NANO

LETTERS

Equilibrium Potential of Free Charge 2009

Vol. 9, No. 3
Carriers in a Bent Piezoelectric 1103-1110
Semiconductive Nanowire
Yifan Gao and Zhong Lin Wang*

School of Materials Science and Engineering, Georgia Institute of Technology,

Atlanta Georgia 30332-0245

Received November 23, 2008; Revised Manuscript Received December 31, 2008

ABSTRACT
We have investigated the behavior of free charge carriers in a bent piezoelectric semiconductive nanowire under thermodynamic equilibrium
conditions. For a laterally bent n-type ZnO nanowire, with the stretched side exhibiting positive piezoelectric potential and the compressed
side negative piezoelectric potential, the conduction band electrons tend to accumulate at the positive side. The positive side is thus partially
screened by free charge carriers while the negative side of the piezoelectric potential preserves as long as the donor concentration is not too
high. For a typical ZnO nanowire with diameter 50 nm, length 600 nm, donor concentration ND ) 1 × 1017 cm-3 under a bending force of
80 nN, the potential in the positive side is <0.05 V and is approximately -0.3 V at the negative side. The theoretical results support the
mechanism proposed for a piezoelectric nanogenerator. Degeneracy in the positive side of the nanowire is significant, but the temperature
dependence of the potential profile is weak for the temperature range of 100-400 K.

Introduction. Nanowires (NWs) and nanobelts made of of piezoelectricity in semiconductors, as one sees in nano-
wurtzite-structured compound semiconductors, such as ZnO generators and the nanopiezotronics.
and GaN,1,2 are piezoelectric. By use of the piezoelectricity Calculations based on the Lippman13 theory have been
of semiconductive ZnO NWs, nanoscale mechanical-electrical carried out for bent piezoelectric nanowires, with an analyti-
energy conversion devices known as the nanogenerators have cal solution for the electric potential derived. The Lippman
been demonstrated,3-7 in which the electric current in an theory can be used to describe bent piezoelectric nanowires
external circuit is driven by the piezoelectric potential created when the donor concentration is extremely low, so that the
by the bent ZnO NW.7 On the basis of the coupled behavior conductivity can be neglected. However, the as-grown ZnO
between piezoelectric and semiconducting properties, nanowires are typically n-type due to unavoidable point
piezotronic effect8 has been revealed, which utilizes the defects.14-20 For semiconductor materials with a significant
piezoelectric potential to modulate the carrier transport amount of free electrons, the Lippman theory cannot be
process in the NW. Examples of nanopiezotronics include directly applied, because the free charge carriers are able to
but are not limited to the piezoelectric field effect transistors,8
distribute all over the material. The statistics of electrons/
piezoelectric diodes,9 and piezotronic strain sensors.10 Al-
holes must be considered besides the phenomenological
though most of the nanogenerators and nanopiezotronics
thermodynamics. The main objective of this paper is to
devices are based on ZnO NWs and nanobelts, the demon-
present a macroscopic-statistical model of piezoelectricity
strated principle applies to a broad range of materials, such
in a laterally bent semiconductive nanowire by considering
as GaN, CdS, and possibly ZnS.
its moderate conductivity in a normal doping range. To be
Nanowires and nanobelts are natural cantilevers that can
specific, we will calculate the electric potential when the
be easily bent to create a large deformation. Although the
application of piezoelectricity in semiconductor devices has thermodynamic equilibrium among free charge carriers is
a long history in the GaN/AlGaN high electron mobility achieved. For applications that directly utilize the piezoelec-
transistors (HEMTs),11,12 the piezoelectric fields in traditional tric potential as the driving force to produce electric power,7
HEMTs are fixed as introduced by interface strain and remain such as the piezoelectric nanogenerators, the results could
“as is” once the heterojunctions are fabricated. In contrast, provide a more realistic picture for their operation mecha-
the mechanical flexibility of piezoelectric compound nanow- nism. For piezotronics21 devices which use the piezoelectric
ires provides a more versatile platform to utilize the physics potential to modulate the charge transport properties,10 the
results will be a good starting point to study the quasi-static
* Corresponding author, [email protected]. charge transport process. Although the calculations in this
10.1021/nl803547f CCC: $40.75  2009 American Chemical Society
Published on Web 02/03/2009
 It is well-known that when free electrons/holes are present
in a piezoelectric material, the carriers will redistribute due
to the electric field established by the polarization. One
famous application of such a redistribution effect is in the
GaN/AlGaN HEMTs, where electrons are accumulated at
the heterojunction to create a two-Dimensional Electron Gas
(2DEG).11 For piezoelectric nanowire applications,7,8 the
mechanical behavior is more complicated, but the physical
pictures are essentially the same. Instead of using a fully
coupled constitutive equation,13 we only write the mechanical
equilibrium and the direct piezoelectric effect:

