High field electron transport properties of bulk ZnO

J. D. Albrecht, P. P. Ruden, S. Limpijumnong, W. R. L. Lambrecht, and K. F. Brennan

Citation: Journal of Applied Physics 86, 6864 (1999); doi: 10.1063/1.371764

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 JOURNAL OF APPLIED PHYSICS VOLUME 86, NUMBER 12 15 DECEMBER 1999

High field electron transport properties of bulk ZnO

J. D. Albrecht and P. P. Ruden
Department of Electrical and Computer Engineering, University of Minnesota, Minneapolis, Minnesota 55455
S. Limpijumnong and W. R. L. Lambrecht
Department of Physics, Case Western Reserve University, Cleveland, Ohio 44106-7079
K. F. Brennan
School of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332
共Received 7 June 1999; accepted for publication 1 September 1999兲
The Monte Carlo method is used to simulate electron transport for electric field strengths up to 350
kV/cm in bulk, wurtzite structure ZnO. The relevant parts of the conduction bands of a
first-principles band structure are approximated by spherically symmetric, nonparabolic valleys
located at the ⌫ and U min symmetry points of the Brillouin zone. It is shown that the analytic
expressions represent the band structure and the density of states well over a range of nearly 5 eV
from the bottom of the conduction band. The simulated electron steady-state drift velocity versus
electric field characteristics are calculated for lattice temperatures of 300, 450, and 600 K. For room
temperature, drift velocities higher than 3⫻107 cm/s are reached at fields near 250 kV/cm.
Examination of the electron energy distributions shows that the strong decrease of the differential
mobility with increasing electric field in the field range studied is to be associated with the
pronounced nonparabolicity of the central valley and not with transfer of electrons to satellite
valleys. © 1999 American Institute of Physics. 关S0021-8979共99兲07224-2兴

I. INTRODUCTION
Zinc oxide is of potential interest as a suitable material
for high temperature, high power electronic devices either as
the active material or as a suitable substrate for epitaxial
growth of group III-nitride compounds.1 Prior to advances in
vapor-phase growth yielding high-quality bulk ZnO
crystals,2 practical applications for semiconducting ZnO
were limited to those requiring only oriented polycrystallites
or powder.3–5 With its large, direct band gap 共3.4 eV兲 and
wurtzite crystal structure, ZnO is similar to GaN. Further-
more, due to its relatively close match in lattice constants, it
may be used as a substrate for GaN and AlN epitaxy. As a
consequence, there is renewed interest in the properties of
ZnO relevant for device applications.
In this article, we present Monte Carlo 共MC兲 simulations
of electron transport versus electric field in bulk, wurtzite
structure ZnO for lattice temperatures of 300, 450, and 600
K. A first-principles electronic band structure using the full-
potential linearized muffin-tin orbital method in the local
density approximation 共FP-LMTO-LDA兲 is used as the basis
from which the parameters of simple analytic expressions for
the three lowest conduction band valleys are determined.
This model conduction band structure is then used in MC
simulations of electron drift. Our simulations indicate that
the velocity versus field curves have broad peaks above 250
kV/cm. Furthermore, we examine the electron energy distri-
bution functions for applied electric fields near the velocity
peak and conclude that the decreasing differential mobility
with increasing electric field is a result of the strongly non-
parabolic nature of the central valley and not due to signifi-
cant transfer of electrons to satellite valleys. Comparison of
the velocity versus field characteristics to those of wurtzite
structure GaN,6 where the energy valley separations are sub-
stantially lower and electron transfer effects are significant,
are presented.
II. BAND STRUCTURE AND SCATTERING MODELS
The conduction bands of the wurtzite phase ZnO band
structure calculated using the FP-LMTO-LDA method are
shown in Fig 1. The band structure is in good agreement
with recent first-principles calculations by Schröer et al.7 and
Massidda et al.,8 but differs somewhat from the older work
of Rossler.9 Details of the band structure calculation tech-
nique will be published elsewhere.10 As is well understood,
the LDA tends to lead to underestimates of the band gaps.
However, results for ZnO and similar large band gap semi-
conductors indicate that self-energy corrections in the frame-
work of the GW approximation yield quasiparticle bands that
are in satisfactory agreement with experimental data for in-
terband transition energies.11 Furthermore, the self-energies
of the conduction band electrons are found to be only weakly
wave-vector dependent. Hence, the conduction bands ob-
tained in the framework of the FP-LMTO-LDA are a reason-
able first approximation for the electron dispersion relevant
to the transport simulation.
Critical features of the conduction bands for the MC
transport simulation are the lowest ⌫ valley 共⌫ 1 symmetry兲
and the satellite valleys located at ⌫ 共⌫ 3 symmetry兲 and at a
U point, U min 共U 1 symmetry兲, which is located two-thirds of
the way between the M and L symmetry points on the edge
of the Brillouin zone. The ⌫ valleys are single 共disregarding
spin兲 and the U valleys have sixfold degeneracy. The appar-
ent minimum at the A symmetry point in Fig. 1 is not a
valley or saddle point, but merely reflects the folding of the

