conduction and the piezoelec-
to a system of fully coupled non-linear partial differential tric and pyroelectric effects, that becomes important for ZnO
equations that, despite their relatively simple structure, can be NWs where these effects are all coupled and must be properly
conveniently manipulated to account for several peculiarities treated to correctly compute the response of interest.
borrowing the key physical parameters from the results of In the following we highlight the main features of our mod-
more complex approaches such as the popular methods of elling approach, providing insights into the relevant physical
density-functional theory (DFT) and density-functional pertur- effects and discussing the main novelty introduced with respect
bation theory (DFPT). to our previous studies.

B. Non-linear piezoelectric effect

A. Theoretical model
In piezoelectric crystals, electrical polarization Pipiezo is
The mechanical elastic, electric voltage, current transport,
produced in the presence of stress σij . In a linear framework,
and thermal behavior of the piezoelectric NW are governed
the polarization vector can be described by using the piezo-
by Newton’s law, Poisson equation, the current continuity
electric strain coefficients eijk as Pipiezo,lin = eijk εjk . Due to
equations and the Fourier equation which read, respectively
crystal symmetry, in hexagonal ZnO wurtzite phase there are
[2], [20] (the index notation is here used for clarity)
only three independent piezoelectric strain coefficients, namely
σij,j = 0 (1a) e31 , e33 , and e15 . As a consequence, using Voigt notation for
( ) the aim of conciseness, the linear constitutive equations read
Di,i = q ND+ + p − NA+ − n (1b)
Jn i,i = −qUn (1c) P1piezo,lin = e15 ε5 (3a)
Jp i,i = +qUp (1d) P2piezo,lin = e15 ε4 (3b)
kij T,j = −qs i , (1e) P3piezo,lin = e31 (ε1 + ε2 ) + e33 ε3 . (3c)

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As evident from (3), electric dipoles are generated along TABLE I

the direction of growth due to mechanical strain components M ATERIAL PROPERTIES OF Z N O (VOIGT NOTATION IS USED )
perpendicular to the growth plane (and consequently parallel
to the c-axis) and parallel to the growth plane, whereas Coordinate index 11=22 12 13=23 33 44=55 66
polarization components in the growth plane are due only Cij [GPa] 209.7 121.1 105.1 210.9 42.47 44.3
to shear strains. Consequently, as explained analytically in κij 7.77 8.91
αij [10−6 K−1 ] 4.75 2.9
[14], under a pure tensile/compressive strain, the polarization γij
-12
z-component is expected to play a major role. [10−6 C/(m2 K)]
As reported in [29], [30], with large strain (this is the case of kij [W/(m K)] 18 18
interest since the ZnO NWs are capable of withstanding large Coordinate index 31=32 33 15=24 311 333 313
elastic deformations up to 15% without breaking) non linear eij [C/m2 ] -0.61 1.15 -0.45 3.98 -5.59 1.21
strain induced polarization can have a profound impact on the
expected performances of devices. In particular, for an accurate
model, it is necessary to account for second order quadratic
dicular to the plane, and the combination of both parallel and
terms in the strain containing parallel and perpendicular strain piezo
perpendicular strain. In addition, Psp is the spontaneous
components and for the spontaneous polarization.
polarization. The strongest non linearities are in the z direction,
Non-linear effects in the piezoelectric properties of semicon-
therefore it is legitimate to neglect the influence on non
ductors [27] have raised significant interest in the past decade.
linearity on e15 , which would couple to small strains.
Calculations of the second order piezoelectric coefficients
Bijklm (or Biην in Voigt notation) [33] have been performed
primarily using ab initio methods and density functional per- C. Pyroelectric effect
turbation theory. Various sets of parameters have been reported The change in electrical displacement Di induced by a
for both zincblende [28], [34]–[36] and wurtzite [26], [29], polarization Pipyro associated with the change in temperature
[30], [37], [38] semiconductors. The aforementioned reports θ along the c-axis is here modelled through the pyroelectric
all highlight the magnitude of the effects as being able to effect [42]. This is explained in more details as follows.
reverse the polarity in the material as predicted using only Firstly we account for the primary pyroelectric effect,
first order coefficients. In this work we rely on the simplified which directly stems from spontaneous polarization charges
model, where non-linearities arising from the shear strains ε4 , that appear as a consequence of a variation in temperature
ε5 and ε6 are neglected, as proposed in [30]. Such coefficients under constant strain in order to prevent thermal expansion or
are obtained using the semiempirical (but also based on ab contraction; the corresponding polarization vector is given by
initio calculated values) Harrison’s model, which had some
success in explaining experimental data in both zincblende Pipyro,I = γi θ . (5)
[39] and wurtzite III-N materials [40], [41], and which has Furthermore we also consider into the model the secondary
recently been applied to modelling of nanowires [26]. pyroelectric effect, which is the result of the piezoelectric
It should be observed that due to the pure axial nature of contribution originated by the elastic strains caused by re-
the solicitation mode of the NW considered in our model, the strained thermal expansion or contraction. The corresponding
shear effects can be neglected in the present study, and con- polarization vector can be expressed through the thermal stress
sequently the non-linearities arising from those. Furthermore, tensor βij = Clmij αlm , where αlm is the thermal expansion
for the same reason, as clearly stated in [29], we neglect the tensor, and the direct piezoelectric tensor eijk , as
second-order dependence of the polarization component in the
growth direction (P3piezo ) and the components on the growth Pipyro,II = eijk αjk θ . (6)
plane (P1piezo and P2piezo ) on the shear strain connected to the Here we neglect the ternary pyroelectric effect that orig-
linear piezoelectric coefficient e15 . Anyway, under different inates from a inhomogeneous temperature distribution that
solecitations, e.g., lateral bending, they could have a potential leads to polarization variation through the flexoelectric effect
impact on nanostructures. tensor fijkl because it is usually negligible in pyroelectrics and
Consequently, we express the constitutive equation for the ferroelectrics in comparison with the primary and secondary
piezoelectric polarization vector P piezo under a non-linear effects. Moreover, to the best of the authors’ knowledge, no
framework as usable experimental data have been found in literature to
P1piezo = P1piezo,lin (4a) precisely quantify this effect.