{ σp ) cpqεq
Di ) eiqεq + κikEk
(1)

where σ is the stress tensor, ε is the strain, b

E is the electric
b is the electric displacement. κik is the dielectric
field, and D
constant, eiq is the piezoelectric constant, and cpq is the
mechanical stiffness tensor. The Voigt-Nye notation24 is
used. Substituting the second equation into Gauss’s law, we
get the equation for the electric field
Figure 1. Piezoelectric potential distribution across the center of a b ) ∂ (eiqεq + κikEk) ) Fe(b) ) ep - en + eND+ - eNA-
ZnO nanowire that is assumed to be an insulator. The coordinate ∇·D
∂xi
system used for the calculation is also defined. The wire is
approximated as a cylinder, with radius a and length l. The nanowire
(2)
is well-affixed on the substrate. The external force fy is exerted at where p is the hole concentration in the valance band, n is
the top, while the boundary traction due to fy is supposed to be the electron concentration in the conduction band, ND + is
uniform across the top surface. The red side is the positive side,
and the blue side is the negative side. The bottom reverse region is the ionized donor concentration, and NA- is the ionized
also plotted. acceptor concentration. Because the as-grown ZnO NWs are
usually n-typed, we adopt p ) NA- ) 0. By introducing
paper are conducted exclusively for n-type ZnO nanowires, b R ) ekqεqîk
D (3.1)
the methodology is directly applicable to any devices with
as the polarization due to piezoelectricity and
a similar design, as long as the building material is
piezoelectric and semiconductive. bR
FR ) - ∇ · D (3.2)
Theoretical Frame. We assume that a ZnO nanowire is as the corresponding piezoelectric charge, eq 2 can be
epitaxially grown along the c axis on a single crystal rewritten for the electric potential φ
substrate, as shown in the schematic of Figure 1. The color
plot of electric potential in Figure 1 is based on a previous ∂2
κik φ ) -(FR - en + eND+) (4)
calculation using the Lippman theory,4 where the red side is ∂xi ∂ xk
positive and the blue side is negative.22 The wire is laterally
bent by a force fy exerted at the top. Previous results indicated The surface charge due to piezoelectricity is calculated
by ΣR ) -n b R, where ∆D
b·∆D b R is the change of D
b R astride
that, for a ZnO NW with zero free charge carrier density,
the tensile surface would show a positive piezoelectric the material surface and b
n is the normal to the surface. For
potential and the compressive side would show a negative simplicity, we have ignored the surface charges introduced
potential. (In this context, by “piezoelectric potential” we by polar surfaces of ZnO.
mean that the potential is created by the polarizations of The redistribution of electrons under thermodynamic
anions and cations in the NW; these charges cannot freely equilibrium is given by the Fermi-Dirac statistics

( )
move as long as the strain is preserved.) In this paper, we
b) - EF
Ec(x
will consider the finite concentration of donors and free n ) NcF1⁄2 - (5.1)
charge carriers in ZnO. kT