0021-8979/99/86(12)/6864/4/$15.00 6864 © 1999 American Institute of Physics

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 J. Appl. Phys., Vol. 86, No. 12, 15 December 1999
FIG. 1. Conduction bands of wurtzite structure ZnO as obtained from a
FP-LMTO-LDA band structure calculation.
band at the Brillouin zone face perpendicular to the hexago-
nal axis, as is readily seen in the ⌫ to A dispersion on the
right-hand side of the figure. Examination of the ⌫ 1 valley
shows a nearly linear dispersion over a wide energy range.
From the band structure calculation, energy separations of
4.4 eV between the ⌫ 1 and ⌫ 3 minima, and 4.6 eV between
the ⌫ 1 and U minima are deduced.
The conduction bands used in the electron transport
simulation are represented by the same form of analytical
multiple-valley model which has been used to study electron
transport in nitride compound semiconductors.6,12 In the
present MC simulation, the ⌫ 1 valley, the ⌫ 3 valley, and the
equivalent U valleys are all represented by the following
spherical, nonparabolic, effective mass expressions:
ប 2 共 k⫺k0X 兲 2
⑀ 共 1⫹ ␣ X ⑀ ⫹ ␤ X ⑀ 2 兲 ⫽ . 共1兲
*
2m 0X
Here ⑀ denotes the electron energy referenced to the mini-
mum energy of a conduction band valley located at k0X . The
* , and the nonparabolicity
low energy effective masses, m 0X
factors, ␣ X and ␤ X , are obtained by matching Eq. 共1兲 to the
conduction bands shown in Fig. 1. This fitting results in ef-
fective masses of 0.17, 0.42, and 0.70m 0 for the ⌫ 1 , ⌫ 3 , and
U valleys, respectively. The corresponding linear nonparabo-
licity factors are 0.66 eV⫺1, 0.15 eV⫺1, and zero for the
modeled energy range. The second order nonparabolicity
factor, ␤ X , is chosen to be nonzero only for the lowest con-
duction band valley, ⌫ 1 . A value of 0.027 eV⫺2 is found to
be consistent with the band structure, which shows a gradual
change in curvature from positive to negative with increasing
energy. All dispersion parameters are taken to be indepen-
dent of temperature. The conduction band density of states
共DOS兲 obtained from the analytical, multiple valley model is
plotted in Fig. 2, together with the DOS calculated directly
from the FP-LMTO-LDA band structure. The agreement is
better than 1% up to 4 eV, and better than 17% at 4.5 eV
above the conduction band minimum.
The MC technique used follows the standard paradigm
of independent particle transport simulations. Details of the
code are documented in Ref. 13 and an excellent general
overview can be found in Ref. 14. Material parameters nec-
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Albrecht et al. 6865
FIG. 2. Conduction band density of states calculated directly from the bands
of Fig. 1 共dots兲 and from the approximate multiple valley model used in the
transport simulation 共solid lines兲.
essary for calculating the scattering probabilities are not as
well known for ZnO as they are for more widely studied
semiconductors. In our calculations, the deformation poten-
tial for intravalley acoustic phonon scattering is taken to be
3.83 eV for all valleys.15 Nonequivalent intervalley scatter-
ing events are taken into account among all three valley
types, with ⌫ 1 ↔U, ⌫ 1 ↔⌫ 3 , and U↔⌫ 3 transfers assumed
to be governed by the same deformation potential fields as
the equivalent intervalley scattering,6 109 eV/cm. In the ab-
sence of data on the Brillouin zone boundary phonons, we
assume a measured transverse optical phonon energy of
0.050 eV to be similar to the relevant Brillouin zone bound-
ary phonon energies for equivalent and nonequivalent inter-
valley scattering. The dependence of the MC simulation re-
sults on the precise value of the intervalley phonon energies
and scattering potential was checked and found to be weak.
In the Fröhlich interaction Hamiltonian, an experimen-
tally determined polar optical phonon energy of 0.072 eV is
used.16 The static and high frequency dielectric constants are
8.2⑀ 0 and 3.7⑀ 0 , respectively.17 Ionized impurity scattering
is included, with an assumed ionized donor density of
1017 cm⫺3 . Compensation is taken to be negligible, which is
consistent with the low compensation levels determined from
recent studies of high quality material.2 Piezoelectric acous-
tic phonon scattering is included in a zinc-blende structure
approximation of the measured18 piezoelectric tensor, similar
to the approximation made in the case of GaN. For tempera-
tures greater than 300 K and high field conditions, the elec-
tron drift velocity is found to be only very weakly affected
by piezoelectric scattering.
III. RESULTS AND DISCUSSION
Results for the electron drift velocity versus electric field
characteristic are plotted in Fig. 3 for various lattice tempera-
tures The peak velocity for 300 K is 3.2⫻107 cm/s at 270
kV/cm. The negative differential mobility for higher fields is
small. Also apparent in Fig. 3 is a change in the differential
mobility of the 300 K curve near 50 kV/cm that corresponds
to the onset of significant spontaneous polar optical phonon
emission as the electrons are accelerated to energies greater
 6866 J. Appl. Phys., Vol. 86, No. 12, 15 December 1999