P2piezo = P2piezo,lin (4b)

( )2 D. Mechanical, dielectric and thermal properties
ε1 + ε2
P3piezo = P3piezo,lin + piezo
Psp + e311 Since the behavior of the hexagonal crystal of ZnO wurtzite
2 is isotropic on the basal plane, the elastic stiffness tensor Cijkl
ε1 + ε2 is here expressed as a 6 × 6 matrix [11] where only five
+ e333 ε23 + e313
ε3 , (4c)
2 independent elastic constants are present, i.e. C11 = C22 ,
where the subscripts 311, 333, and 313 refer, respectively, to C12 , C13 = C23 , C33 , and C44 = C55 , being C66 =
a double strain in the growth plane, a double strain perpen- (C11 − C12 ) /2. The dielectric relative permittivity tensor is

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COMPRESSION z TRACTION 0.01 [C/m2 ]. In our simulations, we assume the band-gap od

F=-f uz F=+f uz
ZnO Eg equal to 3.4 eV and constant although it has been
observed that the quantum confinement effect and doping can
σpiezo = P·un σpiezo = P·un change the band gap of NWs [46], [47], along with the applied
#1 _
_ #1 +

IDS
_ _ un
IDS
+
+ + un strain [48]. The fundamental study on these issues remains
open and is relevant for developing applications of ZnO NWs.
Metal Importantly, it should be noted that observed and predicted size
P3
#1 P3
Va Va effects on the relevant mechanical and piezoelectric parameters
+ + [14], [15] could seriously affect the performance of the device.
- -
IDS
+ ZnO
- III. R ESULTS AND D ISCUSSION
Va
#2
σpiezo
+
+ #2 _
_ The model of the NW under study is shown in Fig. 2: the
+ + _ _
length Lnw and radius Rnw of the NW are, respectively, 2.5
Metal
σpiezo = P·un un #2 σpiezo = P·un un
µm and 100 nm. The NW is assumed n-doped with uniform
donor concentration ND and interconnected by two gold metal
Fig. 2. NW under tensile/compressive strain ε and external bias voltage Va .
contacts at both ends. The c-axis of the NW is assumed to be
oriented along the z-axis and the dc applied bias voltage is
designated as Va with reference polarity as depicted in Fig. 2.
considered uniaxial with only two independent dielectric con-
stants, i.e., κ11 = κ22 and κ33 [43]. A. Linear model
The thermal properties of the NW have been simulated
Figs. 3 show the I-V characteristics under both positive and
through the thermal conductivity tensor kij and the thermal
negative polarities of the bias voltage Va obtained under the
stress tensor βij . We assume the expansion tensor to be uniax-
assumption of a linear piezoelectric effect, for different values
ial and completely described by two coefficients, one along the
of doping concentration ND . The room temperature is T =
c-axis and the other on the basal plane. In addition, we assume
300 K. The physics beneath the behaviour of the current has
that the thermal conductivity is a scalar quantity and for the
been widely explained in [20] and it is here reported for the
determination of its correct value we refer to studies conducted
sake of clarity.
directly on ZnO nanowires because it has been observed that
Under no strain, the conduction properties of the NW are
the measured thermal conductivity is reduced by more than
dominated by the reverse-biased junction that forms at the
one order of magnitude, compared with that of bulk ZnO [44].
source contact, that is the lower metal-semiconductor junction
#2 under positive polarity of the applied bias voltage Va and
E. Boundary conditions the upper junction #1 under reversed negative polarity. Ac-