( 2πmekT
)
3⁄2
In order to focus on the core physics by preventing the Nc ) 2 (5.2)
2
digression to the less relevant problems about the interface h
heterojunctions, we assume that the substrate is also made where the conduction band edge Ec(x b) is a function of space
of ZnO. Such a situation occurs for the ZnO nanowires grown coordinates. Nc, the effective state density of conduction
on GaN substrates via the VLS method,23 because a thin ZnO band, is determined by the effective mass of conduction band
film or ZnO walls usually form beneath the nanowires. Our electrons me and the temperature T. Due to the large strain,
task is to calculate the piezoelectric potential when thermo- the deformation potential might be important. To be specific,
dynamic equilibrium is achieved in the laterally bent nano- the band edge shift ∆Ec is the sum of the electrostatic energy
wires. part and the deformation potential part
1104 Nano Lett., Vol. 9, No. 3, 2009
 ∆V the piezoelectric behavior inside the nanowire itself. Instead
Ec - Ec0 ) ∆Ec ) -eφ + ∆Ecdeform ) -eφ + ac (6)
V of elaborating into the details of the bottom reversed potential
where Ec0 is the conduction band edge of a free-standing region, we model the bottom region mainly to avoid missing
un-deformed semiconductor material; ∆Ecdeform ) ac∆V/V is its contribution to the potential in the nanowire. A more
the band edge shift due to the deformation potential,25 which detailed investigation about the bottom reverse region is
is proportional to the relative volume change ∆V/V, and ac suggested for future research.
is the deformation potential constant. Finally, the activation Numerical Results and Discussion. We use the finite
process of the donors is given by element method (FEM) to solve the nonlinear partial dif-
1 ferential equation posed by eqs 4-7. Symmetry is used so
ND+ ) ND
( )
(7)
EF - ED we only need to solve for the half-space of x > 0. Solution
1 + 2 exp in the other half of space can be immediately derived by
kT
where ED(x b) ) EC(xb) - ∆ED is the position-dependent donor using the mirror symmetry of the x ) 0 plane. In order to
energy level. The constant ∆ED is the activation energy of help the convergence, we first linearize eq 5.1 and eq 7 by
the donors. ND is the concentration of the donors. introducing an extreme case of ultrahigh temperature Thigh.
With eqs 4-7, the piezoelectric potential in a bent ZnO For the convenience of calculations as presented in eq 5.1
nanowire with moderate charger carrier density can be and eq 7, we define the following variables
calculated. It should be pointed out that eqs 4-7 are valid b) - EF
Ec(x
only when the system dimension is not too small. For small η)-
kT
systems, strong confinement requires quantum mechanical
considerations due to discrete bound states. Such an elabora- and
tion in theory is necessary for 2DEG in GaN/AlGaN HEMTs, EF - ED ∆ED
in which the quantum effect is important.11 In the following ηD ) )η+ (8)
kT kT
section we will conduct the calculation for nanowires with When T ) Thigh is large, η and ηD are no longer position-
diameter ∼50 nm or larger, where nonquantum mechanical dependent; the problem is thus linearlized for easy solution.
calculation is still acceptable. Such a size range is typical in As a convergence tool, Thigh by itself is not required to have
experiments.7 realistic physical meaning. Nevertheless, the solutions under
The Fermi level EF is flat all over the bent semiconductor high temperature T ) Thigh do evince some meaningful
nanowire when thermodynamic equilibrium is assumed. insight in physics. In fact, η ≈ ηD ≈ ln(ND/NC) when T )
Because the nanowires are assumed to be grown on a Thigh; therefore ND+ ) n and equ 4 would give an unscreened
substrate whose dimension is much larger than the nanowires, solution as though there were neither donors nor free charge
the substrate can be taken as a vast reservoir that pins the carriers in ZnO. As the system “cools down” from Thigh to
the realistic temperature, the equations become more and
Fermi level. In this paper we assume that the substrate is
more nonlinear. The value of η dictates how degenerate the
made of the same material as the nanowire itself. For system is, with η > -3 being regarded as the highly
nanowires making direct heterogeneous junctions with the degenerate case. As we will see later in the results, the
substrate, depletion regions or charge-accumulation regions problem will involve some degree of degeneracy even when
may form at the bottom junctions, which will not be the donor concentration is relatively low. This is analogous
elaborated in this paper. to the 2DEG regions in GaN/AlGaN HEMTs,11 where
When negligible donor concentration is assumed, the electrons accumulate even when the local doping level is
electric field in a bent piezoelectric nanowire has been solved small.
analytically,4 with the piezoelectric potential shown to be Despite more than a decade of investigations, the nature
independent of the coordinate z in a cylindrical coordinate of the unintentionally introduced donors in ZnO crystal has
system. Due to the Saint-Venant principle approximation, been controversial.15-20,26 Various mechanisms have been
the analytical solution4 is valid only for places that are not proposed, and reports about multiple shallow donor levels
too close to the root of the wire. At the root, finite element can be found in the literature with reported donor activation
analysis (FEA) showed the existence of a potential reversed energies ranging from 30 to 60 meV.15,18,27 Instead of
region if no donor concentration is considered (as seen in complicating the theory with multiple donor levels, we only
the bottom part in Figure 1).4 It can be proved that the consider one single donor level with ∆ED ) 35 meV.18 It
piezoelectric charge FR at the bottom region forms an electric should be pointed out that the methodology and qualitative
dipole, whose potential decays as fast as1/r2 (see Appendix). conclusions in this paper do not rely on the exact number of
Therefore it is legitimate to ignore the bottom reverse regions shallow donor levels and/or their activation energies. We also
when calculating the electric potential in the nanowire under neglect the deep donor levels or surface states which may
zero donor concentration assumption.4 However, when exist in ZnO nanowire28,29 to keep focusing on the central
electrons in conduction band come into the play, the physics. Later we will see that the band edge shift is generally
piezoelectric polarization charges might be screened by less than 0.5 eV except for a small region in the negative
the free charge carriers. Owing to the screening effect, the side of the bottom reverse region. The activation energy for
potential due to the bottom region might decay as slow as the deep donor levels is reported to be much larger than 0.5
1/r. Therefore one needs to model both NW and the substrate. eV in the scale of kT.29 Therefore the neglect of deep donors
Nevertheless, the main purpose of this paper is to investigate should not result in a significant error.
Nano Lett., Vol. 9, No. 3, 2009 1105
Figure 2. Plot of calculated piezoelectric potential φ for ND ) 1 × 1017 cm-3. For easy plot, the bending shape of the nanowire is not
presented. Besides the color plot, equipotential contours for φ ) -0.4, -0.2, -0.1, -0.03, 0.03, 0.1, 0.2, and 0.4 V are also superimposed.
The dimension of the nanowire is a ) 25 nm and l ) 600 nm and the external force is fy ) 80 nN. (a) Plot of φ for T ) 300 K at a cross
section of x ) 0. The blank region at the bottom is the region where φ < -0.4 V. The detail in this region is oversaturated for display
purposes to optimize the color scale in order to show φ in the nanowire. In this paper, we mainly focus on the behavior in the nanowire
and will leave the details about the bottom reverse region for future research. (b) Cross section plot of the electric potential for T ) 300
K at the height z ) 400 nm. Here only half of the space x > 0 is calculated using the mirror symmetry of x ) 0 plane. The plot in the x
< 0 region is derived by a simple reflection of the solution in the x > 0 region. (c and d) Calculation for an extremely high temperature
case of T ) Thigh ) 300000 K in reference to the result received from nanowires without doping. Again the extreme peaks are oversaturated.
(c) The cross section x ) 0. (d) The cross section plot of the electric potential at height z ) 400 nm.