FIG. 3. Results of MC simulations of ZnO electron drift velocity vs electric
field for 300 K 共solid兲, 450 K 共dashed兲, and 600 K 共dash-dotted兲 lattice
temperatures.
than the longitudinal optical phonon energy. This effect is
negligible at 600 K because the emission and absorption
rates are of comparable magnitude at elevated lattice tem-
perature. The 600 K curve is dominated by polar optical
phonon scattering throughout the field range and is nearly
linear up to field strengths of 300 kV/cm.
To examine the velocity peak and negative differential
mobility at 300 K, we plot the calculated electron energy
distributions in Fig. 4 for 300 and 450 kV/cm. At 300 kV/
cm, the velocity decreases with increasing field but the en-
ergy distribution indicates that there is only insignificant
transfer of electrons to the higher valleys. The velocity peak
results from the nonparabolic dispersion of the lowest central
valley. 共This can also be corroborated by removing all satel-
lite valleys which changes the calculated drift velocity by
less than 2% for fields up to 350 kV/cm兲. A similar velocity
versus field feature associated with nonparabolicity was first
reported in an early high-field transport calculation for
GaN.19 To further examine this point, the energy distribution
is plotted in Fig. 4, with the field increased to 450 kV/cm. In
this case, electrons acquire sufficient energy to transfer to the
satellite valleys. This result also is indicative of the field
strength required to cause electrons to exceed the range of
validity of the simple multiple valley model. Clearly, the
FIG. 4. Simulated electron energy distributions for electric field strengths of
300 共⽧兲 and 450 kV/cm 共䊏兲. The lattice temperature is 300 K.
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Albrecht et al.
FIG. 5. Comparison of calculated electron drift velocity vs electric field for
wurtzite structure GaN 共dashed兲 and ZnO 共solid兲 at 300 K.
spike in the distribution is consistent with the large feature in
the DOS associated with the U valleys 共Fig. 2兲. The effects
of the ⌫ 3 valley on the electron transport are minimal com-
pared to the nonparabolicity of the ⌫ 1 valley. This result is
quite different from, e.g., AIN, another wide band gap,
wurtzite structure semiconductor, which also shows a broad
velocity peak at large electric fields. In the AlN case, there is
significant transfer of electrons to satellite valleys20 because
the nearest satellite valley 共centered at U min兲 is only 0.6 eV
above the bottom of the conduction band 共compared to 4.6
eV in the present case兲.
A comparison of the drift velocity of ZnO to the calcu-
lated drift velocity of wurtzite GaN,6 is plotted for 300 K in
Fig. 5. Although the peak velocities are comparable in the
two cases, the peak fields differ considerably, with the peak
field for GaN being about 100 kV/cm lower than that of
ZnO. This arises mainly from the lower satellite valleys in
GaN, which has been demonstrated to exhibit a transferred-
electron effect,6,21 and from the stronger Fröhlich coupling in
ZnO.
In our model for the electron dispersion all anisotropy of
the valleys is neglected. More accurately, the ⌫ 1 valley ef-
fective mass has cylindrical symmetry, and extracting effec-
tive masses from the band structure described above yields
m* 0 储 ⫽0.20m 0 and m 0⬜
* ⫽0.16m 0 , where 储 and ⬜ refer to the
directions parallel to and perpendicular to the hexagonal
crystal axis. Measured effective masses for conduction elec-
trons in ZnO have typically been larger and the sign of the
asymmetry is controversial. For example, Baer22 obtained a
band effective mass m 0⬜ * ⫽0.25m 0 by 共high frequency兲 Far-
aday rotation experiments on degenerately doped samples
with carrier concentrations of 1019 cm⫺3 . One may then
argue,22 based on an analogy to CdS, that m * 0 储 might be about
0.22m 0 . This results in a density of states mass that is about
34% larger than the corresponding spherical mass at the
Fermi energy in our model. It is conceivable that the heavy
doping of the samples affects the electron dispersion signifi-
cantly through the formation of a band tail. However, it is
also possible that an underestimation of the band edge effec-
tive mass in our model is associated with the underestimation
of the band gap that results from the LDA.
 J. Appl. Phys., Vol. 86, No. 12, 15 December 1999 Albrecht et al. 6867

In addition, at low fields, the large Fröhlich coupling computer Institute is gratefully acknowledged. This work
indicates that the effective masses of ZnO must be corrected 共UM and GT兲 was supported in part by NSF under Grant No.
for the polaron mass enhancement, which amounts to ap- ECS-9811366. The work at CWRU was supported by ONR
proximately 16% using our parameters. Zeeman effect mea- under Grant No. N00014-98-1-0160.
surements on donor levels23 have yielded polaron effective
masses of m 0⬜** ⫽0.3m 0 and m **
0 储 ⫽0.38m 0 . In this case, the
sign of the anisotropy agrees with that shown by the band
structure results described above, but the magnitude of the
masses is considerably larger. Because of the uncertainties in 1
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