Finally, under the thermionic emission theory of the current cording to the classical thermionic emission-diffusion theory,
conduction mechanism, we assume that there are two Schottky at low values of the applied bias voltage the current shows a
barriers at the metal-semiconductor junctions whose heights logarithmic dependence
√ on the fourth square of the voltage,
will be modulated by the polarization (piezoelectric and py- i.e., log IDS ∝ 4 Va . With increasing drain voltage, above the
roelectric) charges that appear at the end surfaces of the NW. so-called flat-band voltage VFB , the NW features a saturating
For the thermal problem, we assume that two Kapitza thermal I-Vcharacteristic because the space-charge effect occurs. The
contact resistance [45] are present across the interfaces: the current is dominated by the injected mobile carriers whose
Kapitza resistance assumes that the normal component of concentration is comparable to the ionized donor concentration
the heat flux is continuous across the interfaces, while the ND , and the current IDS shows a linear dependence on the
temperature undergoes a discontinuity which is proportional applied voltage Va , i.e., IDS ∝ Va . Since in the strain-free
to the normal component of the heat flux through an interface case the NW structure is symmetric from an electrical point
parameter, i.e., Q̇S,n = ζ (T − Text ), where ζ is the inverse of view, there I-Vcharacteristic is independent of the polarity
of the interface thermal resistance. of Va .
Applying a compressive/tensile strain, a piezoelectric po-
larization vector P3 occurs in the NW. Under a linear piezo-
F. Numerical scheme electricity assumption, since the dominant e33 coefficient is
To solve the system of equations we adopt a quasi-Fermi positive, the polarization vector P3 is negative/positive un-
formulation [20]: we use as independent variables the electric der compression/traction. Thus, negative/positive piezoelectric
potential Ψ, the mechanical displacement vector u, the tem- charges appear at the upper junction #1 (that is the source
perature T and the two Fermi potentials Φn and Φp . The set under negative polarity of Va ) and positive/negative piezo-
of equations (1) and (2) is strongly non-linear. The relevant electric charges appear at the bottom junction #2 (that is the
equations have been solved through a Finite Element Method source under positive polarity of Va ). The piezoelectric charges
with appropriate iterative non-linear solvers [20]. The relevant modify the Schottky barrier height (SBH) at the reversed-
parameters used in the simulations are reported in Table I. The biased source contact and therefore tune the current transport
piezo
spontaneous polarization Psp is assumed to be equal to - behavior of the NW: negative/positive charges at the source

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Strain[%]: ND=1015 [cm-3] ND=1016 [cm-3] ND=1017 [cm-3]

0.25 2.5 20
-1 3
0.2 -0.75 2 2 15
-0.5

Current [µA]
0.15 -0.25 1.5 1

0
0 10
1

Current [µA]
Current [µA]
Current [µA]

-1
0.1 0.25 5
0.5 0.5 -2

0.05 0.75 -3

1 0 -6 -4 -2 0 2 4
Voltage [V]
6
0
0
-0.5 -5
-0.05 -1
-10
-0.1 -1.5
-0.15 -2 -15
-0.2 -2.5 -20
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
Voltage [V] Voltage [V] Voltage [V]

(a) (b) (c)

Fig. 3. I-V characteristics of NW (length Lnw = 2.5 µm and radius Rnw = 100 nm) under different strains and with different doping concentrations ND
computed by means of the proposed numerical model under a linear piezoelectric assumption.