In contrast to the lack of a universally accepted activation typical concentration around 1017 cm-3,15,18 our calculations
energy and model for the donors, the ZnO band gap of ∼3.4 are made for typical values around ND ) 1 × 1017 cm-3.
eV has long been established.30 Our model does not involve Figure 2a shows the equal-potential lines for ND ) 1 ×
the data on band gap except the fact that the wide band gap 1017 cm-3 and T ) 300 K on the cross section plane x ) 0,
is larger than the possible band shift ∆Ec ) -eφ + ∆Ecdeform. which is right through the axis of the nanowire. Figure 2b
Therefore, the Fermi level is always far away from the gives the equal-potential lines on a cross section perpen-
valence band and we do not need to consider holes or dicular to the nanowire axis and at a height of z ) 400 nm.
acceptors.31 The electrostatic calculation is done under a small strain
The material constants for ZnO used in the calculations assumption, in which the difference between the Lagrangian
are as follows: Young’s modulus E ) 129.0 GPa and Poisson reference frame and Eulerian reference frames is neglected.
ratio ν ) 0.349;2 relative dielectric constants κ⊥r ) 7.77, κ||r For comparison purposes, the results received under the
) 8.91,2 and the piezoelectric constants e31 ) -0.51C/m2, unrealistic temperature of T ) Thigh ) 300000 K is also
e33 ) 1.22C/m2, e15 ) -0.45C/m2.2 Effective mass is m* ) plotted in panels c and d of Figure 2, which correspond to
0.28m0,32 and deformation potential constant is ac ) -6.05 the situation when ZnO were an insulator without any free
eV.25 The change of effective mass due to strain is not charge carriers. The result for T ) Thigh is exactly the same
considered. The nanowire is geometrically approximated as as that given by the analytical solution in ref 4.
a cylinder, with radius a ) 25 nm, and length l ) 600 nm. The electric potential maximum in the positive side of the
The external force is bf ) fyb
ey, fy ) 80 nN, uniformly applied nanowire is significantly reduced from ∼0.3 V in Figure 2d,
at the top surface of the nanowire in a direction b ey which corresponds to an insulator case, to less than 0.05 V
perpendicular to the nanowire axis. The geometry and the in Figure 2b, which considers the moderate doping in ZnO.
external force are adopted as typical estimated numbers in On the other hand, the potential in the compressed side
an atomic force microscopy (AFM) based piezoelectric (negative potential side) is very well preserved. This is
potential detection experiment.7 Since the donor concentra- consistent with the experimental observation that only
tion ND varies according to the growth conditions with a negative pulses are observed in an AFM-based nanogenerator
1106 Nano Lett., Vol. 9, No. 3, 2009
Figure 3. (a and b) Cross section color plot of parameters η (a) and local electron density n (b) for ND ) 1 × 1017 cm-3 and T ) 300 K
at the height z ) 400 nm. Here only half of the space x > 0 is calculated using the mirror symmetry of x ) 0 plane. The plot in the x <
0 region is derived by a simple reflection of the solution in the x > 0 region. (c-e) Line plot of η, n, and φ under different temperatures
along the diameter in (a) and (b). The horizontal axis is the y-coordinate.