Strain[%]: ND=1015 [cm-3] ND=1016 [cm-3] ND=1017 [cm-3]

0.25 -1 2.5 20
3

0.2 -0.75 2 2
15
-0.5
Current [µA]

1
0.15 -0.25 1.5
0
0 10
1

Current [µA]
-1
Current [µA]
Current [µA]

0.1 0.25 -2 5
0.5 0.5
0.05 0.75 -3
-6 -4 -2 0 2 4 6
1 0 Voltage [V] 0
0
-0.5 -5
-0.05 -1
-10
-0.1 -1.5
-0.15 -2 -15
-0.2 -2.5 -20
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
Voltage [V] Voltage [V] Voltage [V]

(a) (b) (c)

Fig. 4. I-V characteristics of NW (length Lnw = 2.5 µm and radius Rnw = 100 nm) under different strains and with different doping concentrations ND
computed under a non-linear piezoelectric assumption.

increase/lower the SBH, thus reducing/increasing the current contribute to enhance or reduce the piezotronic effect, depend-
level under the same bias voltage in comparison with the ing on the bias voltage polarity and magnitudes. The two
strain-free case. effects play a synergic role and all the observed effects are
Importantly, the piezotronic effect is a polar effect, since mainly due to their joint contribution.
piezo
it is natively linked to the c-axis orientation through the At first we note that the spontaneous polarization Psp
crystal structure. Consequently under a positive polarity of the is negative-valued in the case of ZnO: this gives rise to
bias voltage Va , the current is reduced with a tensile strain equivalent piezoelectric charges of negative sign at the upper
and increased with a compressive strain and the behaviour is metal-semiconductor junction #1 and of positive sign at the
exactly opposite under reversed polarity (since the reversed- lower junction. Then, we observe that the second-order terms
biased source contact moves from junction #2 to junction contribute to the previous effect in a more complex role. From
#1), where the current transport is increased by a tensile eqs. (3) and (4) it should be noted that when we reverse the
strain and reduced by a compressive strain. Finally, under sign of the strain, i.e., we move from compression to tension,
the linear assumption, the current presents an odd symmetry the two linear terms of the polarization vector P3piezo change
with respect to the strain ε and to the bias voltage Va , i.e., sign (negative under compression and positive under tension)
I (Va , ε) = −I (−Va , −ε). while the three non-linear terms, beside the spontaneous
polarization, maintain the same sign, positive for the 311 term
B. Non-linear model and negative for the 333 and 313 terms. Hence these terms
add to and subtract from the linear terms depending on the
Figs. 4 show the I-V characteristics under both positive and
sign of the strain. In order to better understand this effect, we
negative polarities of the bias voltage Va obtained under the
rewrite eq. (4c) as
assumption of a non-linear piezoelectric effect. Non-linear
piezoelectricity affects the charge trasport behavior of the P3piezo = 2e31 ε∥ + e33 ε3 +
NW by means of two major factors: primarily a spontaneous piezo
piezo + Psp + e311 ε2∥ + e333 ε23 + e313 ε∥ ε3 , (7)
polarization term Psp appears that is not usually included
into the linear model, and successively the second-order terms where ε∥ is the strain in the growth plane. Introducing the

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Strain[%]:
-1 -0.25 0.50
-0.75 0 0.75 ND=1016 [cm-3] ND=1017 [cm-3]
0.08 -0.5 0.25 1 3
0.6
0.06 2
0.04 0.4
1
0.02 0.2 0

∆Ι [µA]
∆Ι [µA]
∆Ι [µA]

0 0 -1
-0.02 -0.2 -2
-0.04 -0.4 -3
-0.06 15 -3 -4
ND=10 [cm ] -0.6
-0.08 -5
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6
Voltage [V] Voltage [V] Voltage [V]

(a) (b) (c)

Fig. 5. Difference of the current under a tensile/compressive strain with respect to the case under no strain for different doping concentrations ND computed
under a linear (solid line) and non-linear (dotted line) piezoelectric assumption.

0.1 negative piezoelectric charges are located. This effect is clearly

Ppiezo,nl evident in Figs. 3 and 4 and it is always present since
0.05 it is independent of the applied strain, being due to the
non-linear piezoelectric contribution P piezo,nl . Clearly the
P3piezo [C/m2]

0 aforementioned odd symmetry of the current with respect to

Difference
linear 0 the strain and the bias voltage is now completely lost.
Ppiezo,nl
-0.05 Then, the non-linear polarization P piezo,nl substantially
-0.01
contributes to increase the SBH at contact #1 and to reduce
-0.1 non-linear -0.02 the SHB at contact #2, acting through the equivalent surface
piezoelectric charges placed at the interfaces. This moves the
-5 0 +5
-0.15 transition from the logarithmic dependence of the current IDS
-5 -4 -3 -2 -1 0 1 2 3 4 5
on the fourth square of the voltage to the linear dependence
Strain [%]
toward higher voltages for a positive polarity of the bias
Fig. 6. Trend of the linear and non-linear polarization component P3piezo voltage Va and toward smaller values for a negative polarity.
with respect to the tensile/compressive strain ε3 . Remarkably, this is evident in all the presented results in Figs.
4, but especially when the doping concentration ND is low.
Figs. 5 show the absolute current difference ∆I of the I-
Poisson’s ratio ν, eq. (7) can be recast in the following form
Vcharacteristic under a tensile/compressive strain with respect
P3piezo = (e33 − 2e31 ν) ε3 + to the case under no strain for different doping concentrations
( ) ND computed under the linear and non-linear piezoelectric
piezo
+ Psp + e333 − e313 ν + e311 ν 2 ε23 . (8)
assumptions. It should be observed how the piezotronic effect,
Hence, considering the magnitude of all the parameters as i.e., the effectiveness of the strain to tune the I-Vcharacteristic
piezo with respect to the no-strain case, is generally enhanced
in Table I and recalling that ν = 0.349 and Psp =
−0.01 [C/m ], it is possible to plot the trend of the polar-
2 for negative polarities and reduced for positive polarities,
ization vector P3piezo with respect to the tensile/compressive especially for high doping concentrations. This conclusion
strain ε3 as in Fig. 6 under linear or non-linear model. is always true, and actually it is enhanced if we consider
Observing Fig. 6, we note that when the non-linear piezo- the percentage variation of the current, since we previously
electricity is introduced, the polarization component P3piezo is observed a decrease/increase of the magnitude of the current
always shifted toward negative values by the joined contribu- flow for negative/positive polarities. This result is a third effect
tion of the spontaneous polarization and the three non-linear of the non-linear piezoelectricity and is manly due to the fact
terms are mainly dominated by the negative terms, i.e., e333 that, being the non-linear polarization component P piezo,nl
and e313 . This joined effect can be modeled by an equivalent always negative, it always reduces (increase) the SBH at
polarization vector P piezo,nl , accounting for the effect of the contact #2 (#1) that is revered-biased under positive (negative)
non linear piezoelectricity, always negative-valued. polarity of Va thus reducing (increasing) the modulating effect
Consequently, two main affects arise. The current flow is of the applied strain under positive (negative) polarity due to
increased under a positive bias voltage Va , since the SHB the increased (reduced) screening effect of the free electron
at the reversed-biased source junction #2 is reduced by the carriers near the metal junction. From a practical point of view,
positive piezoelectric charges produced by P piezo,nl , whereas this is a very important result of the non-linear piezoelectric
the current flow is reduced under opposite negative polarity model which is missing in the linear model. Obviously, our
of Va , since the source contact moves to junction #1 where explanation is based on first order physical observations: the

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Transactions on Nanotechnology

ND=1015 [cm-3] ND=1016 [cm-3] ND=1017 [cm-3]