Figure 4. (a) Piezoelectric potential φ, (b) parameter η, (c) free electron concentration n, and (d) activated donor center concentration ND+
for different donor concentrations 0.6 × 1017 cm-3 e ND e 2.0 × 1017 cm-3. The dimension of the nanowire is a ) 25 nm, l ) 600 nm
and the external force is fy)80 nN. T ) 300 K. The line plot is along the diameter in Figure 2b and Figure 3a.
experiment using n-type ZnO nanowires.7 It is also consistent charges FR > 0 try to create a positive local potential φ >
with the observation that the output negative potential peak 0, it would result in a downward bending of the local
appears only when the AFM tip touches the compressed side conduction band. When η gets close to or even bigger than
of the nanowire. The decrease of positive potential in this zero, a large amount of free electrons would be injected from
model is due to the in-flow of electrons from the substrate the substrate reservoir into the nanowire to screen the positive
where free charges are abundant. When positive polarization potential.
Nano Lett., Vol. 9, No. 3, 2009 1107
 In the negative potential side (compressed side of the region is much smaller than the wire diameter a, which
nanowire), however, free charge carriers are depleted due implies strong confinement of the conduction band electrons.
to a large negative value of η, leaving only FR + eND+ as This strong confinement might result in stronger quantum
the net charge in eq 4. Let us use the analytical equation effect than that seen in the NW’s undeformed state.
derived in ref 4 to evaluate the concentration of ionic In order to investigate how the variance of ND affects the
polarization charge. Substituting a ) 25 nm, l ) 600 nm, piezoelectric potential, we plot the (a) electric potential φ,
and fy ) 80 nN into (b) parameter η, (c) free electron concentration n, and (d)
fy activated donor center concentration ND+ for different donor
FR ) [2(1 + ν)e15 + 2νe31 - e33] y concentrations 0.6 × 1017 cm-3 < ND < 2.0 × 1017 cm-3
IxxE
under T ) 300 K in Figure 4. It is seen that the electric
whereIxx ) (π/4)a4,4 one gets the typical piezoelectric potential φ is rather insensitive to the donor concentration
polarization charge density FRy)a/e ∼ - 8.8 × 1017 cm-3 in this regime. However, it is expected that φ will be
near the wire surface y ) a, where e is the charge of a single completely neutralized when ND > 1018 cm-3, as we have
electron. When ND ) 1 × 1017 cm-3, FR cannot be totally
screened in the negative side even if all of the electrons are already discussed. In the y < 0 region (stretched side of the
depleted because ND is much smaller than FRy)a/e. For a nanowire), degeneracy is always significant due to large η
nanowire with a very high donor concentration ND > 1018 value (Figure 4b). Therefore, electrons will be accumulated
cm-3, total neutralization with φ ≈ 0 could occur every- in the y < 0 side as seen in Figure 4c and depleted in the
where. Namely, a NW with a high concentration of free compressed side of the nanowire (y > 0). On the other hand,
charge carriers is expected to exhibit a very small piezo- the donor centers are not well activated in the y < 0 side as
electric potential. This result agrees to the experimental seen in Figure 4d, which makes the local electric charge
measurement of a nanogenerator under the illumination of density FR - en + eND+ in the y < 0 side even smaller.
UV light.5 In reality, the doping level in as-grown uninten- Summary. In summary, the behavior of free charge
tionally doped ZnO nanowires is much smaller than 1018 carriers in a bent piezoelectric ZnO nanowire is investigated
cm-3.
under a thermodynamic equilibrium condition. By assuming
The band edge shift ∆Ec comprises of two parts: electric
a flat Fermi level and a homojunction between the ZnO
potential part and the deformation potential part. The
nanowire and the substrate, we arrived at a conclusion that,
Saint-Venant solution for stress in the nanowire is σzz )
for a doping level of ND ) 1 × 1017 cm-3, the compressed
-(fy/Ixx)y(l - z), σxx ) σyy ) 0,4 therefore
side of the nanowire preserves the negative piezoelectric
|∆Ecdeform| ) ac|∆V ⁄ V| ) ac|Tr(ε)| potential, while the stretched side with positive potential is