100 60 10
80 T0 [K]
300 40 0
60 250
40 200 20
150 -10
20 0

∆Ι [%]
∆Ι [%]

∆Ι [%]
0 -20
-20 -20
-40 -30
-40
-60 -40
-60
-80
-100 -80 -50
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
Strain [%] Strain [%] Strain [%]

(a) (b) (c)

Fig. 7. Percentage variation of the current with respect to the case under no strain plotted versus strain for different room temperatures T0 and doping
concentrations ND computed under a linear (solid line) and non-linear (dotted line) piezoelectric assumption (Va = 6 V).

non-linear physical equations are much more complicated and In order to investigate the effect of temperature variations
the non-linear piezoelectricity plays a more complex role on the conduction properties of the NW, we report in Figs. 7
which depends on the magnitude of the bias voltage Va and the percentage variation of current rate I with respect to the
on the doping impurities ND . applied strain ε under a fixed external bias voltage Va = 6 V,
Finally the insets of Figs. 3(b) and 4(b) show the I-V char- at different room temperatures T0 , ranging from 150 K to 300
acteristics under ideal ohmic contacts in order to eliminate the K and for different doping concentrations ND . It should be
effect of the Schottky contacts that could dominate the physical noted that the piezotronic effect increases with the decrease
behaviour of the device. Remarkably, the effect of the non- of temperature (the free electron charges are subject to a
linear piezoelectricity is evident also under this assumption. frozen effect [31] which reduces their mobility) and with
the decreases of the doping concentration since the screening
effect of the piezoelectric charges is strictly depending on
C. Thermal effects the number of free carriers. Nevertheless, it is important to
As reported in [31] a change in room-temperature affects highlight that under non-linear piezoelectricity the dependance
all the physical properties of the NW in a number of ways. of the piezotronic effect on temperature is deeply reduced.
As described in the previous Section, our model accounts for We assumed both the piezoelectric coefficients of the linear
the temperature dependence of all the main processes (e.g., and non-linear model independent of temperature due to lack
free charges densities, intrinsic densities, ionized dopants, of knowledge about this topic. This indicates that at low
motilities, diffusivities, etc.) that affect the conduction mech- temperatures the non-linear polarization contribution P piezo,nl
anism through the NW, and, particulary, it accounts for the predominates over other mechanisms.
pyroelectric effect. At a given room temperature T0 , two main
effects originate form the thermal processes: two temperature IV. C ONCLUSIONS
drops appear across the Kapitza resistances at the metal
We have developed a combined thermo-electro-mechanical
contacts whose temperature is fixed and equal to T0 , and a
model to determine the behaviour of piezoelectric semiconduc-
parabolic-like temperature gradient along the length of the NW
tor NWs. In particular we included non-linear piezoelectric
is developed.
effects: the second-order terms play a significant role. We
Remarkably, the net result of the first effect, that is dominant
have shown that the absolute current difference ∆I of the
with respect to the second one that is negligible [31], is the
I-V characteristic under strain with respect to the case under
generation of equivalent pyroelectric charges that have the
no strain for different doping concentrations is dramatically
same sign of those generated by the non-linear polarization
different and asymmetric, with negative polarities favoured
contribution P piezo,nl . In fact, reminding that the equivalent
compared to positive ones. This is especially true at high
surface pyroelectric charge is given by σpyro = Ppyro · un ≃
doping concentrations. These results provide more insight on
γ33 θ, observing that the pyroelectric coefficient γ33 is negative
the nature of the piezotronic effect in strained NWs.
and that the temperature drops at the metal contacts are always
positive (the NW always increase its temperature with respect
to T0 under an electrical current, despite its sign), we can V. ACKNOWLEDGMENT
easily understand that a negative surface pyroelectric charge Funding for this research is provided through the Ital-
appears at the top contact #1 while a positive surface charge ian Ministry of Research and Education, grant “FIRB
appears at the bottom contact #2. Clearly, the pyroelectric ef- RBFR10VB42”. The authors would like to thank prof. Max A.
fect plays a role similar to that of the spontaneous polarization Migliorato – School of Electrical and Electronic Engineering,
and its effect is non-polar. University of Manchester, Manchester, UK – for valuable

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Transactions on Nanotechnology

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