| | | |
partially screened by free electrons. Charge carriers are
1 - 2ν 1 - 2ν fy
) ac Tr(σ) ) - ac y(l - z) < accumulated at the stretched side of the ZnO nanowire, and
E E Ixx
the compressive side is largely depleted. Degeneracy in the
1 - 2ν fy positive side of the nanowire is significant, but the temper-
ac · a · l ) 55 meV
E Ixx ature dependence of the potential profile is weak in the
As a posterior observation, this value is much smaller than temperature range of 100 K < T < 400 K. Our results
the negative side value of |eφ|; therefore the deformation support the mechanism proposed and demonstrated experi-
potential could have been neglected before the calcula- mentally for piezoelectric nanogenerators7 and nanopi-
tion if the potential magnitude in the negative side is the ezotronics.7,21
main concern. It also indicates that the negative potential
observed in experiments7 should not be due to the deforma- Acknowledgment. Research supported by DARPA (Army/
tion potential band-structure shift but mainly due to piezo- AMCOM/REDSTONE AR, W31P4Q-08-1-0009).
electric effect.
Degeneracy is significant in the screened positive side as Appendix. Analytical Consideration of the Reversed
seen in the η plot in Figure 3a. The degeneracy in the charge Electrostatic Potential at the Bottom of the Nanowire.
accumulation region is due to the piezoelectric effect but To prove the existence of the bottom reverse region and
not due to large donor concentration or low temperature. calculate the amount of charge therein, let us investigate the
Before deformation, η ) η0 ) -3.77 for ND ) 1 × 1017 piezoelectric polarization charge FR, which is defined by eq
cm-3 at T ) 300 K; this is below the degeneracy criterion. 3. By doing this we will be able to calculate the total amount
In order to investigate how temperature affects the free of piezoelectric charge if zero donor concentration is
charge carrier distribution and the final electric potential, we assumed. We suppose that the deformation is not too large;
plotted n, η, and φ for different temperatures (Figure 3, therefore the detailed difference between the Lagrangian and
curves c-e). The variance of n, η, and φ is small for Eulerian coordinate systems can be neglected when we
temperatures in a range of 100 K < T < 400 K. The free investigate the electrostatics as seen in Figure 5. To be
carrier concentration is n ∼ 1015 cm-3 in the depletion region specific, we will consider the problem in a material coordi-
and n ∼ FR/e + ND ∼ 1018 cm-3 in the charge accumulation nate system (x,y,z). For simplicity, we consider a case that
region as seen in Figure 3b. The boundary between the has no doping, i.e., zero conductivity. It is easy to see that
charge accumulation region and the depletion region is quite the piezoelectric polarization charge FR should be antisym-
sharp. We notice that the width of the charge accumulation metric with respect to y
1108 Nano Lett., Vol. 9, No. 3, 2009
 FR(x, -y, z) ) -FR(x, y, z)
Consider a domain VL (dotted part in Figure 5), whose
(9)
[∫∫ Σy
b·σ+
dS ∫∫ dSb · σ
ΣR 0 ] · êz ) 0 (12)

boundary ∂VL consists of four parts: neutral plane y ) 0, Therefore

(∫∫ )
substrate surface z ) 0, nanowire surface, and an imaginal 2(1 + ν)
quad-spherical surface ΣR0 ) {(x,y,z)|x2 + y2 + z2 ) R02, y - ∫∫ Db R b)
· dS
E
e15 b · σ · êz
dS (13)
e 0,z e 0} deep in the substrate with radius R0 . l. Consider Σy ΣR 0

QT,Left, which is defined as the total charge inside VL and on Now consider the far region r ∼ R0 in a spherical
∂VL coordinate(r,θ,φ). The mechanical behavior in the substrate
is a Boussinesq-Cerruti problem which involves a concen-
QT,Left ) ∫∫∫ F dV ) - ∫∫∫ ∇ · Db dV )
R R
trated load.33 The asymptotic behavior of σij can be expressed
VL∪∂VL x2+y2eR02 as σij ) (fy)/(r2)ψijσ(θ,φ), where ψijσ(θ,φ) is the dimensionless
ye0
angular dependence. The leading term is r-2 when there is
- ∫∫ Db R b-
· dS ∫∫ Db R b
· dS (10) a net force fy component in the concentrated load. The
ΣR 0 Σy
contribution due to a pure torque decays faster as r-3 thus
where Σy is the y ) 0 part of ∂VL. The last step in eq 10 is can be neglected. With the unit normal vector n̂ ) niêi on
b R ) 0 outside the ZnO material and
based on the fact that D ΣR0,

(∫∫ )
a simple application of the divergence theorem.
Let us first consider the Σy part in eq 10. By eq 3.1 and - ∫∫ Db R b ) 2(1 + ν) e15
· dS b · σ · êz
dS
Σy
E ΣR 0
eq 1
2(1 + ν)
b R · dS
D b R · êy dA ) DyR dA ) e15γyz dA ) 2(1 + ν) e15σyz dA
b)D
)
E
e15 ∫∫ σ i3ni dA
ΣR 0
E

[
π 2π
2(1 + ν) fy
Therefore )
E ∫ ∫
e15 dθ dφR02sin θ sin θ cos φ 2 ψ13σ(θ, φ) +
R
∫∫ b ) 2(1 + ν) e15 ∫∫
]
π⁄2 π 0
bR
D · dS σyzdA
E fy fy
Σy Σy sin θ sin φ ψ23σ(θ, φ) + cos θ 2 ψ33σ(θ, φ)
R02 R0

(∫∫ )
2(1 + ν) b · σ · êz 2(1 + ν)
) e15 dS (11) ) e15fycangular (14)
E E
Σy
where the dimensionless constant
where σ ) σijêi X êj is the stress tensor without using the
π 2π
Voigt-Nye convention. On the other hand, since the only
external force is fyb
ey on the top surface, the mechanical cangular ) ∫ dθ∫ dφ[sin 2
θ cos φψ13σ(θ, φ) +
π⁄2 π
equilibrium condition requires
sin2 θ sin φψ23σ(θ, φ) + sin θ cos θψ33σ(θ, φ)]
does not dependent on the values of a,l, or fy. It should be
noted that with the Boussinesq-Cerruti theory, cangular can
be calculated. However, in this paper we do not elaborate
on the exact value of cangular but only use the simple fact that
cangular is independent of the wire shape and the magnitude
of the external force. We also note that cangular should not be
much bigger than 1.
On the other hand, it has been proved that, in the nanowire,
the piezoelectric polarization charge is,4
fy
FR ) [2(1 + ν)e15 + 2νe31 - e33]y (15)
IxxE
where Ixx ) ∫CrossSectionx2 dA ) (π/4)a.4 This solution is valid
for places not too close to the substrate, where by “not too
close” it means z . a. The surface charge density ΣR )
-nb·∆Db R due to piezoelectric polarization on the wire surface
has been proved to be 0.4
Integrating eq 15 gives the total charge in the y < 0 part
of the nanowire
8 2(1 + ν)e15 + 2νe31 - e33 l
Qwire,Left ) - f (16)
3π E ay
Figure 5. The figure used to calculate the charge in the bottom While cangular is a constant independent of a, l, or fy, the
reverse region. The total charge in domain VL is proved to be nanowire has a large aspect ratio l/a . 1. Therefore, by
zero. comparing eq 14 and eq 16
Nano Lett., Vol. 9, No. 3, 2009 1109
 |- ∫ ∫ Db R b| , |Qwire,Left|
· dS
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